TW201141818A - Novel azomethine oligomer - Google Patents

Novel azomethine oligomer Download PDF

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TW201141818A
TW201141818A TW100106842A TW100106842A TW201141818A TW 201141818 A TW201141818 A TW 201141818A TW 100106842 A TW100106842 A TW 100106842A TW 100106842 A TW100106842 A TW 100106842A TW 201141818 A TW201141818 A TW 201141818A
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oligomer
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carbon atoms
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Syuji Okamoto
Hikaru Meguro
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Soken Chemical & Amp Engineering Co Ltd
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  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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Abstract

Provided is a novel azomethine oligomer capable of maintaining an adequate carrier mobility as a semiconductor material, and soluble in frequently used organic solvent, for example, a hydrophobic solvent such as toluene etc., an alcoholic solvent such as methanol, ethanol, etc., a glycolic solvent such as propyleneglycol monomethyl ether, etc. or an esteric solvent such as methyl lactate, etc. The present invention relates to a azomethine oligomer characterized by having an aromatic ring-containing conjugated group formed by interbonding an azomethine group and an optionally substituted two-valent aromatic group, in the main chain, and the azomethine group at two terminals of the aromatic ring-containing conjugated group binding with a hydrocarbon group not conjugated with said azomethine group and optionally containing a group having an oxygen atom, a sulfur atom or a cycloalkylene group, and the hydrocarbon group having no reactivity with an aldehyde group and an amino group.

Description

201141818 六、發明說明： 【發明所屬之技術領域】 本發明係有關新穎之偶氮甲川寡聚物。 【先前技術】 關於具有直鏈狀發達之共軛構造之聚偶氮曱川的用途， 廣泛進行研究作為LED、薄膜電晶體、太陽電池等之電子 及光學裝置材料用之有機半導體材料之用途。 通常，以往之聚偶氮甲川為在主鏈中具有芳環、雜環 或芳環及雜環，該等為以偶氮次子基連結之複數芳環及/ 或雜環連繫之共軛系聚合物構造。 在將聚偶氮甲川利用作為有機半導體材料之場合，為 了在基板上形成上述之半導體層，將聚偶氮甲川溶解於溶 劑，將獲得之溶㈣抹在基板上之方法肢且成本亦低。 准上述聚偶氮甲川在上述之每個共輛系為平面性高之剛 直構造之化合物，因此，對於有機溶劑之溶解性差。因此， 不能將聚偶氮甲川溶解於有機溶劑而塗佈在基板上。 因此，提案有將單體在目標基板 聚 偶氮甲川聚合，形成丰藤艚恩> … 導體層之方法（參照專利文獻1)， 惟，該方法過程煩雜且聚偶氮甲川之收率低，不是理想之 方法。 獻1揭不之聚偶氮甲川溶性，見 識到在間-甲盼等質子酸或 合齊“解r 形成可逆之路易士酸-驗對，在該狀態，對 於各劑呈“解性（參照非專利文獻1至4)。 322866 4 201141818 惟，該等質子酸或含有質子酸之有機溶劑難說具有通用 性。另，由於上述有機溶劑呈現腐蝕性，將聚偶氮曱川溶解 於該等溶劑之聚偶氮曱川溶液在工業上之使用受到限制。 專利文獻2揭示關於含有聚偶氮甲川之有機LED元件 之發明，該聚偶氮甲川以下述通式（I)表示。 ——通式（I) 此處，I、R2為第2頁第8行至第13行之化學式201141818 VI. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to novel azomethine oligomers. [Prior Art] For the use of polyazo kawakawa having a linearly developed conjugated structure, the use as an organic semiconductor material for electronic and optical device materials such as LEDs, thin film transistors, and solar cells has been extensively studied. In general, the conventional polyazomethine has an aromatic ring, a heterocyclic ring or an aromatic ring and a heterocyclic ring in the main chain, and these are conjugates of a plurality of aromatic rings and/or heterocyclic rings linked by an azo substituent group. Polymer construction. When polyazomethine is used as an organic semiconductor material, the above-described semiconductor layer is formed on a substrate, and polyazomethine is dissolved in a solvent, and the obtained method is applied to the substrate, and the cost is also low. The above-mentioned polyazomethine is a compound having a high planarity and high rigidity in each of the above-mentioned common vehicles, and therefore has poor solubility in an organic solvent. Therefore, polyazomethine cannot be dissolved in an organic solvent and coated on a substrate. Therefore, there has been proposed a method of polymerizing a monomer on a target substrate polyazomethine to form a conductor layer of Toyowa > (refer to Patent Document 1), but the process is troublesome and the yield of polyazomethine is low. , not the ideal way. Dedicated to the solubility of polyazomethine, it is known that the protonic acid or the combination of the protonic acid or the "resolving r" forms a reversible Lewis acid-inspection. In this state, it is "solvable" for each agent. Non-patent documents 1 to 4). 322866 4 201141818 However, it is difficult to say that such protic acids or organic solvents containing protic acids are versatile. Further, since the above organic solvent exhibits corrosiveness, the use of a polyazo sulfonium solution in which polyazoazolium is dissolved in the solvents is limited in industrial use. Patent Document 2 discloses an invention relating to an organic LED element containing polyazomethine, which is represented by the following general formula (I). - General formula (I) Here, I, R2 are the chemical formula of the 8th to 13th lines of the 2nd page.

中之任何一個， 322866 201141818 或-A為Any one of them, 322866 201141818 or -A

—Η , —CH3. 中之任何一個 上述之選項中不僅有芳環共軛構造，亦有-(CHOm-或 伸環己基等之非共軛構造。 於專利文獻2之[0013]記載將該等聚偶氮曱川在間- 甲紛或笨中進行聚合’將獲得之聚偶氮甲川溶液經由旋轉 塗覆、浸潰塗覆等濕式成膜法在基板（陽極）上成膜後，在 惰性氣體之大氣中加熱，製作聚偶氮曱川層。 惟，於專利文獻2,對於實際上是否合成上述通式〇) 表不之聚偶氮曱川則無任何記載。又，溶解專利文獻2之 聚偶氮曱川之間-甲酚及苯難說具有通用性。又，間-曱酚 如上所述，具有腐蝕性，苯具有致癌性，兩者對於人體都 有害。 “因此，將專利文獻2之聚偶氮曱川溶解於該等間-曱酴 或本之聚偶氮曱川溶液紅業上的利用被限制。另，於專 利文獻2對於上料錢甲収㈣ 其 溶劑(例如乙醇)則未記載也未暗示。爾-之其他 另方面，對於該等在有機溶劑之、、办銥 _ 甲川有經由在其主鏈中之芳環、雜芳=低的聚偶氣 烧基或烧氧基等，使得聚偶i^丨及雜環中導入 DMS0、NMP、間、甲路笪^ 、氣仿、THF、DMF、 甲料之早獨溶劑呈現溶解性的報告（參照 322866 6 201141818 非專利文獻5)。 惟’在該等芳環及/或雜環中導入烷基或烷氧基之原料 單體’由於在商業上無法取得，認為要將上述聚偶氮甲川 之製造工業化有困難。又，使用之溶劑種含有齒素構造， 此時，上述有機溶劑種呈現高沸點。因此，從對於操作者 之健康管理、溶劑之乾燥步驟要求高能量等理由而言，上 述溶劑在工業用之使用不理想。另，於化學構造上在該共 輛系内導入取代基，由於該化合物具有之立踱陳礙，會導 致原來共軛系内之平面性降低、聚偶氮曱川分子内及分子 間之結晶性降低、有機半導體材料必需之載艚#動度變 差。惟，如在立體規則性高之聚（3-己基噻吩）（P3HT)之己 基所見，上述取代基為具有誘發在共軛系分孑内結晶性效 果之烧基等時則無此限制。 [先前技術文獻] 專利文獻 專利文獻1:日本特開平8-113622號公雜 專利文獻2:日本特開平9-194832號公報 非專利文獻 非專利文獻 l:Chem.Mater. 1991, 3，8作 非專利文獻 2:Chem.Mater. 1994，6，I96 非專利文獻 3:Chem.Mater. 1995，7,丨276 非專利文獻 4: Macromolecules 1995, 28，1180 非專利文獻 5 : Macromolecules，vol. 38，Ν〇· 5 ’ 第 1958-1966 頁，2005 322866 201141818 【發明内容】 [發明欲解決之問題] 本發明以提供作為半導體材料，確保充分之載體移動 度且溶解於甲笨等疏水性溶劑、甲醇、乙醇等醇系溶劑、 丙二醇一曱醚等乙二醇系溶劑或乳酸甲酯等酯系溶劑等通 用性高之有機溶劑之新穎偶氮曱川寡聚物為目的。 [解決課題之方法] 本發明為以在主骨架中具有偶氮次曱基與可具有取代 基之二價芳族基互相結合之含有芳族環之共輛基，在該含 有芳族環之共軛基兩末端之偶氮次甲基結合有不與該含有 方族％之共扼基共輕，可具有氧原子、硫原子或環伸貌基 之基之烴基，該烴基與醛基及胺基不具有反應性為特徵之 偶氮甲川寡聚物。 以往之聚偶氮曱川中，聚偶氮甲川為在其主键中具有 方％雜丨衣或方環及雜環，該等以偶氮次甲基連結之複數 芳環及/或雜環連繫之共軛系聚合物構造。該等為用於在聚 偶氮甲川1分子内將載體移動。因此，共軛系聚合物構造 成為聚偶氮甲川在有機溶劑為低溶解性之原因。為了提昇 溶解性，提案有在上述芳環及/或雜環中導入烷基或烷氧基 作為側鍵（非專利文獻5)。惟，該提案之方法，用於合成 該等聚偶氮甲川之原料單體，有在商業上不能取得之問題。 對於此’本發明人根據以下2點觀點之轉換，發明不 僅可溶解於通用性高之溶劑，在工業上亦可容易製造，且 確保作為半導體充分之載體移動度之偶氮甲川寡聚物。 8 322866 201141818 (1) 不是將載體在1分子内移動，而是化合物具有之共軛系 (芳環）在化合物分子間經由7Γ - 7Γ堆疊（在分子間將共軛構 造部分定向）’使載體在分子間移動 (2) 不是將烧基等導入作為聚合物之侧鍵，而是導入作為寡 聚物主鏈之一部分（亦即’將共軛系構造以非共軛間隔基連 結）。 於本發明之偶氮甲川寡聚物，上述烴基較好為選自由 可具有支鏈、可經齒素原子取代之碳數2至512之烷基， 可具有支鏈、可經j素原子取代之碳數2至512之烷氧基， 基中具有趟結合及/或硫醚結合、可經齒素原子取代之碳數 2至512之烴基及可具有取代基之碳數3至50之環烷基所 成組群之任何一個基。 卜上述偶氮甲川寡聚物之分子量較好在150至15000之 範圍内’上述偶氮甲川寡聚物通常對於選自甲酚、曱苯、 ’、環戊基甲醚、丙酮、MEK、MIBK、環戊酮、氯仿、二 甲烧四氯化碳、氯苯、二硫化碳、乙酸乙醋、乙酸丁 酉曰、礼酸甲酯、甲醇、乙醇、異丙醇、苯曱醇、正丁醇、 第三丁醇、戍醆、 乂蜉乙一醇、丙二醇、丙二醇一甲醚、吡啶、 NMP硫酉夂、甲酸、乙酸、鹽酸、乳酸、三乙胺、二丁胺中 之任何—種溶劑或二種以上之共溶劑lGGg，於25°C具有 〇. lg以上之溶解性。 本發明之偶氮甲川寡聚物可以例如下述通式（I)表示。 R Ar—A——R2 , T、 9 322866 201141818 於上述式，Ar為可具有取代基之二價芳族基，或偶氮 次:基與可具有取代基之二價芳族基交互結合之共輛之含 有芳族環之共輛基， A為偶氮次曱基， R及R各自獨立’為可具有支鏈、可經_素原子取代 之碳數2至512之縣，可具有支鏈、可經i素原子取代 之奴數2至512之烧氧基’基中具有㈣合及/或疏鍵結 合、可經i素原子取代之碳數2 i 512之煙基或料有取 代基之碳數3至50之環烷基。 上述二價之芳族基較好為下述式表Any one of the above-mentioned options of -Η, -CH3. includes not only an aromatic ring conjugate structure but also a non-conjugated structure of -(CHOm- or exocyclohexyl group. [0013] The polyazo azokawa is polymerized in a m- or a singularity. The obtained polyazomethine solution is formed on a substrate (anode) by a wet film formation method such as spin coating or dip coating. The polyazo kawakawa layer is produced by heating in an atmosphere of an inert gas. However, in Patent Document 2, there is no description as to whether or not the polyazo kawakawa described above is synthesized. Further, it is difficult to dissolve methacrylic acid and benzene between the polyazo-chuanchuan of Patent Document 2 to have versatility. Further, m-nonphenol is corrosive as described above, and benzene is carcinogenic, both of which are harmful to the human body. "Therefore, the use of the polyazo-indene of Patent Document 2 to dissolve in the meta- 曱酴 or the poly-arsenazo solution red industry is limited. In addition, in Patent Document 2, (4) The solvent (such as ethanol) is not described or implied. In other aspects, for the other, in the organic solvent, the 铱 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲The poly(alk) or the alkoxy group, etc., so that the polyisoacid and the heterocyclic ring are introduced into the DMS0, NMP, m, 甲, 气, THF, DMF, and the early solvent of the material are soluble. Report (refer to 322866 6 201141818 Non-Patent Document 5). However, the raw material monomer which introduces an alkyl group or an alkoxy group in these aromatic rings and/or heterocyclic rings is considered to be commercially unavailable, and it is considered that the above polybutan Nitromethine is difficult to manufacture industrially. Further, the solvent used has a dentate structure. In this case, the organic solvent has a high boiling point. Therefore, it requires high energy for the operator's health management and the solvent drying step. In other words, the above solvents are not ideal for industrial use. Substituting a substituent into the common system in chemical structure, the planarity of the original conjugated system is lowered, and the crystallinity in the intramolecular and intermolecular phases of the polyazo hydrazine is lowered due to the presence of the compound. The mobility of the organic semiconductor material must be poor. However, as seen in the steric group of the highly stereoregular poly(3-hexylthiophene) (P3HT), the above substituents are induced in the conjugated bifurcation. In the case of a base of a crystallizing effect, etc., there is no such limitation. [Prior Art Document] Patent Document 1: Japanese Patent Laid-Open No. Hei 8-113622, No. Hei No. Hei 9-194832, Non-Patent Document Non-Patent Document Document 1: Chem. Mater. 1991, 3, 8 for Non-Patent Document 2: Chem. Mater. 1994, 6, I96 Non-Patent Document 3: Chem. Mater. 1995, 7, 丨276 Non-Patent Document 4: Macromolecules 1995, 28, 1180 Non-Patent Document 5: Macromolecules, vol. 38, Ν〇 5' Page 1958-1966, 2005 322866 201141818 [Disclosure of the Invention] The present invention provides a semiconductor material to ensure sufficient Carrier mobility and dissolution A novel azo-chuanchuan oligomer of a highly versatile organic solvent such as a hydrophobic solvent such as a methyl alcohol, an alcohol solvent such as methanol or ethanol, an ethylene glycol solvent such as propylene glycol monoterpene ether or an ester solvent such as methyl lactate. [Problem to solve the problem] The present invention relates to a common group containing an aromatic ring which has an azo sulfhydryl group and a divalent aromatic group which may have a substituent in the main skeleton, and contains the aromatic group. The azo methine group at both ends of the conjugated group of the family ring is bonded to a hydrocarbon group which is not lightly related to the fluorenyl group containing the steroid group, and may have an oxygen atom, a sulfur atom or a ring-extension group, and the hydrocarbon group An azomethine oligomer characterized by no reactivity of an aldehyde group and an amine group. In the conventional polyazochuan, polyazomethine has a square % heterocyclic or a square ring and a heterocyclic ring in its primary bond, and a plurality of aromatic rings and/or heterocyclic rings linked by an azo methine group. Conjugated polymer structure. These are used to move the carrier within one molecule of polyazomethine. Therefore, the conjugated polymer structure is a cause of low solubility of polyazomethine in an organic solvent. In order to improve the solubility, it is proposed to introduce an alkyl group or an alkoxy group as a side bond in the above aromatic ring and/or hetero ring (Non-Patent Document 5). However, the proposed method for synthesizing the raw materials of the polyazomethine has problems that are not commercially available. According to the conversion of the following two points, the inventors of the present invention can not only be dissolved in a solvent having high versatility, but also can be easily manufactured industrially, and an azomethine oligomer which is sufficient as a carrier mobility of a semiconductor can be secured. 8 322866 201141818 (1) Instead of moving the carrier within 1 molecule, the compound has a conjugated system (aromatic ring) between the molecules of the compound via a 7Γ-7Γ stack (orienting the conjugated moiety between the molecules)' Movement between molecules (2) Instead of introducing a burn group or the like as a side bond of the polymer, it is introduced as a part of the oligomer main chain (that is, 'the conjugated structure is linked by a non-conjugated spacer). In the azomethine oligomer of the present invention, the above hydrocarbon group is preferably selected from an alkyl group having 2 to 512 carbon atoms which may have a branched chain and may be substituted by a dentate atom, and may have a branched chain and may be substituted by a j atom. An alkoxy group having 2 to 512 carbon atoms, a hydrazine-bonded and/or thioether-bonded group, a hydrocarbon group having 2 to 512 carbon atoms which may be substituted by a dentate atom, and a ring having 3 to 50 carbon atoms which may have a substituent Any one of the groups in which the alkyl groups are grouped. The molecular weight of the above azomethine oligomer is preferably in the range of 150 to 15000. The above azomethine oligomer is generally selected from the group consisting of cresol, toluene, ', cyclopentyl methyl ether, acetone, MEK, MIBK. , cyclopentanone, chloroform, dimethyl sulphide carbon tetrachloride, chlorobenzene, carbon disulfide, ethyl acetate, butyl acetate, methyl oxalate, methanol, ethanol, isopropanol, benzofuran, n-butanol, Any solvent or two of tributyl alcohol, hydrazine, decyl alcohol, propylene glycol, propylene glycol monomethyl ether, pyridine, NMP thioindole, formic acid, acetic acid, hydrochloric acid, lactic acid, triethylamine, dibutylamine The above co-solvent lGGg has a solubility of lg. lg or more at 25 °C. The azomethine oligomer of the present invention can be represented, for example, by the following formula (I). R Ar—A—R 2 , T, 9 322866 201141818 In the above formula, Ar is a divalent aromatic group which may have a substituent, or an azo group: a group is bonded to a divalent aromatic group which may have a substituent A common vehicle containing an aromatic ring, A is an azo sulfhydryl group, and R and R are each independently 'a county having a carbon number of 2 to 512 which may have a branch and may be substituted by a silane atom, and may have a branch. a chain, a substitutable number of 2 to 512, which may be substituted by an imine atom, has a (iv) and/or a sparing bond, and a carbon number of 2 i 512 which may be substituted by an imine atom is substituted with a nicotine group or a material. a cycloalkyl group having 3 to 50 carbon atoms. The above-mentioned divalent aromatic group is preferably the following formula

示之任何一個基。Show any base.

CgHi} CgHu /~\ _AHi7 _AH17CgHi} CgHu /~\ _AHi7 _AH17

R=C2-C20 烷基R=C2-C20 alkyl

10 322866 20114181810 322866 201141818

(於上述式，以半括弧括上之部位表示鍵結。） 本發明之偶氮甲川寡聚物適用於半導體用途，經由塗 佈法，在電極上成膜，可製作p-n接合元件。以對於將上 述偶氮曱川养聚物作為P型半導體層或N型半導體層之形 成材料使用，製作之p-n接合元件，將p型半導體側之電 極連接於正極端子，將N型半導體侧之電極連接於負極端 子，可在-5V至+5V之範圍内施加電壓，成為順方向之電力 量/逆方向之電力量>1〇為特徵。 本發明之偶氮甲川寡聚物可經由具有對於下述通式 (II)表示之含有芳族環之化合物1當量，將下述通式（瓜） 表不之煙化合物2當量進行反應之步驟之製造方法製造。 11 322866 201141818 乂一^Ar1一(Α-Αήρ-X (Π)(In the above formula, the portion enclosed by the semi-bracket indicates the bond.) The azomethine oligomer of the present invention is suitable for use in semiconductor applications, and a p-n junction element can be produced by forming a film on the electrode by a coating method. In the pn junction element produced by using the above-described azo xanthium nutrient as a material for forming a P-type semiconductor layer or an N-type semiconductor layer, the electrode on the p-type semiconductor side is connected to the positive electrode terminal, and the N-type semiconductor side is used. The electrode is connected to the negative electrode terminal, and a voltage can be applied in the range of -5 V to +5 V, and the amount of electric power in the forward direction/the amount of electric power in the reverse direction is characterized by 1 〇. The azomethine oligomer of the present invention can be reacted by reacting 2 equivalents of the smoke compound represented by the following formula (guar) with 1 equivalent of the compound containing an aromatic ring represented by the following formula (II). The manufacturing method is manufactured. 11 322866 201141818 乂一^Ar1一(Α-Αήρ-X (Π)

Υ~·丨 (〇)q—R3 (ΠΙ) 於上述式（π) ’二個X同時為醛基或胺基、Υ~·丨(〇)q—R3 (ΠΙ) In the above formula (π) ’, two X are simultaneously an aldehyde group or an amine group,

Ar1為可具有取代基之二價芳基、Ar1 is a divalent aryl group which may have a substituent,

Ar2為可具有取代基之二價芳基、 A為偶氮次曱基、 P為0至5之整數、 p為2以上時，複數存在之Ar2可相同亦可不同； 於上述式（m)，在上述式（Π)之X為醛基時Y為胺基， X為胺基時Y為酸基，Ar2 is a divalent aryl group which may have a substituent, A is an azo sulfhydryl group, P is an integer of 0 to 5, and when p is 2 or more, Ar2 may exist in the same or different plural; in the above formula (m) When X of the above formula (Π) is an aldehyde group, Y is an amine group, and when X is an amine group, Y is an acid group.

Ar為可具有取代基之二價芳族基、 A為偶氮次甲基、 m為0或1、 R及R獨立為氫原子、碳數1至20之烷基或滷素 原子、 Z為具有氧科、麵子或伸祕基之二價基、 i為0或1，Ar is a divalent aromatic group which may have a substituent, A is an azomethine group, m is 0 or 1, R and R are independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, and Z is a divalent group of oxygen, a face, or a secret base, i is 0 or 1,

至12之整數（惟，z為氧原子或硫原 12 322866 201141818 k為1至10之整數， h為2以上時，複數存在之R1可相同亦可不同， j為2以上時，複數存在之R2可相同亦可不同， k為2以上時，複數存在之（-(CHiOh-Uh-CCHR2)广) 可相同亦可不同、 q為0或1、 R3為碳數1至20之烷基、 (-(CHROh-Uh-CCHRlOk-COX-R3 表示之構造中之 碳數為2至512。 上述含有芳族環之化合物較好為選自由下述式表示之 化合物所成組群之至少一種化合物。 13 322866 201141818An integer of up to 12 (except that z is an oxygen atom or a sulfurogen 12 322866 201141818 k is an integer from 1 to 10, and when h is 2 or more, R1 in the plural may be the same or different, and when j is 2 or more, the plural exists. R2 may be the same or different. When k is 2 or more, the plural (-(CHiOh-Uh-CCHR2) wide) may be the same or different, q is 0 or 1, and R3 is an alkyl group having 1 to 20 carbon atoms. (-(CHROh-Uh-CCHRlOk-COX-R3 represents a carbon number in the structure of 2 to 512. The above compound containing an aromatic ring is preferably at least one compound selected from the group consisting of compounds represented by the following formula: 13 322866 201141818

14 322866 20114181814 322866 201141818

15 322866 20114181815 322866 201141818

16 322866 20114181816 322866 201141818

(於上述式，x為醛基或胺基）。 上述烴化合物較好為選自由下述式表示之化合物所成 組群之至少一種化合物。(In the above formula, x is an aldehyde group or an amine group). The hydrocarbon compound is preferably at least one compound selected from the group consisting of compounds represented by the following formulas.

17 322866 20114181817 322866 201141818

OrOr

(於上述式，γ為胺基或醛基，t為5至11之整數）。 [發明之效果] 本發明之偶氮曱川寡聚物作為半導體材料，確保充分 之載體移動度且對於曱苯等疏水性溶劑，曱醇、乙醇等醇 系溶劑，丙二醇一曱醚等二醇系溶劑或乳酸甲酯等酯系溶 劑等通用性高之有機溶劑呈現高溶解性。 因此，根據本發明之偶氮曱川寡聚物，不是如以往之 共軛系高分子化合物，經由真空蒸鍍將偶氮曱川寡聚物在 基板上定向，而是經由塗佈法在基板上形成半導體層。 【實施方式】 [偶氮曱川寡聚物] 以下，對於本發明偶氮甲川寡聚物具有之上述含有芳 族環之共軛基以及烴基作詳細的說明。 <含有芳族環之共軛基> 構成本發明偶氮曱川寡聚物之含有芳族環之共軛基為 由偶氮次曱基與可具有取代基之二價芳族基互相結合、共 軛之構造。 根據該共軛構造，本發明之偶氮曱川寡聚物具有輸送 18 322866 201141818 分子間載體之機能。 上述可具有取代基之二價芳族基之例列舉下述式A 1 至A-24表示之基。 式A — 1(In the above formula, γ is an amino group or an aldehyde group, and t is an integer of 5 to 11). [Effects of the Invention] The azochuanchuan oligomer of the present invention, as a semiconductor material, ensures sufficient carrier mobility, and is a hydrophobic solvent such as fluorene, an alcohol solvent such as decyl alcohol or ethanol, or a diol such as propylene glycol monoterpene ether. A highly versatile organic solvent such as a solvent or an ester solvent such as methyl lactate exhibits high solubility. Therefore, according to the arsenazo polymer of the present invention, the azo anthraquinone oligomer is not oriented on the substrate by vacuum evaporation as in the conventional conjugated polymer compound, but is applied to the substrate via a coating method. A semiconductor layer is formed thereon. [Analysis] [Azopurine oligomer] Hereinafter, the conjugated group containing an aromatic ring and a hydrocarbon group which the azomethine oligomer of the present invention has will be described in detail. <Conjugation group containing an aromatic ring> The conjugate group containing an aromatic ring constituting the azo曱chuan oligomer of the present invention is an azo group and a divalent aromatic group which may have a substituent Combined, conjugated construction. According to the conjugated structure, the azoxanthene oligomer of the present invention has a function of transporting 18 322866 201141818 intermolecular carrier. Examples of the above divalent aromatic group which may have a substituent include the groups represented by the following formulas A 1 to A-24. Formula A-1

於式A-l’Ra為氫原子、鹵素原子、碳數1至a之^ 基或基中含有it結合或烧氧基之碳數1至15之煙義。上述 幽素原子列舉F、C1及Br。於以下之式a〜2炱A〜24亦相 同。 從本發明偶氮甲川寡聚物在分子間高結晶化之觀㈣ 言，較好Ra為氫原子或齒素原子，更好為范德瓦耳斯 der Waals)半徑小之氫原子。 !!式“，仏為1^之整數。為了使本發明之偶氮 :川券聚物在分子間高結晶化，從使在芳環内電子定域化 為更：之觀點而言，Sa較好為偶數，更好Sa為偶數且使 方族基全體具有對稱要素方々 數且使 不是指偶氮卩；丨丨寡㈣分體代。^對稱要素 對稱性。駿麵上心之構㈣基構造部分之 據實際上測〇(射線構造㈣ 根 之構造之對稱性。以下亦相同。子轨道。十异最適當化 又Α為2以上時，複數存在之以可相同亦可不同。 322866 19 201141818 於式A-l，「*」為鍵結，該等結合於偶氮次曱基。於 以下之式A_2至A_24亦相同。 式A — 2 (Rb)sbThe formula A-1'Ra is a hydrogen atom, a halogen atom, a carbon number of 1 to a, or a group having a carbon number of 1 to 15 which is an it bond or an alkoxy group. The above spectroscopy atoms include F, C1 and Br. The same applies to the following equations a~2炱A~24. From the viewpoint of high crystallization between the azomethine oligomers of the present invention (IV), it is preferred that Ra is a hydrogen atom or a dentate atom, more preferably a hydrogen atom having a small radius of van der Waals. In the formula ", 仏 is an integer of 1^. In order to make the azo:chuan valency polymer of the present invention highly crystallized between molecules, from the viewpoint of localizing electrons in the aromatic ring to be more: It is better to have an even number, and it is better that Sa is an even number and that the square group has a symmetry element square number and does not mean azo 卩; 丨丨 ( (4) a split generation. ^ symmetry element symmetry. The basis of the base structure is actually measured (the symmetry of the structure of the root structure of the ray structure (4). The same applies to the sub-orbit. When the tenth is most suitable and the Α is 2 or more, the plural numbers may be the same or different. 322866 19 201141818 In the formula Al, "*" is a bond, which is bonded to the azo sulfhydryl group. The same applies to the following formulas A_2 to A_24. Formula A-2 (Rb)sb

於式A-2，Rb為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮曱川寡聚物在分子間高結晶化之觀點雨言， 較好Rb為氫原子或鹵素原子，更好為范德瓦耳斯半徑小之 氫原子。 於式A-2，Sb為1至3之整數。為了使在分子間高結 晶化，從使在芳環内電子定域化為更小之觀點而言，Sb較 好為奇數，更好Sb為奇數且使芳族基全體具有對稱要素之 方式予以取代。又，Sb為2以上時，複數存在之Rb可相 同亦可不同。In the formula A-2, Rb is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of intermolecular azochuanchuan oligomers of the present invention, it is preferred that Rb is a hydrogen atom or a halogen atom, more preferably a hydrogen atom having a small van der Waals radius. In the formula A-2, Sb is an integer from 1 to 3. In order to achieve high crystallization between molecules, from the viewpoint of localizing electrons in the aromatic ring to be smaller, Sb is preferably an odd number, and it is preferable that Sb is an odd number and the aromatic group has a symmetrical element as a whole. Replace. Further, when Sb is 2 or more, the plural Rbs may be the same or different.

於式 A-3，Xa 為選自 0、S、NH、N(CH3)、N(C2H5)&N(Ph)， 從本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而 言，較好為立體阻礙性小、平面性高之S及NH。 20 322866 201141818 於式A-3，Ya為選自CH及N，從本發明之偶氮甲川寡 聚物在分子間高結晶化之觀點而言，任何一個都好。 於式A-3，Rc為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮甲川寡聚物在分子間高結晶化之觀點而言， 較好Rc為氫原子或鹵素原子，更好為范德瓦耳斯半徑小之 氳原子。 於式A-3，Ya為CH時，Sc為1或2。為了使本發明之 偶氮甲川寡聚物在分子間高結晶化，從使在芳環内電子定 域化為更小之觀點而言，Sc較好為2,更好為Sc為2且使 芳族基全體以具有對稱要素之方式予以取代。又，Sc為2 時，二個Rc可相同亦可不同。另，Ya為CH時，結合於Ya 之Rc亦可與未隣接於Xa之碳原子所結合之Rc結合，形成 環構造。 又，Yb為N時，Sc為1。 式A-4In the formula A-3, Xa is selected from the group consisting of 0, S, NH, N(CH3), N(C2H5) & N(Ph), and the azo-hydrazine oligomer of the present invention is highly crystallized between molecules. From the viewpoint, it is preferable that S and NH are small in steric hindrance and high in planarity. 20 322866 201141818 In the formula A-3, Ya is selected from the group consisting of CH and N, and any one of them is excellent from the viewpoint of high crystallization of the azomethine oligomer of the present invention in the molecule. In the formula A-3, Rc is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azomethine oligomer of the present invention in the intermolecular phase, Rc is preferably a hydrogen atom or a halogen atom, more preferably a ruthenium atom having a small van der Waals radius. In the formula A-3, when Ya is CH, Sc is 1 or 2. In order to make the azomethine oligomer of the present invention highly crystallized between molecules, from the viewpoint of localizing electrons in the aromatic ring to be smaller, Sc is preferably 2, more preferably Sc is 2 and The entire aromatic group is replaced by a symmetrical element. Further, when Sc is 2, the two Rcs may be the same or different. Further, when Ya is CH, Rc bonded to Ya may be bonded to Rc bonded to a carbon atom not adjacent to Xa to form a ring structure. Further, when Yb is N, Sc is 1. Formula A-4

於式A-4, Xb為選自CH2、C(CxH2x+1)2(X為2至20之整 數）、NH、N(CxH2x+1)(X 為 2 至 20 之整數）、N(Ph)及 S，從 本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言， 較好為立體阻礙性小、平面性高之CH2及NH。 21 322866 201141818 於式A-4，Rd為氩原子、鹵素原子、碳數1至8之烷 基或基中含有醚結合或烷氧基之碳數1至8之烴基。從本 發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言，較 好Rd為氫原子或鹵素原子，更好為范德瓦耳斯半徑小之氫 原子。 於式A-4，Sd為1至6之整數。亦即，Rd雖如圖所示， 於式A-4結合於右側之苯環，惟，Rd於式A-4結合於所有 可結合之碳原子。亦即，Rd不僅結合於式A-4右側之苯環， 亦可結合於左側之苯環。鍵結亦相同。於以下之式A-5至 A_24亦相同。 為了使本發明之偶氮曱川寡聚物在分子間高結晶化， 從使在芳環内電子定域化為更小之觀點而言，Sd較好為偶 數，更好Sd為偶數且使芳族基全體以具有對稱要素之方式 予以取代。又，Sd為2以上時，複數存在之Rd可相同亦 可不同。 式A- 5 (Re)sIn the formula A-4, Xb is selected from CH2, C(CxH2x+1)2 (X is an integer from 2 to 20), NH, N(CxH2x+1) (X is an integer from 2 to 20), N (Ph) And S, from the viewpoint of high crystallization between molecules in the azoxanthene oligomer of the present invention, CH2 and NH which are small in steric hindrance and high in planarity are preferable. 21 322866 201141818 In the formula A-4, Rd is an argon atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms containing an ether bond or an alkoxy group. From the viewpoint of high crystallization of the azoxanthene oligomer of the present invention, it is preferred that Rd is a hydrogen atom or a halogen atom, more preferably a hydrogen atom having a small van der Waals radius. In the formula A-4, Sd is an integer from 1 to 6. That is, although Rd is bonded to the benzene ring on the right side in the formula A-4 as shown, only Rd is bonded to all carbon atoms which can be bonded in the formula A-4. That is, Rd is bonded not only to the benzene ring on the right side of the formula A-4 but also to the benzene ring on the left side. The bond is also the same. The same applies to the following formulas A-5 to A_24. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, Sd is preferably an even number from the viewpoint of localizing electrons in the aromatic ring to be smaller, and it is preferable that Sd is an even number and The entire aromatic group is replaced by a symmetrical element. Further, when Sd is 2 or more, the plural Rs may be the same or different. Equation A-5 (Re)s

於式 A-5，Xc 為選自 0、S、NH、N(CxH2xh)2(X 為 1 至 20之整數）及N(Ph)，從本發明之偶氮曱川寡聚物在分子間 高結晶化之觀點而言，較好為立體阻礙性小、平面性高之 0、S 及 NH。 22 322866 201141818 於式A-5，Yb為選自CH及N，從本發明之偶氮甲川寡 聚物在分子間高結晶化之觀點而言，任何一個都好。 於式A-5，Re為氫原子、鹵素原子、碳數1至8之烷 基或基中含有醚結合或烷氧基之碳數1至8之烴基。從本 發明之偶氮甲川寡聚物在分子間高結晶化之觀點而言，較 好Re為氫原子或鹵素原子，更好為范德瓦耳斯半徑小之氳 原子。 於式A-5，Yb為CH時，Se為1至10之整數。為了使 本發明之偶氮曱川寡聚物在分子間高結晶化，從使在芳環 内電子定域化為更小之觀點而言，Se較好為偶數，更好Se 為偶數且使芳族基全體以具有對稱要素之方式予以取代。In the formula A-5, Xc is selected from the group consisting of 0, S, NH, N(CxH2xh)2 (X is an integer from 1 to 20) and N(Ph), from the azochuanchuan oligomer of the present invention in the intermolecular From the viewpoint of high crystallization, it is preferably 0, S, and NH which are small in steric hindrance and high in planarity. 22 322866 201141818 In the formula A-5, Yb is selected from the group consisting of CH and N, and any one of them is excellent from the viewpoint of high crystallization of the azomethine oligomer of the present invention in the molecule. In the formula A-5, Re is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group. From the viewpoint of high crystallization of the azomethine oligomer of the present invention in the intermolecular phase, Re is preferably a hydrogen atom or a halogen atom, more preferably a ruthenium atom having a small van der Waals radius. In the formula A-5, when Yb is CH, Se is an integer of 1 to 10. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, Se is preferably an even number from the viewpoint of localizing electrons in the aromatic ring to be smaller, and it is more preferable that Se is an even number and The entire aromatic group is replaced by a symmetrical element.

Yb為N時，Se為1至8之整數。為了使本發明之偶氮 曱川寡聚物在分子間高結晶化，從使在芳環内電子定域化 為更小之觀點而言，Se較好為偶數，更好Se為偶數且使 芳族基全體以具有對稱要素之方式予以取代。 又，Se為2以上時，複數存在之Re可相同亦可不同。 式A— 6When Yb is N, Se is an integer of 1 to 8. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, Se is preferably an even number from the viewpoint of localizing electrons in the aromatic ring to be smaller, and it is preferable that Se is an even number and The entire aromatic group is replaced by a symmetrical element. Further, when Se is 2 or more, the Re existing in the plural may be the same or different. Formula A-6

於式A-6，Xd為選自CH或N，從本發明之偶氮甲川寡 聚物在分子間高結晶化之觀點而言，任何一個都好。 於式A-6，Rf為氫原子、鹵素原子、碳數1至8之烷基 或基中含有醚結合或烷氧基之碳數1至8之烴基。從本發明 23 322866 201141818 為 '料間高結晶化之觀點而言，較好Rf 為風原子以素料，該衫德瓦 子Rf 於式^，⑽㈣為^^之風原子。 =氮甲川寡聚物在分子間高結晶使 電子定域化為更小之觀點而言， 7在心内 為族基全體以具有對稱要素之 而言，sf較好為:整數，與上述相同之觀點 具有對稱料之㈣且㈣絲全體以 式=為2以上時，複數存在之Rf可相同亦可不同。In the formula A-6, Xd is selected from CH or N, and any one of them is excellent from the viewpoint of high crystallization of the azomethine oligomer of the present invention in the molecule. In the formula A-6, Rf is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms having an ether-bonded or alkoxy group in the group. From the viewpoint of the present invention 23 322866 201141818, from the viewpoint of "high crystallization between materials, it is preferred that Rf is a wind atom and a sulphate, and the singularity Rf is in the formula ^, (10) (d) is a wind atom of ^^. = Nitromethine oligomer in terms of high intermolecular crystallization to make electrons localized to be smaller, 7 In the case of a family having a symmetrical element in the heart, sf is preferably an integer, which is the same as above. When the viewpoint has a symmetrical material (4) and the (four) filaments have a formula = 2 or more, the Rf of the plural may be the same or different.

於式A-7，Rg4氫原子、齒素原子、碳 基或基中含有鱗結合或燒氧基之碳數！至之燒 發明之偶氮尹川寡聚物在分子間高結 從本 子或齒素原子，更好為范德瓦=言，較 原子。 今所半杈小之氫 於式A-7，Sg為1至1〇之举| 苯環連繫之伸乙基上。為了使本發二將二個 而，較好為偶數，更好Sg為偶數且使芳:丄 322866 24 201141818 具有對稱要素之方式予以取代。又，Sg為2以上時，複數 存在之Rg可相同亦可不同。 式A— 8 (叻)汕In the formula A-7, the Rg4 hydrogen atom, the dentate atom, the carbon group or the group contains the carbon number of the scale-bound or alkoxy group! The azo-Yinchuan oligomers invented in the intermolecular high junction from the atom or the dentate atom, preferably van der Waals = words, more atoms. Today's semi-small hydrogen is in the formula A-7, Sg is 1 to 1 | | benzene ring connected to the ethyl. In order to make the second two, preferably even, better Sg is even and the fang: 322 322866 24 201141818 has a symmetrical element instead. Further, when Sg is 2 or more, the Rg existing in the plural may be the same or different. Equation A-8 (叻)汕

於式A-8，Rh為氫原子、鹵素原子、碳數1至8之烷 基或基中含有醚結合或烧氧基之破數1至8之烴基。從本 發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言，較 好Rh為氫原子或鹵素原子，更好為范德瓦耳斯半徑小之氫 原子。 於式A-8，Sh為1至6之整數。為了使本發明之偶氮 曱川寡聚物在分子間高結晶化，從使在芳環内電子定域化 為更小之觀點而言，Sh較好為偶數，更好Sh為偶數且使 芳族基全體以具有對稱要素之方式予以取代。又，Sh為2 以上時，複數存在之Rh可相同亦可不同。 式A— 9In the formula A-8, Rh is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having an ether-bonded or alkoxy group-containing number 1 to 8 in the group. From the viewpoint of high crystallization of the azoxanthene oligomer of the present invention, it is preferable that Rh is a hydrogen atom or a halogen atom, more preferably a hydrogen atom having a small van der Waals radius. In the formula A-8, Sh is an integer from 1 to 6. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, Sh is preferably an even number from the viewpoint of localizing electrons in the aromatic ring to be smaller, and it is preferable that Sh is an even number and The entire aromatic group is replaced by a symmetrical element. Further, when Sh is 2 or more, the Rh existing in the plural may be the same or different. Formula A-9

於式A-9，Xe為選自CH及N。從本發明之偶氮曱川寡 聚物在分子間高結晶化之觀點而言，Xe較好為CH。 於式A-9，Ri為氫原子、鹵素原子、碳數1至8之烷 基或基中含有醚結合或烷氧基之碳數1至8之烴基。從本 25 322866 201141818 =之偶氮甲叫寡聚物在分子間高結晶化之觀點較 原子或《原子，更㈣祕瓦耳斯半徑小之氮 於式A-9，xe為CH時Si λ 1 s *妓权 發明之偶氮甲川寡聚物在分=為了使本 電子定域化為更小之觀點而言，s :曰曰化么，從使在芳環内 為偶數且使芳族基全體以具有更子Si “為N時Si為1至6之^要素^以取代。 而言，Si較好為㈣…整數。從與上述相同之觀點 具有對稱要代1為偶數且使芳族基全體以 式=為2以上時’複數存在之Ri可相同亦可不同。In formula A-9, Xe is selected from the group consisting of CH and N. From the viewpoint of high crystallization between molecules in the azochuanchuan oligomer of the present invention, Xe is preferably CH. In the formula A-9, Ri is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group. From this 25 322866 201141818 = the azo-methyl oligo is higher in the intermolecular crystallization than the atom or "atom, more (four) Mivars radius of nitrogen is less than the formula A-9, xe is CH Si λ 1 s * 偶 发明 发明 发明 发明 发明 = = = = = = = = = = = 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了The whole group is replaced by an element having a more sub-Si "Si when Si is 1 to 6". In terms of Si, Si is preferably an integer of (4). From the same viewpoint as above, it has a symmetry to be an even number and an aromatic When the formula group = 2 or more, the plural of the plural may be the same or different.

於式A-l〇，Rj為氫原子、鹵素 基或基中含㈣結合或烧氧基之碳數礙數1至8之燒 發明之偶氮甲川寡聚物在分子間高結 2烴基。從本 好W為氫原子或齒素原子，更好為范德瓦^觀點而言，較 原子。 耳斯半徑小之氫 於式A-l〇’Sj為1至8之整數。為 甲川寡聚物在分子間高結晶化，從使在/^發明之偶氮 為更小之觀點而言，Sj較好為偶數H内電子定域化 芳族基全體以具有對稱要素之方式 j為偶數且使 '1取代。又，Sj為2 322866 26 201141818 以上時，複數存在之Rj可相同亦可不同。 式 A- 1 1In the formula A-l〇, Rj is a hydrogen atom, a halogen group or a group having a carbon number of 1 or 8 in which the group is bonded or alkoxylated. The azomethine oligomer of the invention has a high hydrocarbon group in the molecule. From the point of view, it is a hydrogen atom or a dentate atom, and more preferably van der Waals. Hydrogen having a small radius of the sigma is an integer of 1 to 8 in the formula A-l〇'Sj. For the high crystallization of the methacrylate oligomer between molecules, from the viewpoint of making the azo of the invention smaller, Sj is preferably an even number of electrons in the H group. j is an even number and is substituted by '1. Further, when Sj is 2 322866 26 201141818 or more, the Rj of the plural number may be the same or different. Formula A- 1 1

於式A-ll，Xf為選自CH及N，從本發明之偶氮甲川 寡聚物在分子間高結晶化之觀點而言，Xf較好為N。 於式A-ll，Rk為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言， 較好Rk為氫原子或鹵素原子，更好為范德瓦耳斯半徑小之 氫原子。 於式A-ll，Xf為CH時，Sk為1至8之整數。為了使 本發明之偶氮曱川寡聚物在分子間高結晶化，從使在芳環 内電子定域化為更小之觀點而言，Sk較好為偶數，更好Sj 為偶數且使芳族基全體以具有對稱要素之方式予以取代。In the formula A-ll, Xf is selected from CH and N, and Xf is preferably N from the viewpoint of high crystallization between molecules in the azomethine oligomer of the present invention. In the formula A-ll, Rk is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azoxanthene oligomer of the present invention in the intermolecular phase, Rk is preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom having a small van der Waals radius. In the formula A-ll, when Xf is CH, Sk is an integer of 1 to 8. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, from the viewpoint of localizing electrons in the aromatic ring to be smaller, Sk is preferably an even number, and more preferably Sj is an even number and The entire aromatic group is replaced by a symmetrical element.

Xf為N時Sk為1至6之整數。從與上述相同之觀點 而言，Sk較好為偶數，更好Sk為偶數且使芳族基全體以 具有對稱要素之方式予以取代。When Xf is N, Sk is an integer of 1 to 6. From the same viewpoint as described above, Sk is preferably an even number, and it is more preferable that Sk is an even number and the entire aromatic group is substituted with a symmetrical element.

Sk為2以上時，複數存在之Rk可相同亦可不同。 式 A- 1 2When Sk is 2 or more, the Rk in the plural may be the same or different. Formula A- 1 2

27 322866 201141818 於式A-12，Xg為選自CH及N，從本發明之偶氮甲川 寡聚物在分子間高結晶化之觀點而言，Xg較好為N。 於式A-12，Rm為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮甲川寡聚物在分子間高結晶化之觀點而言， 較好Rm為氫原子或鹵素原子，更好為范德瓦耳斯半徑小之 氫原子。 於式A-12，Xg為CH時，Sm為1至8之整數。為了使 本發明之偶氮曱川寡聚物在分子間高結晶化，從使在芳環 内電子定域化為更小之觀點而言，Sm較好為偶數，更好Sm 為偶數且使芳族基全體以具有對稱要素之方式予以取代。27 322866 201141818 In the formula A-12, Xg is selected from CH and N, and Xg is preferably N from the viewpoint of high crystallization between molecules in the azomethine oligomer of the present invention. In the formula A-12, Rm is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azomethine oligomer of the present invention in the intermolecular phase, Rm is preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom having a small van der Waals radius. In the formula A-12, when Xg is CH, Sm is an integer of 1 to 8. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, from the viewpoint of localizing electrons in the aromatic ring to be smaller, Sm is preferably an even number, and more preferably Sm is an even number and The entire aromatic group is replaced by a symmetrical element.

Xg為N時Sm為1至6之整數。從與上述相同之觀點 而言，Sm較好為偶數，更好Sm為偶數且使芳族基全體以 具有對稱要素之方式予以取代。When Xg is N, Sm is an integer of 1 to 6. From the same viewpoint as described above, Sm is preferably an even number, and it is more preferable that Sm is an even number and the entire aromatic group is substituted with a symmetrical element.

Sm為2以上時，複數存在之Rm可相同亦可不同。 式 A— 1 3When Sm is 2 or more, the Rm in the plural may be the same or different. Equation A-1 3

於式 A-13，Xh 為選自 0、S、NH、N(CH3)、N(C2H5)及 N(Ph)。從本發明偶氮曱川寡聚物之分子内共軛系之平面性 高度之觀點而言，較好為S、NH。 於式A-13，Rn為氫原子、鹵素原子、碳數1至8之烷 28 322866 201141818 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮甲川寡聚物在分子間高結晶化之觀點而言， 較好Rn為氩原子、碳數1至8之烷基或碳數1至8之烷氧 基，更好為范德瓦耳斯半徑小之氫原子。 於式A-13，Sn為1至4之整數。Sn為2以上時，複 數存在之Rn可相同亦可不同。為了使本發明之偶.氮甲川寡 聚物在分子間高結晶化，從使在芳環内電子定域化為更小 之觀點而言，Sn較好為2至4之整數，更好為2或4。 式 A-14In the formula A-13, Xh is selected from the group consisting of 0, S, NH, N(CH3), N(C2H5) and N(Ph). From the viewpoint of the planarity of the intramolecular conjugated system of the azochuanchuan oligomer of the present invention, S and NH are preferred. In the formula A-13, Rn is a hydrogen atom, a halogen atom, and an alkyl group having 1 to 8 carbon atoms. 322866 201141818 A hydrocarbon group having a carbon number of 1 to 8 containing an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azomethine oligomer of the present invention in the intermolecular phase, Rn is preferably an argon atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably Van der Waals has a small radius of hydrogen atoms. In the formula A-13, Sn is an integer of 1 to 4. When Sn is 2 or more, the Rn present in the plural may be the same or different. In order to make the azomethine oligomer of the present invention highly crystallized between molecules, Sn is preferably an integer of 2 to 4 from the viewpoint of localizing electrons in the aromatic ring to be smaller, more preferably 2 or 4. Formula A-14

於式 A-14，Xi 為選自 0、S、NH、N(CH3)、N(C2H5)及 N(Ph)，從本發明偶氮曱川寡聚物之分子内共軛系之平面性 高度之觀點而言，較好為S、NH。 於式A-14，Rp為氳原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言， 較好Rp為氩原子、碳數1至8之烷基或碳數1至8之烷氧 基，更好為范德瓦耳斯半徑小之氩原子。 於式A-14，Sp為1至8之整數。Sp為2以上時，複 數存在之Rp可相同亦可不同。為了使本發明之偶氮曱川寡 聚物在分子間高結晶化，從使在芳環内電子定域化為更小 29 322866 201141818 之觀點而言，Sp較好為4至8之整數，更好為4或8。 式 A- 1 5In the formula A-14, Xi is selected from the group consisting of 0, S, NH, N(CH3), N(C2H5) and N(Ph), and the planarity of the intramolecular conjugated system of the azochuanchuan oligomer of the present invention From the viewpoint of height, it is preferably S or NH. In the formula A-14, Rp is a halogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of intermolecular azochuanchuan oligomers of the present invention, Rp is preferably an argon atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably An argon atom with a small radius of van der Waals. In the formula A-14, Sp is an integer from 1 to 8. When Sp is 2 or more, the Rp of the plural may be the same or different. In order to make the azoxanthene oligomer of the present invention highly intermolecularly crystallized, Sp is preferably an integer of 4 to 8 from the viewpoint of localizing electrons in the aromatic ring to a smaller 29 322866 201141818. Better for 4 or 8. Formula A- 1 5

於式A-15，Xj為選自CH及N，從本發明之偶氮甲川 寡聚物原料由商業上取得之容易度之觀點而言，較好為 CH。 於式A-15，Rq為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言， 較好Rq為氫原子、碳數1至8之烷基或碳數1至8之烷氧 基，更好為范德瓦耳斯半徑小之氳原子。 於式A-15，Xj為CH時，Sq為1或2。Sq為2時，2 個存在之Rp可相同亦可不同。為了使本發明之偶氮甲川寡 聚物在分子間高結晶化，從使在芳環内電子定域化為更小 之觀點而言，Sq較好為2。 又，Xj為N時，Sq為0。In the formula A-15, Xj is selected from the group consisting of CH and N, and is preferably CH from the viewpoint of the commercial availability of the azomethine oligomer raw material of the present invention. In the formula A-15, Rq is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azozaindene oligomer of the present invention, it is preferred that Rq is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably It is a small atom of van der Waals with a small radius. In the formula A-15, when Xj is CH, Sq is 1 or 2. When Sq is 2, the two existing Rp may be the same or different. In order to make the azomethine oligomer of the present invention highly crystallized between molecules, Sq is preferably 2 from the viewpoint of localizing electrons in the aromatic ring to be smaller. Further, when Xj is N, Sq is 0.

於式A-16，Xk為選自S及0，從本發明之偶氮曱川寡 聚物原料由商業上取得之容易度之觀點而言，較好為S。 30 322866 201141818 於式A-l6，Rr為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言， 較好Rr為氫原子、碳數1至8之烷基或碳數1至8之烷氧 基，更好為范德瓦耳斯半徑小之氫原子。 於式A-16，Sr為1至4之整數。Sr為2以上時，複 數存在之Rr可相同亦可不同。為了使本發明之偶氮曱川寡 聚物在分子間高結晶化，從使在芳環内電子定域化為更小 之觀點而言，Sr較好為3或4，更好為4。In the formula A-16, Xk is selected from S and 0, and from the viewpoint of the ease of commercial use of the azochuanchuan oligomer raw material of the present invention, S is preferable. 30 322866 201141818 In the formula A-l6, Rr is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of intermolecular azochuanchuan oligomers of the present invention, Rr is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably It is a hydrogen atom with a small radius of van der Waals. In the formula A-16, Sr is an integer from 1 to 4. When Sr is 2 or more, the Rr of the plural may be the same or different. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, Sr is preferably 3 or 4, more preferably 4, from the viewpoint of localizing electrons in the aromatic ring to be smaller.

於式A-l7，Rs為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言， 較好Rs為氫原子、碳數1至8之烷基或碳數1至8之烷氧 基，更好為范德瓦耳斯半徑小之氫原子。 於式A-17，Ss為1或2。Ss為2時，2個存在之Rs 可相同亦可不同。為了使本發明之偶氮曱川寡聚物在分子 間高結晶化，從使在芳環内電子定域化為更小之觀點而 言，Ss較好為2。In the formula A-1, Rs is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azoxanthene oligomer of the present invention, it is preferred that Rs is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably It is a hydrogen atom with a small radius of van der Waals. In the formula A-17, Ss is 1 or 2. When Ss is 2, the two existing Rs may be the same or different. In order to make the azoxanthene oligomer of the present invention highly crystallized in the molecule, Ss is preferably 2 from the viewpoint of localizing electrons in the aromatic ring to be smaller.

31 322866 201141818 於式A-l8，Rt為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言， 較好Rt為氫原子、碳數1至8之烷基或碳數1至8之烷氧 基，更好為范德瓦耳斯半徑小之氳原子。 於式A-18，St為1至4之整數。St為2以上時，複 數存在之Rt可相同亦可不同。為了使本發明之偶氮曱川寡 聚物在分子間高結晶化，從使在芳環内電子定域化為更小 之觀點而言，St較好為偶數且使芳族基全體以具有對稱要 素之方式予以取代。 (Ru)su31 322866 201141818 In the formula A-l8, Rt is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms having an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization between molecules in the azoxanthene oligomer of the present invention, Rt is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably It is a small atom of van der Waals with a small radius. In the formula A-18, St is an integer from 1 to 4. When St is 2 or more, the Rt of the plural may be the same or different. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, from the viewpoint of localizing electrons in the aromatic ring to be smaller, St is preferably an even number and has an aromatic group as a whole. The way of symmetrical elements is replaced. (Ru)su

於式A-19，Ru為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮甲川寡聚物在分子間高結晶化之觀點而言， 較好Ru為氫原子、碳數1至8之烷基或碳數1至8之烷氧 基，更好為范德瓦耳斯半徑小之氫原子。 於式A-19，Su為1或2。Su為2時，2個存在之Ru 可相同亦可不同。為了使本發明之偶氮曱川寡聚物在分子 間高結晶化，從使在芳環内電子定域化為更小之觀點而 言，較好Su為2且使芳族基全體以具有對稱要素之方式予 32 322866 201141818 以取代。 式A- 2 0In the formula A-19, Ru is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azomethine oligomer of the present invention in the intermolecular phase, Ru is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably Van der Waals has a small radius of hydrogen atoms. In the formula A-19, Su is 1 or 2. When Su is 2, the two Rus present may be the same or different. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, from the viewpoint of localizing the electrons in the aromatic ring to be smaller, it is preferable that Su is 2 and the aromatic group is provided as a whole. The way of symmetrical elements is replaced by 32 322866 201141818. Formula A- 2 0

* (Rv)Sv 於式A-20，Rv為氫原子、鹵素原子、碳數1至15之 烷基或在基中含有醚結合或烷氧基之碳數1至15之烴基。 從本發明之偶氮甲川寡聚物在分子間高結晶化之觀點而 言，較好Rv為氫原子、碳數1至15之烷基或碳數1至15 之烷氧基，更好為范德瓦耳斯半徑小之氫原子。 於式A-20，Sv為1至6之整數。Sv為2以上時，複 數存在之Rv可相同亦可不同。為了使本發明之偶氮曱川寡 聚物在分子間高結晶化，從使在芳環内電子定域化為更小 之觀點而言，較好Sv為偶數且使芳族基全體以具有對稱要 素之方式予以取代。 式A- 2 1* (Rv)Sv In the formula A-20, Rv is a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms or a hydrocarbon group having 1 to 15 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azomethine oligomer of the present invention between molecules, Rv is preferably a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 15 carbon atoms, more preferably Van der Waals has a small radius of hydrogen atoms. In the formula A-20, Sv is an integer from 1 to 6. When Sv is 2 or more, the Rv of the plural may be the same or different. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, from the viewpoint of localizing electrons in the aromatic ring to be smaller, it is preferred that Sv is an even number and that the aromatic group has a whole The way of symmetrical elements is replaced. Formula A-2 1

於式A-21，Rx為氫原子、鹵素原子、碳數1至8之烷 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而言， 較好Rx為氳原子、碳數1至8之烷基或碳數1至8之烷氧 33 322866 201141818 基’c急瓦耳斯半徑小之氫原子。 可相同;同匕為1或2。Sx為2時，2個存在之Rx Η古处曰 馮了使本發明之偶氮曱川募聚物在分子 Γ化’從使在芳環内電子找化為更小之觀點而 吕，較好Sxg2。 式A- 2 2In the formula A-21, Rx is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms which contains an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azoxanthene oligomer of the present invention in terms of intermolecular high crystallization, Rx is preferably a halogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having a carbon number of 1 to 8 33 322866 201141818 'c Urgent gassius small hydrogen atoms. Can be the same; the same is 1 or 2. When Sx is 2, two existing Rx Η 曰 了 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使 使Good Sxg2. Formula A-2 2

於式A-22，Rv去匕 >h, ^ . ^ ^灯為氫原子、函素原子、碳數1至15之 土彳合有醚結合或烷氧基之碳數1至15之烴基。 言，較好R V A &丨养聚物在分子間高結晶化之觀點而 之&氧至15之縣或雜1至15 於式A〜22瓦耳斯半徑小之氮原子。 數存在之Ry可相^ ^至4之整數。办為2以上時，複 聚物在分子^結^。為了使本發明之減甲川寡 之觀點而言，較^日’從使在芳環内電子定域化為更小 要素之方式取代偶數，且使芳族基全體以具有對稱 式A- 2 3In the formula A-22, Rv is deuterium >h, ^ . ^ ^ The lamp is a hydrogen atom, a functional atom, a carbon number of 1 to 15 and a hydrocarbon group having an ether bond or an alkoxy group having 1 to 15 carbon atoms. . In other words, it is preferred that the R V A & 丨 聚物 在 高 高 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧The Ry present in the number can be an integer from ^^ to 4. When the ratio is 2 or more, the polymer is ligated in the molecule. In order to make the invention of the invention, it is preferable to replace the even number in such a manner that electrons are localized into smaller elements in the aromatic ring, and the aromatic group is made to have a symmetric formula A - 2 3

於式為氫原子、 (Rz)Sz 鹵素原子、碳數1至8之烷 322866 34 201141818 基或在基中含有醚結合或烷氧基之碳數1至8之烴基。從 本發明之偶氮甲川寡聚物在分子間高結晶化之觀點而言， 較好Rz為氫原子、碳數1至8之烷基或碳數1至8之烷氧 基，更好為范德瓦耳斯半徑小之氫原子。 於式A-23，Sz為1至6之整數。Sz為2以上時，複 數存在之Rz可相同亦可不同。為了使本發明之偶氮曱川寡 聚物在分子間高結晶化，從使在芳環内電子定域化為更小 之觀點而言，較好Sz為偶數，且使芳族基全體以具有對稱 要素之方式予以取代。 式A- 2 4 *The formula is a hydrogen atom, a (Rz)Sz halogen atom, an alkyl group having 1 to 8 carbon atoms 322866 34 201141818 or a hydrocarbon group having 1 to 8 carbon atoms having an ether bond or an alkoxy group in the group. From the viewpoint of high crystallization of the azomethine oligomer of the present invention in the intermolecular phase, Rz is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably Van der Waals has a small radius of hydrogen atoms. In the formula A-23, Sz is an integer from 1 to 6. When Sz is 2 or more, the Rz of the plural may be the same or different. In order to make the azoxanthene oligomer of the present invention highly crystallized between molecules, from the viewpoint of localizing electrons in the aromatic ring to be smaller, it is preferable that Sz is an even number and the aromatic group is made entirely Replace it with a symmetrical element. Formula A- 2 4 *

於式A-24，Raa為氬原子、鹵素原子、碳數1至8之 烷基或在基中含有醚結合或烷氧基之碳數1至8之烴基。 從本發明之偶氮曱川寡聚物在分子間高結晶化之觀點而 言，較好Raa為氫原子、碳數1至8之烷基或碳數1至8 之烷氧基，更好為范德瓦耳斯半徑小之氫原子。 於式A-24，Saa為1至6之整數。Saa為2以上時， 複數存在之Raa可相同亦可不同。為了使本發明之偶氮甲 川寡聚物在分子間高結晶化，從使在芳環内電子定域化為 更小之觀點而言，較好Saa為偶數，且使芳族基全體以具 有對稱要素之方式予以取代。 於上述含有芳族環之共軛基，該等二價芳族基經由偶 35 322866 201141818 氮次曱基連妹，彼 码氮次曱基與二價芳族基交互結合，進行 共輛之構造。又 入— 一價芳族基之數即使為1個亦可。 有芳族環之共軛基中之芳族基通常為5個以下，從 本發月之偶氮甲川寡聚物在溶劑之溶解性、分子内共軛、 分子間之結晶性 义觀點而言’較好為1至5個。將偶氮次 曱基與二價芳族其^ 礼人 矢I父互結合之方法於後述之本發明偶氮甲 川寡聚物之製造大、1 衣w方法之項目中說明。 <烴基> 口且構，本發明偶氮甲川寡聚物之上述烴基，只要是具有 ^二有氧原子、琉原子或伸環烧基之基，不與上述含有芳 衣之’、扼基進行共d⑮基及胺基*具有反應性者即 可’並無特別限制。與㈣及胺基不具有反應性之意義在 後述之本發明偶氮甲川寡聚物製造方法之項目中說明。 該烴基賦予本發明之偶氮曱川寡聚物在有機溶劑 溶解性。 上述烴基之例列舉可具有支鏈、可經自素原子取代之 碳數2至512之烷基，可具有支鏈、可經齒素原子取代之 碳數2至512之烷氧基，在基中具有醚結合及/或硫醚結 合、可經函素原子取代之碳數2至512之烴基，以及可具 有取代基之碳數3至50之環烷基。 上述i素原子之例列舉氟原子、氣原子及填原子。 上述環烷基中之取代基列舉函素原子、碳數丨至6之 烧基及碳數1至6之烧氧基。又’環院基可具有複數之環 狀構造，另，該環狀構造可經由伸烷基連結。 322866 36 201141818 上述烧基之碳數，從本發明之偶氮甲川寡聚物在有機 溶劑的親和性及在固體狀態分子間之結晶性並存之觀點而 言’較好為3至20 ’更好為4至12，最好為6至12。 上述烧氧基之碳數’從本發明之偶氮曱川寡聚物在有 機溶劑的親和性及在固體狀態分子間之結晶性並存之觀點 而言’較好為3至20，更好為4至12，最好為6至12。 在上述基中具有醚結合及/或硫醚結合，可經_素原子 取代之烴基之碳數，從本發明之偶氮甲川寡聚物在有機溶 劑的親和性及在固體狀態分子間之結晶性並存之觀點而 言’較好為3至20，更好為4至12，最好為6至12。 上述可具有取代基之環烧基之碳數，從本發明之偶氮 甲川寡聚物在有機㈣的親和性及在固體㈣分子間之姓 晶性並存之觀點而言’較好為3至30，更好為6至15 Γ ，成本發明偶氮"(寡聚物之烴基，從在有機溶劑之 水^之觀點而言，此甲苯等為較低極性，為了表現在疏 =焉之溶劑之溶解性，較好為具有燒基之構造。為了表 、士於醇系、二醇系、酯系溶劑之溶解性， ^ 為基中具有醚結合構造者 土較好 子系溶劑之絲h + 現對於含有自素原 τ冷綃之命解性，上述烴基較好為基 鹵素原子取代）構造者^ ，、有自素原子（經 <偶氮甲川寡聚物> 於本發明之偶氮甲川寡聚物，在 環之共軛ώ 上說明之含有芳族 由偶氮”基結合。 322866 37 201141818 CH3(CH2)7-In the formula A-24, Raa is an argon atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms in the group containing an ether bond or an alkoxy group. From the viewpoint of high crystallization of the azoxanthene oligomer of the present invention, it is preferred that Raa is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably It is a hydrogen atom with a small radius of van der Waals. In the formula A-24, Saa is an integer from 1 to 6. When Saa is 2 or more, the Raa of the plural number may be the same or different. In order to make the azomethine oligomer of the present invention highly crystallized between molecules, from the viewpoint of localizing electrons in the aromatic ring to be smaller, it is preferred that Saa is an even number and that the aromatic group is entirely The way of symmetrical elements is replaced. In the above-mentioned conjugated group containing an aromatic ring, the divalent aromatic group is bonded to the divalent aromatic group via the couple 35 322866 201141818, and the cross-linking of the divalent aromatic group is carried out to carry out the construction of the common vehicle. . Further - even if the number of monovalent aromatic groups is one. The aromatic group in the conjugated group having an aromatic ring is usually 5 or less, and from the viewpoint of solvent solubility, intramolecular conjugate, and intermolecular crystallinity of the azomethine oligomer of the present month 'It is preferably 1 to 5. The method of combining the azo sulfhydryl group with the divalent aromatic group and the genus I parent can be explained in the item of the method for producing azo azo oligomer of the present invention which will be described later. <Hydrocarbon group> The above-mentioned hydrocarbon group of the azomethine oligomer of the present invention is not the same as the above-mentioned aryl group, as long as it has a group having a dioxane atom, a ruthenium atom or a cycloalkyl group. The group which carries out the total d15 group and the amine group* is reactive, and there is no particular limitation. The meaning of the reactivity with (4) and the amine group is explained in the item of the method for producing an azomethine oligomer of the present invention to be described later. The hydrocarbon group imparts solubility in an organic solvent to the azokawachuan oligomer of the present invention. Examples of the above hydrocarbon group include an alkyl group having 2 to 512 carbon atoms which may have a branch, which may be substituted by a self-atomic atom, and an alkoxy group having 2 to 512 carbon atoms which may have a branched chain and may be substituted by a dentate atom. A hydrocarbon group having 2 to 512 carbon atoms which has an ether bond and/or a thioether bond, which may be substituted by a functional atom, and a cycloalkyl group having 3 to 50 carbon atoms which may have a substituent. Examples of the above-described imine atom include a fluorine atom, a gas atom, and a filling atom. The substituents in the above cycloalkyl group include a functional group atom, a carbon number of 丨 to 6 and an alkoxy group having 1 to 6 carbon atoms. Further, the ring-shaped structure may have a plurality of ring-like structures, and the ring-shaped structure may be connected via an alkyl group. 322866 36 201141818 The carbon number of the above-mentioned alkyl group is preferably from 3 to 20' from the viewpoints of the affinity of the azomethine oligomer of the present invention in an organic solvent and the crystallinity between molecules in a solid state. It is 4 to 12, preferably 6 to 12. The carbon number of the above-mentioned alkoxy group is preferably from 3 to 20, more preferably from 3 to 20, from the viewpoint of the affinity of the azokawachuan oligomer of the present invention in an organic solvent and the crystallinity between molecules in a solid state. 4 to 12, preferably 6 to 12. The carbon number of the hydrocarbon group which has an ether bond and/or a thioether bond in the above group, which can be substituted by a _ atom, the affinity of the azomethine oligomer of the present invention in an organic solvent and the crystallization between molecules in a solid state From the viewpoint of sexual coexistence, 'it is preferably from 3 to 20, more preferably from 4 to 12, most preferably from 6 to 12. The carbon number of the above-mentioned cycloalkyl group which may have a substituent is preferably from 3 to 3 from the viewpoint of the affinity of the azomethine oligomer of the present invention in the organic (four) and the crystallinity between the solid (tetra) molecules. 30, more preferably 6 to 15 Γ, the cost of the invention azo " (the hydrocarbon group of the oligomer, from the point of view of the water in the organic solvent, this toluene, etc. is of lower polarity, in order to behave in the The solubility of the solvent is preferably a structure having a burnt group. For the solubility of the solvent, the alcohol-based, the diol-based, or the ester-based solvent, ^ is a solvent having a good bond of the ether-bonded structure. h + is now a structure containing a self-priming τ cold enthalpy, the above-mentioned hydrocarbon group is preferably a halogen atom-substituted structure, and has a self-atomic atom (via <azo azo oligo]> The azomethine oligomer, which is described on the conjugate fluorene of the ring, contains an aromatic group bonded by an azo group. 322866 37 201141818 CH3(CH2)7-

-C=N-C=N

N=C. (CH2)7CH3N=C. (CH2)7CH3

CH3(CH2)7----N=C C=N--(CH2)7CH3 該構造，含有芳族環之共扼基為在i位及4位 ^次:基之伸苯基，烴基為辛基之構造。C=N為偶氮次甲 土 ’雖然根據該方向’在共輛系内之共扼狀態不同 認為上述共轆狀態於含有笨基等非雜原子之芳族， 於分子間之結晶性沒有很大的影響。另一認^ ^ 口比咬基等雜環時，根據偶氮次甲基之 ^料為 對於分子間之結晶性有影響。亦即，偶氮次甲=態 構成偶氮次甲基之N及C中，N向著接近雜環 之雜原子接近成偶氮甲川之n時mi起在本發明^雜甲環 寡聚物固體狀態中分子内共軛系之擴張，又 【甲川 =構造受到很大的影響而較佳。本發明之偶氣= 物在溶液狀態，以上述偶氮次甲基令之N 丨养聚 為基礎’期待顯示對於金屬離子之金屬化效果原子 :果等，經由上述效果之相互作用，偶氮 ：： 模板（template)化。 戈物破 本發明之偶氮甲川寡聚物其構造中具有上述 於該部分未具有結晶性，所以對於廣 土由 劑，例如疏水性溶劑、醇系溶劑、_ 回 樣有機溶 ^ -醇溶劑或醋系溶削顯 322866 38 201141818 示高溶解性。 更具體而言，上述偶氮曱川寡聚物通常對於選自曱酚、 曱苯、THF、環戊基曱基醚、丙酮、ΜΕΚ、MIBK、環戊酮、 氯仿、二氯甲烧、四氯化碳、氣苯、二硫化碳、乙酸乙酯、 乙酸丁酯、乳酸曱酯、曱醇、乙醇、異丙醇、苯曱醇、正 丁醇、第三丁醇、戊醇、乙二醇、丙二醇、丙二醇一曱醚、 吡啶、NMP、硫酸、甲酸、乙酸、鹽酸、乳酸、三乙胺、二 丁胺中之任何一種溶劑或二種以上之共溶劑100g，於25 °〇通常具有O.lg以上，較好1至10g之溶解性。又，如在 [先前技術]段所述，甲酚或氯苯等為具有腐蝕性或對於人 體有害。於本發明，該等通常少量混合於其他之曱苯等廣 用性高之溶劑中，作為共溶劑使用。 如此，對於廣用性高、多種有機溶劑之溶解性高之本 發明之偶氮曱川寡聚物，即使未具有如以往聚偶氮曱川之 聚合物構造，輸送電子及電洞等載體之機能高，適用於半 導體用途。 本發明之偶氮曱川寡聚物具有高載體輸送機能係根據 以下之理由。亦即，偶氮曱川寡聚物與親和性高之同類彼 此（亦即烴基為烴基同類彼此、含有芳族環之共軛基為含有 芳族環之共軛基同類彼此）疊合。因此，在含有芳族環之共 軛基堆疊處，載體可自由移動。亦即，對於以往之聚偶氮 曱川係根據分子内特定構造以確保載體移動度，於本發明 係根據分子間之堆疊以確保載體之移動度。 如以上之說明，本發明之偶氮曱川寡聚物具有高載體 39 322866 201141818 輸送機能，適用於半導則途，且對於廣雜高之有機溶 劑顯示高賴性。賴，使料切減f川寡聚物溶解 於廣用性高之有機溶劑獲得之偶氮甲川寡聚物溶液，經由 旋轉塗覆或浸潰塗覆之塗佈法’可安全且容易的在基板上 形成半導體層。 將具有該等載體輸送機能之本發明偶氮甲川寡聚物之 溶液塗佈在電極上進行歧，可製作p_n接合林。將偶 氮甲川寡聚物作為P型半導體層形成材料使用時，N型半 導體層由使用顯示比偶氮曱川寡聚物之離子化電位（eV)值 更大之電子親和力（eV)之半導體材料（例如富勒烯 (Fuller·))形成。又，將偶氮甲川絲物使料為請 半導體層形成㈣時’P型半導體層岐錢示比偶氣甲 川寡聚物之電子親和力（eV)值更小之離子化電位之半導體 材料（例如：聚（3-己基嗔吩））製作。 更具體而言’將本發明之偶氮曱川募聚物使用作為N 型半導體層之形成材料時，將偶氮曱川寡㈣㈣塗佈在 負極電極基板上，乾燥，製作膜。在該膜上以塗佈或蒸鍍 P型半導體材料等進行成膜，在獲得之？型半導體廣上經 由將正側之電極蒸鍵’可製作P-η接合元件。X，將本發 明之偶氮f)丨丨絲物❹作為p料導體層之形成材料 b夺’將N型半導體材料以塗佈或蒸链等在負側電極基板上 成膜，在其膜上將贱甲川絲祕液塗佈、乾燥，形成 P型半導體層，另，在上“型半導體層將正極電極蒸链， 可製作p-n接合元件。該等p塑及N型半導體材料接合體 40 322866 201141818 ，由此操作製成之p-nCH3(CH2)7----N=CC=N--(CH2)7CH3 In this structure, the fluorenyl group containing an aromatic ring is in the i position and the 4 position: the phenyl group of the group, the hydrocarbon group is octyl The structure of the base. C=N is an azo-sub-soil 'Although the conjugate state in the common-vehicle system differs from the conjugate state in the common direction to the aromatic group containing a non-hetero atom such as a stupid base, and the crystallinity between the molecules is not very high. Great impact. When the other is a heterocyclic ring such as a dimethyl group, the azo methine group has an influence on the crystallinity between molecules. That is, in the N and C of the azo methine group, the N is close to the hetero atom of the hetero ring and is close to the n of the azomethine, and the mi is in the present invention. The expansion of the intramolecular conjugate system in the state, and [Kawagawa = structure is greatly affected and better. The argon gas of the present invention is in a solution state, based on the above-mentioned azomethine-based N 丨 agglomeration, and it is expected to exhibit a metallization effect on a metal ion: an atom, etc., through the interaction of the above effects, azo :: Template (template). The azomethine oligomer of the present invention has the above-mentioned structure having no crystallinity in the structure, and therefore, for a broad-based agent, for example, a hydrophobic solvent, an alcohol solvent, and an organic solvent. Or vinegar-based melt-cutting 322866 38 201141818 shows high solubility. More specifically, the above azochuanchuan oligomer is generally selected from the group consisting of nonylphenol, anthracene, THF, cyclopentyl decyl ether, acetone, hydrazine, MIBK, cyclopentanone, chloroform, dichloromethane, and tetra Carbon chloride, gas benzene, carbon disulfide, ethyl acetate, butyl acetate, decyl lactate, decyl alcohol, ethanol, isopropanol, benzofuran, n-butanol, tert-butanol, pentanol, ethylene glycol, Any one of propylene glycol, propylene glycol monoterpene ether, pyridine, NMP, sulfuric acid, formic acid, acetic acid, hydrochloric acid, lactic acid, triethylamine, dibutylamine or 100 g of two or more kinds of cosolvents, usually having an O at 25 °. More than lg, preferably from 1 to 10 g. Further, as described in the [Prior Art] section, cresol or chlorobenzene or the like is corrosive or harmful to humans. In the present invention, these are usually mixed in a small amount in a solvent having a high degree of versatility such as other terpene, and used as a cosolvent. In this way, the azoxanthene oligomer of the present invention having high solubility and high solubility in various organic solvents does not have a polymer structure such as the conventional polyazo-xanthine, and transports carriers such as electrons and holes. High performance for semiconductor applications. The azoxanthene oligomer of the present invention has a high carrier transport function for the following reasons. That is, the azochuanchuan oligomers are superimposed on each other with the same affinity (i.e., the hydrocarbon group is a hydrocarbon group similar to each other, and the conjugate group containing an aromatic ring is a conjugate group containing an aromatic ring, and the like). Therefore, at the stack of conjugated groups containing an aromatic ring, the carrier is free to move. That is, in the case of the conventional polyazo hydrazine system to ensure carrier mobility according to a specific structure within the molecule, the present invention is based on the inter-molecular stacking to ensure the mobility of the carrier. As described above, the azoxanthene oligomer of the present invention has a high carrier 39 322866 201141818 transport function, is suitable for semi-conducting, and exhibits high affinity for a wide range of organic solvents. Lai, the azo azo oligomer solution obtained by dissolving the chuan oligomer in a highly versatile organic solvent, and the coating method by spin coating or dipping coating can be safely and easily A semiconductor layer is formed on the substrate. A solution of the azomethine oligomer of the present invention having such a carrier transport function is coated on an electrode to carry out dissection, whereby a p_n junction forest can be produced. When the azomethine oligomer is used as a P-type semiconductor layer forming material, the N-type semiconductor layer is made of a semiconductor using an electron affinity (eV) which exhibits a larger ionization potential (eV) value than the azokawa oligo. A material such as Fullerene is formed. Further, when the azomethine filament material is formed into a semiconductor layer (4), the P-type semiconductor layer exhibits an ionization potential semiconductor material having a smaller electron affinity (eV) value than the azo gas methacrylate oligomer (for example). : Poly(3-hexyl porphin)). More specifically, when the azokawachuan polymer of the present invention is used as a material for forming an N-type semiconductor layer, azobismuthene (tetra) (iv) is applied onto a negative electrode substrate and dried to form a film. The film is formed by coating or vapor-depositing a P-type semiconductor material or the like on the film, and is obtained? The type semiconductor can be made to form a P-n junction element by vaporizing the electrode on the positive side. X, the azo f) ruthenium ruthenium of the present invention is used as a material for forming a p-type conductor layer, and the N-type semiconductor material is formed on the negative-side electrode substrate by coating or evaporation, and the film is formed thereon. The 贱甲川丝秘液 is applied and dried to form a P-type semiconductor layer, and a pn junction element can be produced by evaporating a positive electrode on the upper "type semiconductor layer. The p-type and N-type semiconductor material bonded body 40 is formed. 322866 201141818, the pn made by this operation

層之厚度通常為10至900nm。例如 接合元_ 電池、 域。 >上古^ Λ述離子化電位及電子親和力各別以H0M0(最 局占有軌道）及L_最低非占有執道）可由實驗求得。 H_可根據日本專利第11247()3號公報記栽之光電子 分光法，使用理研計器公司製造之AC 2求得。 -求得電化學之氧化電位’換算為麵〇之方法具體而言 例示求得試料之氧化起始電位換算之方法。 氧化起始電位為在對於目的試料進行循環伏安法 (^clic V〇ltammetry)(cv)之測定獲得之測定結果中，求 =從基線至氧化電流開始流動時之電位。必要時進行從測 疋中使用之參考電極換算為標準氫電極基準，另經由在 該值加入對於真空準位之標準氫電極之值（常 5 得 HOMO(eV)。 . 求 ^接著，求得LUM0之方法列舉求得電化學還原準位，換 异為LUM0之方法及從試料之紫外線_可見光吸收圖譜之吸 收起始波長及上述求得之Η〇Μ〇值換算為LUM〇<方法。 _經由電化學測定求得LUM0時，與上述求得HOMO時相 同，以CV進行測定試料之還原電位，同樣地經由換算，求 得 LUM0 。 / 從吸收起始波長求得LUM0時，將試料在玻璃基板上經 由疑轉塗覆使成為約數十奈米厚度，進行製膜，對於形成 41 322866 201141818 之膜進行紫外線-可見光吸收圖譜之測定，於獲得之測定結 果中，作為從基線開始吸收時之波長λ (加〇 ’可求得n及收 起始波長。將該值換算為電子伏特（eV) ’獲得之值作為能 隙能量（匕811(1旦3?61^『忌7)(6¥)。另，將由如上述操作求得 之HOMO(eV)除以該能隙能量（ey)，可求得LUM0。 關於偶氮甲川寡聚物半導體特性之調整，可參照通常 共軛系聚合物之見解，用與一般調整法相同之方法可調整 上述半導體特性。 本發明偶氮甲川寡聚物之p型半導體特性，可經由調 整分子之離子化電位而提昇。例如經由以下之2個方法，° 可將分子之離子化電位變大。 ⑴作為共軛系(含有芳族環之共軛基)，選擇電子豐富之 萘、蒽等縮環系單位The thickness of the layer is usually from 10 to 900 nm. For example, the junction element _ battery, domain. >The ancients ^ The ionization potential and electron affinity are determined by experiments. H0M0 (most occupied orbit) and L_ minimum non-occupational behavior can be obtained experimentally. H_ can be obtained by using the photoelectron spectroscopy method described in Japanese Patent No. 11247() No. 3, using AC 2 manufactured by Riken Keiki Co., Ltd. - A method of converting the oxidation potential of the electrochemical portion into a surface enthalpy is specifically exemplified by a method for calculating the oxidation initiation potential of the sample. The oxidation initiation potential is a measurement result obtained by measurement of cyclic voltammetry (cv) for the intended sample, and the potential at which the flow starts from the baseline to the oxidation current. If necessary, the reference electrode used in the measurement is converted to the standard hydrogen electrode reference, and the value of the standard hydrogen electrode for the vacuum level is added at this value (of course, HOMO(eV) is obtained. The method of LUM0 exemplifies the method of obtaining the electrochemical reduction level, changing the difference to LUM0, and converting the initial wavelength of absorption from the ultraviolet-visible absorption spectrum of the sample and the above-mentioned calculated enthalpy value into a LUM〇< method. When LUM0 is obtained by electrochemical measurement, the reduction potential of the sample is measured by CV in the same manner as in the case of obtaining HOMO described above, and LUM0 is obtained by conversion in the same manner. / When LUM0 is obtained from the absorption start wavelength, the sample is obtained. On the glass substrate, the film was formed to have a thickness of about several tens of nanometers by suspected transfer coating, and the film formed of 41 322866 201141818 was subjected to measurement of the ultraviolet-visible absorption spectrum, and the obtained measurement result was taken as absorption from the baseline. The wavelength λ (added 〇 ' can be obtained by n and the starting wavelength. The value is converted into electron volts (eV) 'the value obtained as the energy gap energy (匕 811 (1 den 3? 61 ^ "tab 7") 6¥). Also, will The HOMO (eV) obtained by the above operation is divided by the energy gap energy (ey) to obtain LUM0. Regarding the adjustment of the characteristics of the azomethine oligomer semiconductor, reference can be made to the knowledge of the usual conjugated polymer. The semiconductor characteristics can be adjusted by the same method as the general adjustment method. The p-type semiconductor characteristics of the azomethine oligomer of the present invention can be improved by adjusting the ionization potential of the molecule. For example, by the following two methods, the molecule can be The ionization potential becomes large. (1) As a conjugated system (a conjugated group containing an aromatic ring), a condensed ring system such as an electron-rich naphthalene or an anthracene is selected.

選擇具有電子不足 使共輛系内之電子密度變低，將電 代基導入共軛系申， 將電子定域化。 從具有如上所沭儡舳—+ bThe electron density in the common vehicle system is selected to be low, and the electron group is introduced into the conjugate system to localize the electron. From having the above 沭儡舳—+ b

體特性之本發明偶氮甲川 將該偶氮甲川寡聚物使用 322866 42 201141818 作為p型半導體層或n型半導 n ^ 亍等媸層之形成材料而製作之 p-n接合70件，在P型半導The azo hydride of the present invention is a pn-bonded 70 piece of azo-bonded azo-method oligo used as a material for forming a p-type semiconductor layer or an n-type semiconducting n ^ 亍 layer, such as a p-type Semi-guide

型半導體狀魏連極錢正料子，在N 員才為子，在-5V至+5V之範圍内施 加電=使順方向之電力量/逆方向之電子量〉1〇。 例如Γ=本發明之偶氣曱川寡聚物，可使用作為 上ϋ·，:厂體。又’上述ρ型半導體層與電極之間、 與電極之間，各可以另外之方法設置電 洞注入層、電子注入層。 本發月偶氮甲川寡聚物之分子量，從溶劑溶解性及分 子内結晶性並存之觀點而言’較好在15〇至15_之範圍 :mi500至10000之範圍内。分子量之調整方法於 明錢”丨丨絲物之製造方法之項目中說明。 (偶氬甲川养聚物之具體例） 作為以上說明之本發明偶氮甲川寡聚物 舉以下通式（I)表示之化合物。 R1- (i) •A—-Ar——a——r2 氮次=:=具:取代基之二價芳族基或偶 之含有芳基交互結合進行共軛 μ 5 聽上述二鮮職之例列舉上述式 又，於24表不之基’更具體之例列舉下述式表示之基。 下述式，半括弧括上之部位為鍵結。 43 322866The type of semiconductor-like Weilian is the material of the material. In the case of the N member, the power is applied in the range of -5V to +5V. The amount of electricity in the forward direction/the amount of electrons in the opposite direction is >1〇. For example, Γ = the argon gas of the present invention, which can be used as a sputum. Further, a hole injection layer or an electron injection layer may be separately provided between the p-type semiconductor layer and the electrode and between the electrodes. The molecular weight of the azomethine oligomer of the present invention is preferably in the range of 15 Å to 15 Å from the viewpoint of solvent solubility and crystallinity in the molecule: mi 500 to 10,000. The method for adjusting the molecular weight is described in the item of the method for producing the squid. The specific example of the argon-methine oligomer is the following formula (I). The compound represented by R1-(i) •A—Ar—a—r2 nitrogen====: The divalent aromatic group of the substituent or the aryl group containing the aryl group is conjugated μ 5 The example of the second job is listed in the above formula, and the base of the formula is shown in the following table. More specifically, the following formula is used. The following formula, the portion of the semi-bracket is a bond. 43 322866

S 201141818S 201141818

ΟΜβ /=(ΟΜβ /=(

-CH> ^ W ♦ 你办ih冰Sk-CH> ^ W ♦ You do ih ice Sk

44 322866 201141818 該等中’從本發明偶氮曱川寡聚物於固體狀態分子間 尚結晶性之觀點而言，較好為以下例示之二價芳族基。44 322866 201141818 These are preferably the divalent aromatic groups exemplified below from the viewpoint of the crystallinity of the azochuanchuan oligomer of the present invention in a solid state.

於上述式（I)，A為偶氮次曱基（c=N或N=C)，將作為 製造本發明偶氮甲川寡聚物之原料基質使用之後述烴化合 45 322866 201141818 物及含有芳族環之化合物，根據選擇作成二胺體及二醛體 中的任何—種，其方向不同。又，於通式（I)中之Ar_A , 二個偶氮次甲基不隣接。 於式（I) ’ 及R2獨立為可具有支鏈、可經函素原子 取代之碳數2至512之烷基，可具有支鏈、可經齒素原子 取代之碳數2至512之烧氧基，基中具有騎合及/或_ 結合、可經齒素原子取代之碳數2至512之烴基或可具有 取代基之碳數3至50之環烷基。1^及y較好列舉與在上 述〈烴基&gt;之說明較佳烴基列舉為相同之基。 、 以上說明之本發明偶氮甲川寡聚物，由於在分子間令 有芳族環之共減堆疊處，載體可自由移動，所以適用衣 半導體用途。又，由於對於甲苯等疏水性溶劑，甲醇、乙 醇等醇系溶劑，丙二醇一曱_二醇系溶劑或乳酸甲㈣ 醋系溶劑等廣祕高之有機溶劑具有高溶解性，因此，伯 用f本發明之贱曱川絲物轉於上述有機溶劑獲得之 偶亂曱川絲物溶液，經由塗佈法可容易地在基板上形 半導體層。 接著’對於本發明偶氮甲川絲物的製造方法加以說 明。 [本發明偶氮曱川寡聚物之製造方法] 本發明偶氮曱川寡聚物之製造方法具有對於下述通式 (⑴表示之含有芳族環之化合物1當量，將下述通式（m) 表示之烴化合物2當量進行反應之步驟。 322866 46 201141818 X—Ar1—(A-Ar2)p~~X (Π) /r1 r2 \ Y—(Z)丨一(CH)j—(0)q—R3 (ΠΙ) 於式（ii)，二個x同時為醛基或胺基’於式（m) ’式 (II)之X為醛基時γ為胺基，X為胺基時Y為醛基。 亦即，經由利用醛基與胺基的反應，對於含有芳族環 之化合物1分子，將烴化合物2分子進行反應，獲得本發 明之偶氮甲川寡聚物。 &lt;通式（II)表示之含有芳族環之化合物&gt; 於上述式（II)，二個X如前述，同時為醛基或胺基。In the above formula (I), A is an azo sulfhydryl group (c=N or N=C), which is used as a raw material substrate for producing the azomethine oligomer of the present invention, and is described later as a hydrocarbon compound 45 322866 201141818 and contains aromatic The compound of the family ring is selected to be any of the diamine and the dialdehyde, and the direction thereof is different. Further, in Ar_A in the formula (I), the two azomethine groups are not adjacent. The formula (I) ' and R2 are independently an alkyl group having 2 to 512 carbon atoms which may be substituted by a functional atom, and may have a branched chain and a carbon number of 2 to 512 which may be substituted by a fang atom. An oxy group having a hydrocarbon group of 2 to 512 carbon atoms or a cycloalkyl group having 3 to 50 carbon atoms which may have a substituent, which may be substituted by a cyclin atom. 1 and y are preferably listed in the same manner as the preferred hydrocarbon group described in the above <hydrocarbon group>. The azomethine oligomer of the present invention described above is suitable for clothing semiconductor applications because the carrier can be freely moved at the co-depositing stack of aromatic rings between molecules. In addition, in the case of a hydrophobic solvent such as toluene, an alcohol solvent such as methanol or ethanol, or a high-viscosity organic solvent such as a propylene glycol mono-diol solvent or a lactic acid methyl ketone solvent has high solubility. The 贱曱川丝物 of the present invention is transferred to the above-mentioned organic solvent, and the semiconductor layer can be easily formed on the substrate via a coating method. Next, a method for producing the azomethine filament of the present invention will be described. [Manufacturing Method of Azo-Xinchuan Oligomer of the Present Invention] The method for producing an azochuanchuan oligomer of the present invention has a formula of the following formula (1), which contains an aromatic ring-containing compound, and has the following formula. (m) shows the step of reacting 2 equivalents of the hydrocarbon compound. 322866 46 201141818 X—Ar1—(A-Ar2)p~~X (Π) /r1 r2 \ Y—(Z)丨一(CH)j—( 0) q—R3 (ΠΙ) In formula (ii), two x are both aldehyde or amine 'in formula (m) 'Formula (II) where X is an aldehyde group, γ is an amine group, and X is an amine group. When Y is an aldehyde group, that is, by reacting an aldehyde group with an amine group, a molecule of the hydrocarbon compound 2 is reacted with respect to a molecule of the compound containing an aromatic ring to obtain the azomethine oligomer of the present invention. The compound containing an aromatic ring represented by the formula (II) &gt; In the above formula (II), the two Xs are as described above, and are an aldehyde group or an amine group.

Ar1為可具有取代基之二價芳族基，其具體例列舉上述式 A-1至A-24表示之基。 於上述式（II)，Ar2為可具有取代基之二價芳族基，其 具體例與Ar1之具體例相同。 於式（II)，A為偶氮次曱基，如後述地經由選擇作為 製造含有芳族環之化合物之原料基質使用之化合物，其方 向不同。 於式（II)，p為0至5之整數，從本發明偶氮甲川寡 聚物共輛系之擴張及對於溶劑之溶解性並存之觀點而言， 較好為1至3之整數。又，n9 lv μ 口太μ. . 9 入Ρ马2以上時，稷數存在之紅2 可相同亦可不同β 322866 47 201141818 (取得通式（i i)表示之含有芳族環之化合物之方法） 於通式（II)，p為0之含有芳族環之化合物市場上有 販賣，可容易取得。 p為1以上時之含有芳族環之化經由將市售之化合物 進行反應，可容易取得。 於通式（II)，Ar1及Ar2均為伸苯基，以X為胺基之場 合為例，則例如經由以下之反應，獲得p為1之含有芳族 環之化合物。Ar1 is a divalent aromatic group which may have a substituent, and specific examples thereof include the groups represented by the above formulas A-1 to A-24. In the above formula (II), Ar2 is a divalent aromatic group which may have a substituent, and specific examples thereof are the same as those of the specific example of Ar1. In the formula (II), A is an azo sulfhydryl group, and the compounds used as a raw material substrate for producing a compound containing an aromatic ring are selected as described later, and the directions thereof are different. In the formula (II), p is an integer of from 0 to 5, and is preferably an integer of from 1 to 3 from the viewpoint of the expansion of the azomethine oligomer system of the present invention and the solubility of the solvent. Further, the n9 lv μ port is too μ. . 9 when the hummer is 2 or more, the red number 2 of the number of turns may be the same or different β 322866 47 201141818 (Method for obtaining a compound containing an aromatic ring represented by the general formula (ii) In the formula (II), a compound containing an aromatic ring having a p of 0 is commercially available and can be easily obtained. When the p is 1 or more, the aromatic ring-containing compound can be easily obtained by reacting a commercially available compound. In the general formula (II), Ar1 and Ar2 are each a phenyl group, and in the case where X is an amine group, for example, a compound having an aromatic ring having a p of 1 can be obtained by the following reaction.

詳細之該等對-胺基苯甲醛1分子與1，4-二胺基苯1 分子進行反應，獲得通式（II)之含有芳族環之化合物之反 應之反應條件，表示於實施例之&lt;原料1之合成 &gt;之項目。 又，p為2之含有芳族環之化合物可經由將上述反應 重複進行（在上述反應獲得之偶氮甲川化合物中將對-胺基 苯曱醛進行反應）獲得，又，如以下之操作，可以一個階段 之反應獲得。 48 322866 201141818Specifically, the reaction conditions of the reaction of the p-aminobenzaldehyde 1 molecule with the 1,4-diaminobenzene 1 molecule to obtain the aromatic ring-containing compound of the formula (II) are shown in the examples. &lt;Synthesis of Raw Material 1&gt; Further, the compound containing an aromatic ring having p of 2 can be obtained by repeating the above reaction (reacting p-aminobenzaldehyde in the azomethine compound obtained by the above reaction), and further, as follows. It can be obtained in one stage of reaction. 48 322866 201141818

OHCOHC

CHO + H2NCHO + H2N

NH2 + 詳細之該等u—工胺基笨i分子與 行反應’獲得通式（⑴表示之含有芳姨環 之反應條件表示於實施例之&lt;原料2 〇心 之化應，可獲得…=環 由於胺基與醛基之反應性高，上 分接觸混合等，可容㈣行。《反應經㈣原料成 二=可=將胺編基進行反應之公知慣用的 汉應保件實施。通常，反應溫度為 通常為2至48小時。 。至断，反應時間 反可使用乙酸乙醋或乙酸丁物系溶劑，甲 本成一甲本專芳族性溶劑，，或環戊基曱 劑’ MEK或環戊酮等酮系溶劑，間、土二— 性芳族溶劑（較好於賴媒化反應3本料質子' f甲p ^ 节件中使用），氣仿… 氣甲说、四^誠氯苯等含㈣素原子之溶劑，撕、 、対或W等質子接受性_(較好.於賴媒化反應 條件中使用）及乙腈或苯曱腈等腈系溶劑。 如以上之說明，作為本發明偶氮曱川寡聚物製造原科 49 201141818 之含有芳族狀化合物市場上有㈣，或將㈣品進行反 應，可容易取得。 (含有芳族環之化合物之具體例） 以上說明之含有芳族環之化合物之具體例列舉下述 式表示之化合物。NH2 + in detail the u------------------------------ = ring due to the high reactivity of the amine group and the aldehyde group, the upper part of the contact mixture, etc., can be accommodated in (4). The reaction is carried out by (4) the raw material into two = can be used to carry out the reaction of the amine-based group. Usually, the reaction temperature is usually from 2 to 48 hours. To the time of the reaction, the reaction time can be reversed using ethyl acetate or butyl acetate solvent, and the present invention is a mono-specific aromatic solvent, or a cyclopentyl tanning agent. a ketone solvent such as MEK or cyclopentanone, a medium-sex-aromatic aromatic solvent (preferably used in the catalyzed reaction 3 protons of the material 'f-p^), gas imitation... a solvent containing a (tetra) atom such as chlorobenzene, a proton accepting property such as tearing, ruthenium or ruthenium (preferably used in the reaction conditions) and a nitrile solvent such as acetonitrile or benzoquinone. Illustratively, the aromatic compound containing the azoazokawa oligomer of the present invention is manufactured on the market 49 201141818. , Or (iv) for the reaction product can be easily achieved. (Specific examples of the compound containing the aromatic rings) of the above-described specific examples of the compound containing aromatic rings include a compound represented by the following formula.

50 322866 20114181850 322866 201141818

x χx χ

NN

C$Hl3C$Hl3

X 51 322866 201141818X 51 322866 201141818

52 322866 20114181852 322866 201141818

於上述式，x為醛基或胺基。 &lt;通式（M)表示之煙化合物&gt; 再度表示通式（瓜）。 / R1 R2 \ Y—(Ar-Ater^(CH)h—(Z)j—(CH)七(〇&gt;q—R3 (ΠΙ) 於上述式，Y如前所述，於式（II)，X為醛基時Y為胺 基，X為胺基時Υ為醛基。 於式（m)，Ar為可具有取代基之二價芳族基，其具體 例列舉上述式A-1至A-24表示之基。 於上述式（III) ’ A為偶氮次曱基，如後述，經由選擇 作為製造烴化合物之原料基質使用之化合物，其方向不同。 於式（III)，m為0或1，m為1時，Y-Ar-A表示之部 53 322866 201141818 分σ與含㈣族環之化合物騎反應，成為偶氮次甲 成為構成本發明偶氮甲川絲物巾含有芳麵之 一都公。 、土·&lt;» 於式（III)，R1及R2獨立為氫原子 ▼ 一μ&quot;,、, π双i主之起 基或函素原子H R2從對於有機溶劑之溶解性及成則 膜之結晶性之觀點而言细錢原子及碳數⑴ 於式（πυ，ζ為具有氧原子、硫原子或伸環烧基之土一 h基’從原料在商業上比較容易取得之點而言，較好為氧 於式（III)，i為0或卜時，煙化 有㈣合（氧原子）、硫_合（硫原子）或伸環烧基 於式（ΠΙ)，h及j獨立為G至12之整數，較好為i 整數。惟，z魏原子或硫原子時，W同時為 於式（Iii)，k為1至1Q之整數，較好為丨至5之整數。 又’於式(III)，h為2以上時，複數存在之RI可相同 亦可不同’j為2以上時，複數存在之r2可相同亦可不同， 於式（III)，k為2以上時，複數存在之 (-(CHR X-Uy-CCHR2)〗-)可相同亦可不同。 於式（ni)，u〇或，通式（1⑴表示之 化合物成為具纽氧基。從本發明之偶氮甲川S聚物對於 通用之有機溶劑賦予親和性之觀點而t，q較好為b、 於式（in)，R3為碳數1至2〇之烧基，較好為碳數】 至15之烧基。 322866 54 201141818 另，（-(CHR'-Uy-aHRW-COX-R3表示之構造中之 碳數為2至512，較好為4至256。 (取得通式（111)表示之烴化合物之方法） 於通式（ΙΠ)，m為0之烴化合物市場上有販賣，可容 易取得。 m為1時之烴化合物經由將市售之化合物進行反應， 可容易取得。 於通式（III)，以Ar為伸苯基、m為1、 (-(CHiOh-Uh-aHR2)〗-：^為伸庚基、q為0、R3為甲基時 為例，經由例如以下之反應，獲得m為1之含有芳族環之 化合物。In the above formula, x is an aldehyde group or an amine group. &lt;Smoke compound represented by the formula (M)&gt; Again, the formula (melon) is represented. / R1 R2 \ Y—(Ar-Ater^(CH)h—(Z)j—(CH)7(〇&gt;q—R3 (ΠΙ) is in the above formula, Y is as described above, in formula (II) When X is an aldehyde group, Y is an amine group, and when X is an amine group, hydrazine is an aldehyde group. In the formula (m), Ar is a divalent aromatic group which may have a substituent, and specific examples thereof include the above formula A-1 to The group represented by A-24. The above formula (III) 'A is an azo sulfhydryl group, and as described later, the direction is different by selecting a compound used as a raw material substrate for producing a hydrocarbon compound. In the formula (III), m is 0 or 1, when m is 1, Y-Ar-A represents the part 53 322866 201141818 points σ reacts with the compound containing the (qua) ring, and becomes azo methine to form the azomethine silk towel of the present invention containing the fragrant surface. One is public. ·土·&lt;» In formula (III), R1 and R2 are independently hydrogen atoms ▼ a μ&quot;,, π double i main radical or a functional atom H R2 from the dissolution of organic solvents From the viewpoint of the crystallinity of the film and the film, the atomic atom and the carbon number (1) are in the formula (πυ, ζ is an earth having an oxygen atom, a sulfur atom or a ring-forming group. In terms of the point of achievement, it is better In the formula (III), when i is 0 or Bu, the fuming has a (tetra) (oxygen atom), a sulfur-sulfur (sulfur atom) or an exocyclic ring based on the formula (ΠΙ), and h and j are independently an integer of G to 12. Preferably, it is an integer of i. However, when z is a Wei atom or a sulfur atom, W is at the same formula (Iii), and k is an integer from 1 to 1Q, preferably from 丨 to an integer of 5. Further 'in formula (III) When h is 2 or more, the RIs in the plural may be the same or different. When 'j is 2 or more, the r2 in the plural may be the same or different. When the formula (III) and k are 2 or more, the plural exists (- (CHR X-Uy-CCHR2)--) may be the same or different. In the formula (ni), u〇 or the compound represented by the formula (1(1) becomes a neooxy group. From the azomethine S polymer of the present invention From the viewpoint of imparting affinity to a general organic solvent, t, q is preferably b, in the formula (in), and R3 is a calcining group having 1 to 2 carbon atoms, preferably a carbon number to 15 alkyl group. 54 201141818 Further, (-(CHR'-Uy-aHRW-COX-R3 represents a carbon number in the structure of 2 to 512, preferably 4 to 256. (Method of obtaining a hydrocarbon compound represented by the general formula (111)) a hydrocarbon compound of the formula (ΙΠ), m is 0 It is sold on the market and can be easily obtained. The hydrocarbon compound having a m of 1 can be easily obtained by reacting a commercially available compound. In the formula (III), Ar is a phenyl group and m is 1, (-( CHiOh-Uh-aHR2)--: ^ is a heptyl group, q is 0, and R3 is a methyl group. For example, a compound containing an aromatic ring having m of 1 is obtained by the following reaction.

詳細之該等辛醛1分子與1,4-二胺基苯進行反應，獲 得通式（III)表示之烴化合物之反應之反應條件，表示於實 施例&lt;原料9之合成&gt;之項目。 以上之反應獲得具有Y為胺基之烴化合物，惟，若將 使用之反應原料變更為1，4-二曱醯基苯及1-胺基辛烷，獲 得具有Y為醛基，偶氮次曱基之方向為相反之烴化合物。 55 322866 201141818 由於胺基與路基之反應性高，上述反應可容易進行。 該4反應可根據將胺基與路基進行反應之公知慣用的 反應條件實施。通常，反應溫度為3〇至12〇艽，反應時間 通常為2至48小時。 、反應/谷劑可使用乙酸乙酯或乙酸丁酯等酯系溶劑，甲 苯或二甲苯等芳族性溶劑，碰或環戊基甲㈣等峻系溶 劑1MEK^環戊酮等酮系溶劑，間m笨料質子供予 性方族溶劑（較好於酸觸媒化反應條件中使用），氣仿Γ二 ^曱烷四氣乙烧或氯苯等含有έ素原子之溶劑，騰、 如以上之說明， 條二::::r苯=:=於_媒化反應 料之烴化合物， 易取得。 明，作為本發明偶氮次曱基寡聚物製造原 市場上有販售或將市售品進行反應，可容Specifically, the reaction conditions of the reaction of the hydrocarbon compound represented by the general formula (III) by reacting one molecule of the octanal with the 1,4-diaminobenzene are shown in the item &lt;Synthesis of the raw material 9&gt; . The above reaction obtains a hydrocarbon compound having Y as an amine group. However, if the reaction raw material to be used is changed to 1,4-dimercaptobenzene and 1-aminooctane, an aldehyde group having Y is obtained, and an azo group is obtained. The direction of the thiol group is the opposite hydrocarbon compound. 55 322866 201141818 The above reaction can be easily carried out due to the high reactivity of the amine group with the road base. The 4 reaction can be carried out according to well-known and customary reaction conditions for reacting an amine group with a road base. Usually, the reaction temperature is from 3 Torr to 12 Torr, and the reaction time is usually from 2 to 48 hours. For the reaction/treat, an ester solvent such as ethyl acetate or butyl acetate, an aromatic solvent such as toluene or xylene, or a ketone solvent such as 1MEK^cyclopentanone such as cyclopentylmethyl (tetra) may be used. a m-proton-proton-following solvent (preferably used in acid-catalyzed reaction conditions), a gas-like oxime, a gas, or a chlorobenzene-containing solvent containing a halogen atom, The above description, Article 2::::r benzene =: = hydrocarbon compound in the _communication reaction material, easy to obtain. As a manufacturer of the azo sulfhydryl oligomer of the present invention, it is commercially available or can be reacted in a commercial product.

322866 56 201141818322866 56 201141818

於上述式，Y為胺基或醛基，t為5至11之整數。 &lt;反應&gt; 於本發明偶氮甲川寡聚物之製造方法，對於上述通式 (π)表示之含有芳族環之化合物1當量，將上述通式（m) 表示之烴化合物2當量進行反應。經由適當選擇（調節）含 有芳族環之化合物及烴化合物之分子量，可調節獲得之本 發明偶氮曱川寡聚物之分子量。 於該反應，含有芳族環之化合物具有之2個胺基或醛 57 322866 201141818 基與烴化合物具有之酸基或胺基進行反應’形成偶氮次甲 基，偶氮次甲基與二價芳族基交互結合’形成共軛之構造 (含有芳族環之共輛基）。由於烴化合物除了參予與含有芳 族環之化合物之反應之醛基或胺基以外，沒有與醛基或胺 基具有反應性之部位’所以上述反應之後不會引起與含有 芳族環化合物或烴化合物之反應’不會獲得聚偶氮曱川， 而是獲得偶氮甲川寡聚物。 上述反應之反應溫度通常為30至120°C ’從反應效率 之觀點而言，較好為60至l〇〇°c。 上述反應之反應時間通常為2至48小時，從反應效率 之觀點而言，較好為6至24小時。 於上述反應，可使用間-曱酚、二甲基苯酚、苯酚、樟 腦磺酸、萘酚、甲酸、乙酸、丙酸、鹽酸及硫酸之一般酸觸 媒化之加成反應中使用之觸媒。又，與一般驗觸媒化之加成 反應使用之相同之鹼’亦可作為在上述反應之觸媒使用。 另’上述反應之反應溶劑可使用乙酸乙酯或乙酸丁酯 等酯系溶劑，曱苯或二曱苯等芳族性溶劑，THF或環戊基 曱基醚等醚系溶劑，MEK或環戊酮等酮系溶劑，間-曱酚或 苯酚等質子供予性芳族溶劑（較好於酸觸媒化反應條件中 使用），氯仿、二氣曱烷、四氯乙烷或氯苯等含有鹵素原子 之溶劑’ NMP、DMF、吡啶或哌啶等質子接受性溶劑（較好於 鹼觸媒化反應條件中使用）及乙腈或苯曱腈等腈系溶劑。該 等中’從反應效率之觀點而言，較好為間-曱酚、甲苯_間_ 曱盼共溶劑、THF、環戊基曱基_及環戊酮。 58 322866 201141818 由於與醛基及胺基之反應性高，上述反應容易進行。 所以，本發明之偶氮甲川寡聚物從容易取得之原料可容易 地製造。又，上述偶氮甲川寡聚物沒有非專利文獻5所記 載的具有在主鏈中之芳環、雜環或芳環及雜環中導入烷基 或烷氧基等之聚偶氮甲川之原料單體在商業上不能取得， 在工業化有困難的問題點。 [實施例] ， &lt;原料1之合成&gt;In the above formula, Y is an amino group or an aldehyde group, and t is an integer of 5 to 11. &lt;Reaction&gt; In the method for producing an azomethine oligomer of the present invention, one equivalent of the hydrocarbon compound represented by the above formula (m) is obtained for one equivalent of the compound containing an aromatic ring represented by the above formula (π). reaction. The molecular weight of the obtained azochuanchuan oligomer of the present invention can be adjusted by appropriately selecting (adjusting) the molecular weight of the compound containing an aromatic ring and the hydrocarbon compound. In the reaction, the compound containing an aromatic ring has two amine groups or aldehydes. 57 322866 201141818 The group reacts with an acid group or an amine group of a hydrocarbon compound to form an azo methine group, an azo methine group and a divalent group. The aromatic groups interact in combination to form a conjugated structure (a common vehicle containing an aromatic ring). Since the hydrocarbon compound has no site reactive with an aldehyde group or an amine group other than the aldehyde group or the amine group which reacts with the compound containing an aromatic ring, the above reaction does not cause an aromatic ring-containing compound or The reaction of the hydrocarbon compound 'does not obtain polyazochuan, but obtains an azomethine oligomer. The reaction temperature of the above reaction is usually from 30 to 120 ° C. From the viewpoint of the reaction efficiency, it is preferably from 60 to 10 ° C. The reaction time of the above reaction is usually from 2 to 48 hours, and from the viewpoint of reaction efficiency, it is preferably from 6 to 24 hours. In the above reaction, a catalyst used in an addition reaction of a general acid-catalyzed reaction of m-nonylphenol, dimethylphenol, phenol, camphorsulfonic acid, naphthol, formic acid, acetic acid, propionic acid, hydrochloric acid, and sulfuric acid can be used. . Further, the same base used in the addition reaction of the general catalytic reaction can also be used as a catalyst for the above reaction. Further, the reaction solvent for the above reaction may be an ester solvent such as ethyl acetate or butyl acetate, an aromatic solvent such as toluene or diphenylbenzene, an ether solvent such as THF or cyclopentyl decyl ether, MEK or cyclopentane. a ketone solvent such as a ketone, a protic aromatic solvent such as m-nonylphenol or phenol (preferably used in an acid-catalyzed reaction condition), or a chloroform, dioxane, tetrachloroethane or chlorobenzene. A solvent for a halogen atom, a proton-receiving solvent such as NMP, DMF, pyridine or piperidine (preferably used in alkali-catalyzed reaction conditions) and a nitrile-based solvent such as acetonitrile or benzoquinone. From the viewpoint of reaction efficiency, it is preferably m-nonylphenol, toluene-m-co-solvent, THF, cyclopentyl fluorenyl and cyclopentanone. 58 322866 201141818 The above reaction is easy to proceed due to high reactivity with an aldehyde group and an amine group. Therefore, the azomethine oligomer of the present invention can be easily produced from a readily available raw material. In addition, the azomethine oligomer does not have a raw material of polyazomethine having an alkyl group, an alkoxy group or the like introduced into an aromatic ring, a heterocyclic ring, an aromatic ring or a heterocyclic ring in the main chain described in Non-Patent Document 5. Monomers are not commercially available, and problems in industrialization are difficult. [Examples], &lt;Synthesis of Raw Material 1&gt;

在經氮置換之l〇〇mL休連克管（Schlenk tube)中投入 1，4-伸苯基二胺（ι，4-二胺基苯）2. 70g(25. Ommol)、間-曱 酚5g、曱苯30g ’邊攪拌邊將反應溶液加熱至7(rc。之後 以3小時在上述溶液中滴下將對-胺基苯甲醛121g (10. Ommol)溶解於甲苯3〇g之溶液。之後進行攪拌3小時 完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烧、乙醇洗淨。經由此獲得淡黃色由之 通式（II)表示之含有芳族環之化合物167g(收率：79〇心 FAB-MS : m/z=212[M+H]+。 ° &lt;原料2之合成&gt;The 1,4-phenylenediamine (i,4-diaminobenzene) was added to a nitrogen-substituted l〇〇mL Schlenk tube. 2.70 g (25. Ommol), m- 曱The reaction solution was heated to 7 (rc) with stirring of 5 g of phenol and 30 g of toluene. Then, a solution of p-aminobenzaldehyde 121 g (10. Ommol) dissolved in 3 g of toluene was added dropwise to the above solution over 3 hours. After that, the reaction was completed by stirring for 3 hours. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum dried, washed with hexane and ethanol, whereby a yellowish color represented by the formula (II) was obtained. 167 g of compound of aromatic ring (yield: 79 〇 heart FAB-MS: m/z = 212 [M+H] + ° ° &lt;Synthesis of Starting Material 2 &gt;

在經氮置換之l〇〇mL休連克管中投入對笨二甲醛 322866 59 201141818 (1’4-二曱醢基苯）3.35g(25.0mmol)、間-曱盼5g、曱笨 3〇g ’邊攪拌邊將反應溶液加熱至7〇°c。之後以3小時在 上述溶液中滴下將1,4-伸苯基二胺LOSgdQ.oonHnoU溶 解於曱苯3〇g之溶液。之後進行攪拌3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙醇、乙腈洗淨。經由此獲得淡黃 色固體之通式（II)表示之含有芳族環之化合物2. 67g(收 率：79%)。FAB-MS : m/z=341[M+H]+。 〈原料3之合成&gt;In the nitrogen-substituted l〇〇mL Hughen tube, the p-dialdehyde 322866 59 201141818 (1'4-dimercaptobenzene) 3.35g (25.0mmol), the inter-presence 5g, the stupid 3〇 The mixture was heated to 7 ° C with stirring. Thereafter, a solution of 1,4-phenylenediamine LOSgdQ.oonHnoU dissolved in toluene 3 〇g was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 3 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane, ethanol and acetonitrile. The compound containing an aromatic ring represented by the formula (II) thus obtained as a pale yellow solid was 2.67 g (yield: 79%). FAB-MS: m/z = 341 [M+H]+. <Synthesis of Raw Material 3>

F F 在經氮置換之l〇〇mL休連克管中投入對苯二甲醛 3· 35g(25. Oramol)、間-曱酚5g、曱苯3〇g，邊攪拌邊將反 應溶液加熱至7(TC。之後以3小時在上述溶液中滴下將 2, 3, 5, 6-四氟-1，4-伸苯基二胺 1.8〇g(l〇. Ommol)溶解於 甲苯30g之溶液。之後進行攪拌3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙醇、乙腈洗淨。經由此獲得淡黃 色固體之通式（II)表示之含有芳族環之化合物2. 43g(收 率：59%)。FAB-MS : m/z = 413[M+H]+。 &lt;原料4之合成&gt; 60 322866 201141818FF Into a nitrogen-substituted l〇〇mL wicking tube, put phthalaldehyde 3·35g (25. Oramol), m-nonyl phenol 5g, fluorene benzene 3〇g, and heat the reaction solution to 7 while stirring. (TC. Thereafter, a solution of 2,3,5,6-tetrafluoro-1,4-phenylenediamine 1.8 〇g (10 mmol) in 3 ml of toluene was added dropwise to the above solution over 3 hours. The reaction was completed by stirring for 3 hours. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum dried and washed with hexane, ethanol and acetonitrile, whereby a pale yellow solid was obtained by the formula (II). A compound containing an aromatic ring 2. 43 g (yield: 59%). FAB-MS: m/z = 413 [M+H] + &lt;Synthesis of starting material &gt; 60 322866 201141818

在經氮置換之100mL休連克管中投入對笨二甲酸 3. 35g(25. Ommol)、間-曱酚5g、甲笨3〇g，邊撥摔邊將反 應溶液加熱至70°C。之後以3小時在上述溶液中滴下將 2, 6-二胺基吡啶1· 09g(10. Ommol)溶解於甲笨3〇g之溶液。 之後進行攪拌3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾舞’以己烧、乙醇、乙猜洗淨。經由此爽得:炎^ 色固體之通式（II)表示之含有芳族環之化合物2. ggg(收 率：70%)。FAB-MS : ιη/ζ= 342[Μ+ΗΓ。 &lt;原料5之合成&gt;Into a 100 mL Leisurek tube that was replaced with nitrogen, 3.35 g (25. Ommol), m-nonylphenol 5 g, and a stupid 3 〇g were charged, and the reaction solution was heated to 70 ° C while dropping. Thereafter, a solution of 2,6-diaminopyridine (10.0 g) (10. Ommol) dissolved in 3 g of 3 g was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 3 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum-dried and washed with hexane, ethanol, and B. Thus, the compound containing the aromatic ring represented by the formula (II) of the inflammatory solid is 2. ggg (recovery rate: 70%). FAB-MS : ιη/ζ= 342[Μ+ΗΓ. &lt;Synthesis of Raw Material 5&gt;

在經氮置換之lOOinL休連克管中投入2,5_β塞吩二甲駿 3.50g(25.0mmol)、間-曱酚5g、曱苯30g,邊攪拌邊將反 應溶液加熱至70°C。之後以3小時在上述溶液中滴下將 2, 6-二胺基吡啶1. 09g(10. Ommol)溶解於甲苯3〇§之溶液。 之後進行攪拌3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將.遭縮 液真空乾燥，以己烷、乙醇、乙腈洗淨。經由此獲得淡黃 色固體之通式（II)表示之含有芳族環之化合物2· 32g(收 322866 61 201141818 率：66%)。FAB-MS : m/z = 354[M+H]+。 &lt;原料6之合成&gt;2,5_β phenoxymer 3.50 g (25.0 mmol), m-nonylphenol 5 g, and toluene 30 g were placed in a nitrogen-substituted lOOinL Hughen tube, and the reaction solution was heated to 70 ° C while stirring. Then, a solution of 1.09 g (10. Ommol) of 2,6-diaminopyridine dissolved in toluene was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 3 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the condensed solution was vacuum dried and washed with hexane, ethanol and acetonitrile. The compound containing the aromatic ring represented by the formula (II) thus obtained as a pale yellow solid 2·32 g (yield 322866 61 201141818: 66%). FAB-MS : m/z = 354 [M+H]+. &lt;Synthesis of Raw Material 6&gt;

CHOCHO

OHC 在經氮置換之100mL休連克管中投入2, 6-吡啶二曱醛 3. 38g(25. Ommol)、間-甲盼5g、曱苯30g，邊擾拌邊將反 應溶液加熱至70°C。之後以3小時在上述溶液中滴下將 2, 6-二胺基°比0定1. 09g(10. Ommol)溶解於曱苯30g之溶液。 之後進行攪拌3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己院、乙醇、乙腈洗淨。經由此獲得淡黃 色固體之通式（II)表示之含有芳族環之化合物2. 40g(收 率：70%)。FAB-MS : m/z=344[M+H]+。 &lt;原料7之合成&gt;OHC was charged with 2,6-pyridinedifurfural 3.38 g (25. Ommol), m-panning 5 g, and toluene 30 g in a nitrogen-substituted 100 mL wicking tube, and the reaction solution was heated to 70 while stirring. °C. Then, a solution of the 2,6-diamine group at a ratio of 0.19 g (10. Ommol) dissolved in 30 g of toluene was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 3 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum dried and washed with hexane, ethanol, and acetonitrile. 40g (receiving rate: 70%) of the compound containing an aromatic ring represented by the formula (II) thus obtained as a pale yellow solid. FAB-MS: m/z = 344 [M+H]+. &lt;Synthesis of Raw Material 7&gt;

在經氮置換之100mL休連克管中投入1,4-伸苯基二胺 2. 70g(25. Ommol)、間-甲紛5g、甲苯30g，邊授拌邊將反 應溶液加熱至70°C。之後以3小時在上述溶液中滴下將對 苯二曱醛1.34g(10.0mmol)溶解於曱苯30g之溶液。之後 進行攪拌3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙醇、乙腈洗淨。經由此獲得淡黃 62 322866 201141818 色固體之通式（II)表示之含有芳族環之化合物2. 52g(收 率：80%)。FAB-MS : m/z=315[M+H]+。 &lt;原料8之合成&gt;The 1,4-phenylenediamine 2.70 g (25. Ommol), m-methyl 5 g, and toluene 30 g were placed in a nitrogen-substituted 100 mL wicking tube, and the reaction solution was heated to 70° while mixing. C. Thereafter, a solution of 1.34 g (10.0 mmol) of p-benzoaldehyde was dissolved in 30 g of toluene in the above solution over 3 hours. Thereafter, stirring was carried out for 3 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane, ethanol and acetonitrile. 52g (increased rate: 80%) of the compound containing an aromatic ring represented by the formula (II) of the yellowish color of 62 322866 201141818. FAB-MS: m/z = 315 [M+H]+. &lt;Synthesis of Raw Material 8&gt;

在經氮置換之100mL休連克管中投入2, 3, 5, 6-四氟 -1，4-伸苯基二胺4. 50g(25. Ommol)、間-曱盼5g、曱苯 30g，邊攪拌邊將反應溶液加熱至70°C。之後以3小時在 上述溶液中滴下將對苯二曱醛1. 34g(10. Ommol)溶解於曱 苯30g之溶液。之後進行攪拌3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙醇、乙腈洗淨。經由此獲得淡黃 色固體之通式（II)表示之含有芳族環之化合物2. 98g(收 率：65%)。FAB-MS : m/z = 459[M+H]+。 &lt;原料9之合成&gt;2, 3, 5, 6-tetrafluoro-1,4-phenylenediamine 4, 50 g (25. Ommol), m-p, 5 g, toluene 30 g were placed in a nitrogen-substituted 100 mL leisurely tube. The reaction solution was heated to 70 ° C while stirring. Then, a solution of 1.34 g (10. Ommol) of p-benzoic aldehyde in 30 g of hydrazine was dropped in the above solution over 3 hours. Thereafter, stirring was carried out for 3 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane, ethanol and acetonitrile. 98. (According rate: 65%) of the compound containing an aromatic ring represented by the formula (II) thus obtained as a pale yellow solid. FAB-MS : m/z = 459 [M+H]+. &lt;Synthesis of Raw Material 9&gt;

在經氮置換之lOOmL休連克管中投入1，4-伸苯基二胺 2. 70g(25. Ommol)、間-曱酚5g、甲苯30g，邊攪拌邊將反 應溶液加熱至70°C。之後以3小時在上述溶液中滴下將辛 醛1. 42g(10. Ommol)溶解於曱苯30g之溶液。之後進行攪 拌3小時完成反應。 63 322866 201141818 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙醇、乙腈洗淨。經由此獲得淡黃 色固體之通式（Π)表示之烴化合物1. g6g(收率：80%)。 FAB-MS : m/z = 233[M+H]+ 〇 &lt;原料10之合成&gt;The 1,4-phenylene diamine 2.70 g (25. Ommol), m-nonylphenol 5 g, and toluene 30 g were placed in a 100 mL Leisurel tube replaced with nitrogen, and the reaction solution was heated to 70 ° C while stirring. . Then, a solution in which octyl oxide 1.42 g (10. Ommol) was dissolved in 30 g of toluene was added dropwise to the above solution over 3 hours. Thereafter, the reaction was completed by stirring for 3 hours. 63 322866 201141818 After removing the volatile solvent in the reaction solution by evaporation, the concentrate was vacuum dried and washed with hexane, ethanol and acetonitrile. The hydrocarbon compound represented by the formula (Π) of the pale yellow solid thus obtained was 1. g 6 g (yield: 80%). FAB-MS : m/z = 233 [M+H] + 〇 &lt;Synthesis of Raw Material 10&gt;

在經氮置換之lOOmL休連克管中投入對苯二甲醛 3. 35g(25. Ommol)、間-曱酚5g、曱苯3〇g，邊攪拌邊將反 應溶液加熱至70°C。之後以3小時在上述溶液中滴下將2-乙基己胺1. 29g(10. 0_〇1)溶解於曱苯3〇g之溶液。之後 進行授摔3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙醇、乙腈洗淨。經由此獲得淡黃 色固體之通式（π)表示之烴化合物h94g(吹率：79幻。 FAB-MS ： m/z=246[M+H]+ ° &lt;原料11之合成&gt;To the 100 mL Leisure Link tube which was replaced with nitrogen, 3.35 g (25. Ommol), m-nonylphenol 5 g, and toluene 3 〇g were charged, and the reaction solution was heated to 70 ° C while stirring. Thereafter, a solution of 1.29 g (1. 0_〇1) of 2-ethylhexylamine dissolved in 3 〇g of fluorene was dropped in the above solution over 3 hours. After that, the reaction was carried out for 3 hours. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane, ethanol and acetonitrile. The hydrocarbon compound h94g represented by the formula (π) thus obtained as a pale yellow solid (blowing rate: 79 phantoms. FAB-MS: m/z = 246 [M+H] + ° &lt; Synthesis of Raw Material 11 &gt;

OHCOHC

在經氮置換之lOOmL休連克管中投入對笨二^酸 3. 35g(25. 0咖1)、間-甲盼5g、甲笨30g，邊麟邊將反 應溶液加熱至70°C。之後以3小時在上述溶液中滴下將4_ 322866 64 201141818 第三丁基環己胺1. 55g(l〇. Ommol)溶解於甲苯3〇g之溶液。 之後進行攪拌3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙醇、乙腈洗淨。經由此獲得淡黃 色固體之通式（ΠΙ)表示之烴化合物1.87g(收率：69%)。 FAB-MS : m/z=272[M+H]+。 &lt;原料12之合成&gt;The reaction solution was heated to 70 ° C while the nitrogen was replaced by a nitrogen-substituted lOOmL wicking tube of 3.35 g (25. 0 ca 1), m-p. 5 g, and 30 g. Then, a solution of 4_322866 64 201141818, tert-butylcyclohexylamine 1.55 g (10 mmol) in 3 μg of toluene was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 3 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane, ethanol and acetonitrile. Thus, 1.87 g of a hydrocarbon compound represented by the formula (ΠΙ) of a pale yellow solid was obtained (yield: 69%). FAB-MS: m/z = 272 [M+H]+. &lt;Synthesis of Raw Material 12&gt;

OHC 在經氮置換之lOOmL休連克管中投入對苯二曱醛 3. 35g(25. Ommol)、間-曱酚5g、甲苯30g，邊攪拌邊將反 應溶液加熱至70eC。之後以3小時在上述溶液中滴下將 3-（2-乙基己基氧基）丙胺1. 87g(10. Ommol)溶解於曱苯 30g之溶液。之後進行攪拌3小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾知’以己烧、乙猜洗淨。經由此獲得淡黃色固體 之通式（HO表示之烴化合物2. 28g(收率：75%)。FAB-MS : m/z= 304[M+H]+。 [實施例1]OHC In a 100 mL Leisure Link tube with nitrogen substitution, 3.35 g (25. Ommol), m-nonylphenol 5 g, and toluene 30 g were charged, and the reaction solution was heated to 70 eC with stirring. Then, a solution of 3.87 g (10. Ommol) of 3-(2-ethylhexyloxy)propylamine in 30 g of toluene was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 3 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum-dried and washed with hexane and B. Thus, a formula of a pale yellow solid (hydrocarbon compound represented by HO: 2.28 g (yield: 75%). FAB-MS: m/z = 304 [M+H] +. [Example 1]

在經氮置換之20mL休連克管中投入十一烷醛4. 26g 65 322866 201141818 (25. Ommol)、間-曱酚5g、甲苯30g ’邊攪拌邊將反應溶液 加熱至70°C。之後以3小時在上述溶液中滴下將3. 4〇g (10· Ommol)合成之原料1溶解於甲苯30g之溶液。之後進 行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥’以己烷、二乙醚洗淨。經由此獲得淡黃色固 體之本發明偶氮曱川寡聚物3. 09g(收率：60%)。FAB-MS : πι/ζ= 516[Μ+Η]+ ° [實施例2 ] ohc-〇-^n-〇-n=-〇~ CHO 4- Η2Ν^ 在經氮置換之100mL休連克管中投入2-乙基己胺 3. 23g(25. Ommol)、間-曱酚5g、曱苯3〇g ’邊攪拌邊將反 應溶液加熱至70°C ^之後以3小時在上述溶液中滴下將 3. 40g(l〇· 〇_〇1)合成之原料2溶解於甲苯3〇g之溶液。之 後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙腈洗淨。經由此獲得淡黃色固體 之本發明偶氮甲川寡聚物4. 50g(收率：80%)〇FAB-MS:m/z ^563[M+H]+。 [實施例3] 66 322866 201141818The reaction solution was heated to 70 ° C while stirring with a nitrogen-substituted 20 mL wicking tube of undecyl aldehyde 4.26 g 65 322866 201141818 (25. Ommol), m-nonylphenol 5 g, and toluene 30 g'. Thereafter, a solution of 3.4 g (10·Ommol) of the starting material 1 was dissolved in 30 g of toluene in the above solution over 3 hours. Thereafter, the mixture was stirred for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane and diethyl ether. The azochuanchuan oligo of the present invention was thus obtained in a pale yellow solid, 3.09 g (yield: 60%). FAB-MS : πι / ζ = 516 [Μ + Η] + ° [Example 2] ohc-〇-^n-〇-n=-〇~ CHO 4- Η2Ν^ 100mL Leisure Link tube replaced by nitrogen 2-ethylhexylamine 3.23 g (25. Ommol), m-nonylphenol 5 g, fluorene benzene 3 〇 g ' while stirring, the reaction solution was heated to 70 ° C ^ and then dripped in the above solution for 3 hours. A raw material 2 synthesized by 3.40 g (l〇·〇_〇1) was dissolved in a solution of 3 μg of toluene. Thereafter, stirring was carried out for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane and acetonitrile. The azomethine oligomer of the present invention was thus obtained as a pale yellow solid, 4. 50 g (yield: 80%) of 〇FAB-MS: m/z </ s[M+H]+. [Embodiment 3] 66 322866 201141818

在經氮置換之100mL休連克管中投入十一烧醛4. 26g (25. Ommol)、間-曱驗5g、曱苯30g，邊攪拌邊將反應溶液 加熱至70°C。之後以3小時在上述溶液中滴下將丨，7-二胺 基芴1· 96g(10. OOmmol)溶解於甲笨3〇g之溶液。之後進行 攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙腈洗淨。經由此獲得黃色固體之 本發明偶氮曱川寡聚物3· 26g(收率：65%)。FAB-MS : m/z = 501[M+H]+。 [實施例4]In a 100 mL Leisure Link tube which was replaced with nitrogen, 11.26 g (25. Ommol), 5 g of m-benzene and 30 g of toluene were charged, and the reaction solution was heated to 70 ° C while stirring. Thereafter, a solution of ruthenium, 7-diamino hydrazine, 1.96 g (10.0 mmol) dissolved in 3 〇g was added dropwise to the above solution over 3 hours. Thereafter, the reaction was completed by stirring for 6 hours. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane and acetonitrile. Thus, the azochuanchuan oligomer of the present invention was obtained in a yellow solid (32.6 g (yield: 65%). FAB-MS : m/z = 501 [M+H]+. [Example 4]

在經氣置換之1 OOinL休連克管中投入_2~乙基己胺 3. 23g(25. Ommol)、間-甲酚5g、曱苯3〇g，邊攪拌邊將反 應溶液加熱至7 0 C。之後以3小時在上述溶液中滴下將 4. 12g(10· OOmmol)合成之原料3溶解於曱苯3〇g之溶液， 之後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烧、乙腈洗淨。經由此獲得黃色固體之 322866 67 201141818 本發明偶氮曱川寡聚物3. 49g(收率：55%)。FAB_MS : m/z ， =635[M+H]+ 〇 [實施例5]Into a gas-substituted 1 OOinL vacant tube, 2-3~ethylhexylamine 3.23g (25. Ommol), m-cresol 5g, fluorene benzene 3〇g were added, and the reaction solution was heated to 7 while stirring. 0 C. Thereafter, a solution of 4.12 g (1.0 mmol) of the raw material 3 synthesized in 3 〇g of fluorene was dissolved in the above solution over 3 hours, and the mixture was stirred for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum dried and washed with hexane and acetonitrile. Thus, a yellow solid was obtained. 322866 67 201141818 The azochuanchuan oligomer of the present invention was 3.49 g (yield: 55%). FAB_MS : m/z , =635 [M+H]+ 〇 [Example 5]

在經氮置換之100mL休連克管中投入2_乙基己胺 3.23g(25.0mmol)、間-曱酚5g、曱苯3〇g，邊攪拌邊將反 應溶液加熱至7G°C：。之後以3小時在域錄中滴下將 3· 41g(10. Ommol)合成之原料4溶解於甲苯之溶液。之 後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烧、二乙戰淨。經由此獲得淡黃色固 體之本發明偶I甲川寡聚物3.38g(收率：6〇%)qFAB_ms: m/z= 564[M+H]+ ° [實施例6]2-N-hexylamine 3.23 g (25.0 mmol), m-nonylphenol 5 g, and toluene 3 〇g were placed in a nitrogen-substituted 100 mL wicking tube, and the reaction solution was heated to 7 G ° C while stirring. Then, a solution in which 3.41 g (10. Ommol) of the starting material 4 was dissolved in toluene was added dropwise to the domain for 3 hours. Thereafter, stirring was carried out for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum dried, and the mixture was burned and killed. 3.38 g (yield: 6〇%) qFAB_ms of the present invention was obtained as a pale yellow solid (yield: 6〇%): m/z = 564 [M+H] + ° [Example 6]

CHO +CHO +

在經氮置換之100mL休連克管中投入2_乙基己胺 3. 23g(25. Ommol)、間-曱酚5g、甲笨3〇g，邊攪拌邊將反 322866 68 201141818 應溶液加熱至70 C。之後以3小時在上述溶液中滴下將 3. 53g(10· OOmmol)合成之原料5溶解於甲苯3〇g之溶液。 之後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、二乙醚洗淨。經由此獲得淡黃色固 體之本發明偶氮甲川寡聚物3.46g(收率：60%)。FAB-MS : m/z^ 576[M+H]+。 [實施例7]2-ethylhexylamine 3.23g (25. Ommol), m-nonylphenol 5g, and azine 3〇g were placed in a nitrogen-substituted 100 mL leisurely tube, and the anti-322866 68 201141818 solution was heated while stirring. To 70 C. Thereafter, 3.53 g (1.0 mmol) of the starting material 5 was dissolved in the above solution over 3 hours to dissolve a solution of 3 g of toluene. Thereafter, stirring was carried out for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane and diethyl ether. Thus, 3.46 g of the azomethine oligomer of the present invention (yield: 60%) was obtained as a pale yellow solid. FAB-MS : m/z^ 576[M+H]+. [Embodiment 7]

OHCOHC

CHOCHO

__ 在經氮置換之l〇〇mL休連克管中投入4_正辛基苯胺 5. 13g(25. Ommol)、間-曱酚5g、甲苯3〇g，邊攪拌邊將反 應溶液加熱至7(TC。之後以3小時在上述溶液中滴下將 3.43g(l〇.〇mm〇l)合成之原料6溶解於曱苯3〇g之溶液。之 後進行攪拌6小時完成反應。 、將反應溶液中之揮發性溶劑經由蒸發除去後，將滚縮 液真工乾燥’以己燒、二乙_洗淨。經由此獲得紅褐色固 體之本發明偶氮曱川养聚物4. 31g(收率：6〇%)。FAB-MS : m/z = 718[M+H]+ ° [實施例8] 322866 69 201141818__ 4 - n-octyl aniline 5. 13g (25. Ommol), m-nonylphenol 5g, toluene 3 〇g were added to a nitrogen-substituted l〇〇mL wicking tube, and the reaction solution was heated while stirring to After 7 (TC), the raw material 6 synthesized by 3.43 g (l〇.〇mm〇l) was dissolved in the above solution for 3 hours, and then dissolved in a solution of 3 〇g of fluorene. After stirring for 6 hours, the reaction was completed. After the removal of the volatile solvent in the solution is carried out by evaporation, the tumbling liquid is dried, and the azo hydrazine broth of the present invention is obtained as a reddish brown solid. Rate: 6〇%). FAB-MS: m/z = 718[M+H]+ ° [Example 8] 322866 69 201141818

在經氮置換之lOOmL休連克管中投入4-正辛基笨胺 5.13g(25.0mmol)、間-曱酚5g、曱苯30g，邊攪拌邊將反 應溶液加熱至70°C。之後以3小時在上述溶液中滴下將 4, 4’ -聯苯二曱醛2. 10g(10. OOmmol)溶解於曱笨30g之溶 液。之後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙腈洗淨。經由此獲得淡黃色固體 之本發明偶氮曱川募聚物3. 50g(收率：60%)〇FAB-MS:m/z = 585[M+H]+。 [實施例9] H2N—+ 在經氮置換之lOOmL休連克管中投入十一烷醛4. 26g (25. Ommol)、間-曱酚5g、甲苯30g ’邊攪拌邊將反應溶液 加熱至70°C。之後以3小時在上述溶液中滴下將3. 14g (10· Ommol)合成之原料7溶解於甲苯30g之溶液。之後進 行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙腈洗淨。經由此獲得淡黃色固體 70 322866 201141818 之本發明偶氮甲川寡聚物5. 05g(收率：78%)。FAB-MS : m/z = 647[M+H]+。 [實施例10]To the 100 mL Leisurek tube which was replaced with nitrogen, 5.13 g (25.0 mmol), m-nonylphenol 5 g, and toluene 30 g were charged, and the reaction solution was heated to 70 ° C while stirring. Thereafter, 4,4'-biphenyldialdehyde (2. 4'-biphenyldialdehyde) (0.1 g) (10. 00 mmol) was dissolved in the above solution for 3 hours to dissolve in 30 g of a solution. Thereafter, stirring was carried out for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane and acetonitrile. The azo kawachuan polymer of the present invention thus obtained was a pale yellow solid 3. 50 g (yield: 60%) 〇FAB-MS: m/z = 585 [M+H]+. [Example 9] H2N-+ was charged with undecylaldehyde 4.26 g (25. Ommol), m-nonylphenol 5 g, toluene 30 g' in a nitrogen-substituted lOOmL wicking tube. The reaction solution was heated while stirring. 70 ° C. Thereafter, a solution of 3.14 g (10·Ommol) of the starting material 7 dissolved in 30 g of toluene was added dropwise to the above solution over 3 hours. Thereafter, the mixture was stirred for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane and acetonitrile. 05g (Yield: 78%) of the azomethine oligomer of the present invention was obtained by the light yellow solid 70 322866 201141818. FAB-MS : m/z = 647 [M+H]+. [Embodiment 10]

在經氮置換之100mL休連克管中投入十一烷醛4.26g (25. Ommol)、間-甲酚5g、曱苯30g，邊攪拌邊將反應溶液 加熱至70°C。之後以3小時在上述溶液中滴下將4. 58g (10. Ommol)合成之原料8溶解於甲苯30g之溶液。之後進 行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙腈洗淨。經由此獲得淡黃色固體 之本發明偶氮甲川寡聚物6.32g(收率：80%)〇FAB-MS:m/z = 791[M+H]+ ° [實施例11] 〇hc~C3~^~^~ch〇 +4.16 g (25. Ommol), m-cresol 5 g, and toluene 30 g of undecylaldehyde were placed in a nitrogen-substituted 100 mL wicking tube, and the reaction solution was heated to 70 ° C while stirring. Then, a solution of 4.58 g (10. Ommol) of the starting material 8 dissolved in 30 g of toluene was added dropwise to the above solution over 3 hours. Thereafter, the mixture was stirred for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane and acetonitrile. 6.32 g of the azomethine oligomer of the present invention thus obtained as a pale yellow solid (yield: 80%) 〇FAB-MS: m/z = 791 [M+H] + ° [Example 11] 〇hc~C3 ~^~^~ch〇 +

在經氮置換之1 OOmL休連克管中投入5.81g(25. Ommol) 合成之原料9、間-曱酚5g、甲苯3〇g，邊攪拌邊將反應溶 液加熱至70°C。之後以3小時在上述溶液中滴下將4, 4，-聯苯二曱醛2. 10g(10· Ommol)溶解於曱苯3〇g之溶液。之 322866 71 201141818 後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥’ m乙腈洗淨^經由此獲得淡黃色固體 之本發明偶氮曱川养聚物4. 47g(收率：8〇%)。FAB_MS : m/z =639 [M+H ]+。 [實施例12]5.81 g (25. Ommol) of the synthesized raw material 9, m-nonylphenol 5 g, and toluene 3 〇g were placed in a nitrogen-substituted 1 000 mL wicking tube, and the reaction solution was heated to 70 ° C while stirring. Then, a solution of 4,4,-biphenyldialdehyde (1.2 g (10·Ommol)) dissolved in 3 〇g of guanidine was dropped in the above solution over 3 hours. After 322866 71 201141818, the reaction was completed by stirring for 6 hours. After the argon-dissolved polymer of the present invention was obtained in a light yellow solid, 4. 47 g (yield: 8 %), the volatile solvent in the reaction solution was removed by evaporation. ). FAB_MS : m/z =639 [M+H ]+. [Embodiment 12]

+ OHC+ OHC

N-NN-N

h2n 在經氮置換之100mL#連克管中投入6. 13g(25. Ommol) 合成之原料10、間-曱盼5g、甲苯30g，邊攪拌邊將反應 溶液加熱至70T：。之後以3小時在上述溶液中滴下將2,5-雙（胺基苯基）-1，3, 4-噁二唑2· 52g(10. Ommol)溶解於曱 笨30g之溶液。之後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後’將濃縮 液真空乾燥，以己烧、乙腈洗淨。經由此獲得黃褐色固體 之本發明偶氮甲川寡聚物4. 95g(收率：7〇%)。FAB-MS : m/z = 707[M+H]+。 [實施例13] h2XXh2 + 〇HC~^NH0^ 72 322866 201141818 在經氮置換之100虹休連克管中投入6. 79g(25. Onunol) 合成之原料11、間-曱酚5s、曱苯3〇g，邊攪拌邊將反應 溶液加熱至70°C。之後以3小時在上述溶液中滴下將2,6-二胺基吡啶1. 〇9g(l〇. Ommol)溶解於甲苯30g之溶液。之 後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以己烷、乙腈洗淨。經由此獲得淡黃色固體 之本發明偶氮甲川寡聚物4· 00g(收率：65%)。FAB-MS: m/z = 616[M+H]+ 〇 [實施例14]H2n 6.13 g (25. Ommol) of the starting material 10, m-p. 5 g, and toluene 30 g were placed in a nitrogen-substituted 100 mL # gram tube, and the reaction solution was heated to 70 T with stirring. Thereafter, a solution of 2,5-bis(aminophenyl)-1,3,4-oxadiazole 2·52 g (10. Ommol) dissolved in 30 g of hydrazine was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum dried, washed with hexane and acetonitrile. The thus obtained azomethine oligomer of the present invention was 4.95 g (yield: 7 % by weight). FAB-MS : m/z = 707 [M+H]+. [Example 13] h2XXh2 + 〇HC~^NH0^ 72 322866 201141818 6.79g (25. Onunol) synthesized raw material 11, m-nonylphenol 5s, fluorene benzene in a nitrogen-substituted 100 rainbow squirrel tube 3 〇 g, the reaction solution was heated to 70 ° C while stirring. Then, a solution of 2,6-diaminopyridine 1. 〇9 g (10 mmol) in 30 g of toluene was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried in vacuo and washed with hexane and acetonitrile. Thus, the azomethine oligomer of the present invention was obtained in a pale yellow solid (yield: 65%). FAB-MS: m/z = 616 [M+H] + 〇 [Example 14]

在經氮置換之lOOmL休連克管中投入5. 51g(25. 〇mm〇1) 合成之原料12、間-甲酚5g、甲笨30g’邊攪拌邊將反應 溶液加熱至701。之後以3小時在上述溶液中滴下將3, 6_ 二胺基咔唑1. 97g(10. Ommol)溶解於甲苯3〇g之溶液，之 後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真二乾燥，以己烧、乙腈洗淨。經由此獲得淡黃色固體 之本發明偶氮甲川寡聚物4· 27g(收率：6〇%)。FAB_MS : m/z = 712[M+H]+ 〇 322866 73 201141818 [比較例1]The reaction solution was heated to 701 while stirring 5.10 g (25. 〇mm 〇 1) of the starting material 12, m-cresol 5 g, and keb 30 g while stirring with a nitrogen-substituted lOOmL. Thereafter, a solution of 1.97 g (10. Ommol) of 3,6-diaminocarbazole dissolved in 3 μg of toluene was added dropwise to the above solution over 3 hours, and the mixture was stirred for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was dried, and washed with hexane and acetonitrile. Thus, the azomethine oligomer of the present invention was obtained in a pale yellow solid by 4·27 g (yield: 6〇%). FAB_MS : m/z = 712 [M+H]+ 〇 322866 73 201141818 [Comparative Example 1]

在經氮置換之20mL休連克管中投入苯甲酿〇. 85gInto the 20 mL Leisure Link tube replaced by nitrogen, put the benzoquinone into the pot. 85g

之後以3小時在上述溶液中滴下將2，7—二胺基芴〇 至70 L 52g (2· 66mmol)溶解於間-曱酚5g之溶液。之後進行攪拌6小 時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥’以熱己烧、乙腈、ψ醇洗淨。經由此獲得黃 色固體之偶氮曱川寡聚物0. 65g(收率：61%)。FAB-MS: m/z = 373[M+H]+。 [比較例2]Thereafter, a solution in which 2,7-diamino hydrazine to 70 L of 52 g (2.66 mmol) was dissolved in 5 g of m-nonylphenol was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum dried and washed with hot hexane, acetonitrile and methanol. The azo chuanchuan oligo of the yellow solid was obtained in an amount of 0.65 g (yield: 61%). FAB-MS: m/z = 373 [M+H]+. [Comparative Example 2]

在經乱置換之2〇mL休連克管中投入全氟苯曱醛L 56g (7.98mmol)、間、甲酚1〇g’邊攪拌邊將反應溶液加熱至7〇 C。之後以3小時在上述溶液中滴下將2, 7-二胺基芴0. 52g (2. 66mmol)溶解於間-曱酚5g之溶液。之後進行攪拌6小 時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥’以熱己烷、乙腈、甲醇洗淨。經由此獲得黃 色固體之偶氣甲川寡聚物0. 52g(收率：35%)。FAB-MS: m/z 74 322866 201141818 = 553[M+H]+° [比較例3 ]The reaction solution was heated to 7 〇 C while stirring the perfluorobenzaldehyde L 56 g (7.98 mmol) and m-cresol 1 〇g' in a 2 mL mL wick tube. Thereafter, a solution of 2,7-diamine oxime 0.52 g (2.66 mmol) dissolved in 5 g of m-nonylphenol was added dropwise to the above solution over 3 hours. Thereafter, stirring was carried out for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum dried and washed with hot hexane, acetonitrile and methanol. The 52 g (yield: 35%) of the azo gas oligomer of the yellow solid was obtained. FAB-MS: m/z 74 322866 201141818 = 553[M+H]+° [Comparative Example 3]

在經氮置換之2〇mL休連克管中投入苯曱醛〇. 85g (7. 98mmol)、間~甲酚i〇g’邊攪拌邊將反應溶液加熱至7〇 。(：。之後以3小時在上述溶液中滴下將丨，5_二胺基萘〇 42轻 (2. 66mmol)溶解於間_甲紛5g之溶液。之後進行授拌6小 時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以熱己烷、乙腈、甲醇洗淨。經由此獲得黃 色固體之偶氮甲川寡聚物〇. 43g(收率：48%)°FAB-MS: m/z = 335[M+H]+ 〇 [比較例4]The reaction solution was heated to 7 Torr while stirring with a nitrogen-substituted 2 〇 mL wicking tube of 85 g (7. 98 mmol) and m-cresol i 〇 g'. (: After that, a solution of hydrazine, 5-diaminonaphthoquinone 42 light (2.66 mmol) was dissolved in 5 g of the mixture, and the reaction was carried out for 6 hours to complete the reaction. After the volatile solvent in the solution was removed by evaporation, the concentrated liquid was dried in vacuo and washed with hot hexane, acetonitrile, and methanol to obtain a yellow solid azomethacrylate oligomer. 43 g (yield: 48%) °FAB-MS: m/z = 335 [M+H]+ 〇 [Comparative Example 4]

在經氮置換之20mL休連克管中投入苯甲鳝〇 85g (7.98mraol)、間-甲酚l〇g，邊攪拌邊將反應溶液加熱至7〇 。(：。之後以3小時在上述溶液中滴下將2, 3, 5, 6-四甲基 -1，4-伸苯基二胺0. 44g(2. 66mmol)溶解於間-甲紛5g之溶 液。之後進行攪拌6小時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 322866 75 201141818 液真空乾燥，以熱己烷、乙腈、曱醇洗淨。經由此獲得黃 色固體之偶氮甲川寡聚物〇. 58g(收率：64%)。FAB_MS : m/z = 341[M+H]+。 [比較例5 ]Benzoic acid 85 g (7.98 mraol) and m-cresol l〇g were placed in a nitrogen-substituted 20 mL wicking tube, and the reaction solution was heated to 7 Torr with stirring. (:. After 2 hours in the above solution, 2, 3, 5, 6-tetramethyl-1,4-phenylenediamine 0. 44g (2.66 mmol) was dissolved in the mixture - 5g The solution was stirred for 6 hours to complete the reaction. After the volatile solvent in the reaction solution was removed by evaporation, the concentrated 322866 75 201141818 solution was vacuum dried and washed with hot hexane, acetonitrile and methanol. Azomethine oligomer 〇. 58 g (yield: 64%). FAB_MS: m/z = 341 [M+H] + [Comparative Example 5]

在經氮置換之20mL休連克管中投入2_胺基芴145g 。(7.98麵1)、間-曱_ 1()g，邊麟邊將反應溶液加熱至^ °C。之後以3小時在上述溶液中滴下將對苯二曱醛〇.36忌 (2. 66麵1)溶解於間-甲盼5g之溶液。之後進行授摔6小 時完成反應。 將反應溶液中之揮發性溶劑經由蒸發除去後，將濃縮 液真空乾燥，以熱己烧、乙腈、轉洗淨。經由此獲得黃 色固體之偶氮曱川寡聚物〇 41g(收率：33%&gt;FAB_MS:m/z =461[M+H]+ ° &lt;溶解性之評估&gt; 評估實施例1至14及比較例1至5獲得之偶氮甲川寡 聚物在下述表1表示之溶劑之溶解性。 76 322866 201141818 [表 1-1] 表1_ 1A 2-amino group 145 g was placed in a nitrogen-substituted 20 mL wicking tube. (7.98 face 1), m-曱_ 1 () g, while heating the reaction solution to ^ ° C. Thereafter, a solution of p-benzofurald oxime. 36 bogey (2.66 face 1) was dissolved in methane-prone 5 g in the above solution over 3 hours. After that, the reaction was completed in 6 hours. After the volatile solvent in the reaction solution was removed by evaporation, the concentrate was vacuum dried, washed with hot hexane, acetonitrile, and washed. Thus, 41 g of azo曱chuan oligomer oligomer of yellow solid was obtained (yield: 33% &gt; FAB_MS: m/z = 461 [M+H] + ° &lt;Evaluation of Solubility&gt; Evaluation Example 1 to The solubility of the azomethine oligomer obtained in 14 and Comparative Examples 1 to 5 in the solvent shown in the following Table 1. 76 322866 201141818 [Table 1-1] Table 1_1

有機 溶劑 實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 試樣 實施 例6 實施 例7 實施 例8 實施 例9 實施 你i in 實施 /«•111 甲酵 A A A A A A A A A A Λ 乙醇 A A A A A A A A A A A 乙腈 A B B B A A A B B B D 丙酮 A A B A A A A A A A A IPA A A B B A A A A A B A THF A A A A A A A A A A A MEK A A A A A A A A A A A 甲苯 A A A A A A A A A A A PGM A A A A A A A A A A A 乳酸 甲酯 A A A A A A A A A A AOrganic Solvent Example 1 Example 2 Example 3 Example 4 Example 5 Sample Example 6 Example 7 Example 8 Example 9 Implementation You i in Implementation / «• 111 A fermentation AAAAAAAAAA 乙醇 Ethanol AAAAAAAAAAA Acetonitrile ABBBAAABBBD Ace AABAAAAAAAA IPA AABBAAAAABA THF AAAAAAAAAAA MEK AAAAAAAAAAA Toluene AAAAAAAAAAA PGM AAAAAAAAAAA Methyl lactate AAAAAAAAAAA

[表 1-2] 表1-2 試樣 有機溶劑 實施例 12 實施例 13 實施例 14 比較例1 比較例2 比較例3 比較例4 比較例5 甲醇 A A A C C C C c 乙醇 A B C C C c C c 乙腈 B c C C c c c c 丙辆 C c c C c c c c IPA B c c C c c c c THF A A A C c c c c MEK A A A c c c c c 曱笨 A A A c c c c c PGM A A A c c c c r 乳酸甲酯 A A A c c c c c A:於室溫（25°C )可溶（在100g之溶劑溶解〇. ig以上）、B:加熱可溶（於室溫溶解於1〇〇g 溶劑者未達o. ig，加熱至各種溶劑之沸點成為可溶）、c:不溶（即使加熱，溶解於i〇〇g 溶劑者未達〇. lg)。 IPA:異丙醇THF:四氫呋喃MEK:甲基乙基酮PGM :丙二醇一甲醚 根據表1明瞭具有柔軟構造之烴基及剛直構造之含有 芳族環之共輥基之本發明偶氮甲川寡聚物，溶解於至少一 種甲醇、乙醇、乙腈、丙酮、IPA、THF、MEK、甲苯、PGM 及礼酸甲g旨中之任何—種之溶劑，另_方面，明瞭僅由剛 77 322866 201141818 直構造之含有芳族環之共軛基形成之比較例之偶氮曱川寡 聚物對於上述溶劑全都未顯示溶解性。 【圖式簡單說明】 無 【主要元件符號說明】 無 78 322866[Table 1-2] Table 1-2 Sample organic solvent Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Methanol AAACCCC c Ethanol ABCCC c C c Acetonitrile B c CC Cccc C C cc C cccc IPA B cc C cccc THF AAAC cccc MEK AAA ccccc 曱 AAA ccccc PGM AAA ccccr Methyl acrylate ccccc A: soluble at room temperature (25 ° C) (dissolved in 100 g of solvent). Ig or more), B: heat soluble (dissolved in 1〇〇g solvent at room temperature, not reached o. ig, heated to the boiling point of various solvents to become soluble), c: insoluble (even if heated, dissolved in i〇〇 g Solvents do not reach 〇. lg). IPA: isopropanol THF: tetrahydrofuran MEK: methyl ethyl ketone PGM: propylene glycol monomethyl ether According to Table 1, the azomethine oligomerization of the present invention having a soft-structured hydrocarbon group and a rigid structure-containing common roll group containing an aromatic ring a solvent dissolved in at least one of methanol, ethanol, acetonitrile, acetone, IPA, THF, MEK, toluene, PGM, and glucosinolate, and in other respects, the structure is only straightened by just 77 322866 201141818 The azo曱chuan oligomer of the comparative example in which the conjugated group containing an aromatic ring was formed showed no solubility to all of the above solvents. [Simple diagram description] None [Main component symbol description] None 78 322866

Claims (1)

201141818 七、申請專利範圍： 1. 一種偶氮甲川寡聚物，其特徵為：在主骨架中具有偶氮 次甲基與可具有取代基之二價芳族基交互結合進行共 軛之含有芳族環之共軛基， 該含有芳族環之共輛基兩末端之偶氮次甲基，結合 有不與該含有芳族環之共輛基共輛而可具有氧原子、硫 原子或伸環烷基之基之烴基， 該烴基係與醛基及胺基不具有反應性。 2. 如申凊專利範圍第1項所述之偶氮甲川寡聚物，其中， 该經基為選自由可具有支鏈、可經齒素原子取代之碳數 2至512之燒基，可具有支鏈、可經齒素原子取代之碳 數2至512之院氧基，基中具有醚結合及/或硫鱗結 合、可經i素原子取代之碳數2至512之烴基及可具有 取代基之碳數3至50之環烷基所成組群中之任何一個 基。 3·如申請專利範圍第1項或第2項所述之偶氮甲川寡聚 物’其中，該偶氮甲川寡聚物的分子量在150至i5qqq 之範圍内。 4·如申請專利範圍第1項至第3項中任一項所述之偶氮甲 川寡聚物’其中，該偶氮曱川寡聚物對於選自甲紛、甲 苯、THF、環戊基曱基趟、丙酮、MEK、ΜIBK、環戊綱 氯仿、二氣甲烷、四氣化碳、氯苯、二硫化碳、乙酸乙 酯、乙酸丁酯、乳酸曱酯、甲醇、乙醇、異丙醇、笨甲 醇、正丁醇、第三丁醇、戊醇、乙二醇、丙二醇、内一 1 322866 201141818 醇一曱趟、β比α定、NMP、硫酸、曱酸、乙酸、鹽酸、乳 酸、三乙胺、二丁胺中之任何一種溶劑或二種以上之共 溶劑100g，於25°c具有0. lg以上之溶解性。 5. 如申請專利範圍第1項至第4項中任一項所述之偶氮曱 川寡聚物，其中，該偶氮曱川寡聚物為下述通式（I)表 不者. R1-A-Ar-A-R2 ⑴ (於上述式，Ar為可具有取代基之二價芳族基或偶氮次 曱基與可具有取代基之二價芳族基交互結合進行共輛 之含有芳族環之共軛基， A為偶氮次曱基， R1及R2獨立為可具有支鏈、可經鹵素原子取代之 碳數2至512之烷基，可具有支鏈、可經鹵素原子取代 之碳數2至512之烷氧基，基中具有醚結合及/或硫醚 結合、可經鹵素原子取代之碳數2至512之烴基或可具 有取代基之碳數3至50之環烷基）。 6. 如申請專利範圍第5項所述之偶氮甲川寡聚物，其中， 該二價芳族基為下述式表示之任何一個基 2 322866 201141818201141818 VII. Patent application scope: 1. An azomethine oligomer characterized by having an azo methine group in a main skeleton and a divalent aromatic group capable of having a substituent to be conjugated to contain a aryl group. a conjugated group of a family ring, the azo methine group at both ends of the common group containing an aromatic ring, combined with a common vehicle group not containing the aromatic ring, may have an oxygen atom, a sulfur atom or a stretching a hydrocarbon group of a cycloalkyl group which is not reactive with an aldehyde group and an amine group. 2. The azomethine oligomer according to claim 1, wherein the radical is selected from the group consisting of a base having 2 to 512 carbon atoms which may have a branch and may be substituted by a dentate atom. a hydrocarbon having 2 to 512 carbon atoms which may be substituted by a dentate atom, having an ether bond and/or a sulfur scale bond in the group, a hydrocarbon group having 2 to 512 carbon atoms which may be substituted by an i atom, and may have Any one of the group consisting of a cycloalkyl group having 3 to 50 carbon atoms of the substituent. 3. The azomethine oligomer as described in claim 1 or 2 wherein the azomethine oligomer has a molecular weight in the range of 150 to i5qqq. 4. The azomethine oligomer according to any one of claims 1 to 3, wherein the azochuanchuan oligomer is selected from the group consisting of methyl benzene, toluene, THF, and cyclopentyl. Mercaptopurine, acetone, MEK, ΜIBK, cyclopentachloroform, di-methane, tetra-carbonized carbon, chlorobenzene, carbon disulfide, ethyl acetate, butyl acetate, decyl lactate, methanol, ethanol, isopropanol, stupid Methanol, n-butanol, tert-butanol, pentanol, ethylene glycol, propylene glycol, inner 1 322866 201141818 alcohol monoterpene, beta ratio α, NMP, sulfuric acid, citric acid, acetic acid, hydrochloric acid, lactic acid, triethyl The solubility of 0.1 g or more at 25 ° C is 100 g of any one of the amine and the dibutylamine. 5. The azochuanchuan oligomer according to any one of the above-mentioned claims, wherein the azokawachuan oligomer is represented by the following formula (I). R1-A-Ar-A-R2 (1) (In the above formula, Ar is a divalent aromatic group or a azoindenyl group which may have a substituent, and a divalent aromatic group which may have a substituent is mutually bonded and carried out together. a conjugated group containing an aromatic ring, A is an azo-indenyl group, and R1 and R2 are independently an alkyl group having 2 to 512 carbon atoms which may have a branch and may be substituted by a halogen atom, may have a branched chain, may be halogen-containing An alkoxy group having 2 to 512 carbon atoms substituted by an atom, a hydrocarbon group having 2 to 512 carbon atoms which may have an ether bond and/or a thioether bond, may be substituted by a halogen atom, or a carbon number of 3 to 50 which may have a substituent Cycloalkyl). 6. The azomethine oligomer according to claim 5, wherein the divalent aromatic group is any one represented by the following formula 2 322866 201141818 3 322866 201141818 (於上述式，以半括弧括上之部位表示鍵結）。 7. 如申請專利範圍第1項至第6項中任一項所述之偶氮曱 川寡聚物，其中，對於將該偶氮曱川寡聚物使用作為P 型半導體層或N型半導體層之形成材料所製作之p-n 接合元件，P型半導體側之電極連接在正極端子，N型 半導體側之電極連接在負極端子，可在-5V至+5V之範 圍内施加電壓，成為順方向之電力量/逆方向之電力量 &gt;1.0。 8. —種申請專利範圍第1項所述之偶氮曱川寡聚物之製 造方法，其特徵為：具有對於下述通式（II)表示之含有 芳族環之化合物1當量，將下述通式（Π)表示之烴化合 物2當量進行反應之步驟： X-—Ar1—(Α-Αήρ~~X (Π)3 322866 201141818 (In the above formula, the part enclosed in semi-brackets represents the bond). 7. The azokawachuan oligomer according to any one of the preceding claims, wherein the azokawachuan oligomer is used as a P-type semiconductor layer or an N-type semiconductor. a pn junction element made of a layer forming material, an electrode on the P-type semiconductor side is connected to the positive electrode terminal, and an electrode on the N-type semiconductor side is connected to the negative electrode terminal, and a voltage can be applied in a range of -5 V to +5 V to become a forward direction. The amount of power / the amount of power in the reverse direction &gt; 1.0. 8. The method for producing an azochuanchuan oligomer according to the first aspect of the invention, which is characterized in that the compound having an aromatic ring represented by the following formula (II) is equivalent to 1 equivalent. The step of reacting 2 equivalents of the hydrocarbon compound represented by the formula (Π): X--Ar1—(Α-Αήρ~~X (Π) (於上述式（II)，二個X同時為醛基或胺基， Ar1為可具有取代基之二價芳族基、 Ar2為可具有取代基之二價芳族基、 A為偶氮次曱基、 p為0至5之整數、 p為2以上時，複數存在之Ar2可相同亦可不同； 4 322866 201141818 於上述式（III)，在上述式（11)之χ為醛基時γ為 胺基，X為胺基時γ為醛基， Ar為可具有取代基之二價芳族基、 A為偶氮次曱基、 m為〇或1、 R及R2獨立為氫原子、碳數1至2〇之烷基或鹵素 原子、 Z為具有氧原子、硫原子或伸環烷基之二價基、 i為0或1， h及j獨立為〇至12之整數（惟’ z為氧原子或硫 原子時’ h及j同時為1以上）、 k為1至1〇之整數， h為2以上時’複數存在之Ri可相同亦可不同， j為2以上時，複數存在之R2可相同亦可不同， k為2以上時，複數存在之（_(CHRl)h_(z)i_(CHR2)广) 可相同亦可不同、 q為0或1、 R3為碳數1至20之烷基、 (-(CHRVUKCHR2)广）k-(〇)q-R3 表示之構造中 之碳數為2至512)。 9.如申請專利範圍第8項所述之偶氮甲川寡聚物之製造 方法，其中，該含有芳族環之化合物為至少一種選自由 下述式表示之化合物所成組群之化合物： 5 322866 201141818 x X(In the above formula (II), two X are both an aldehyde group or an amine group, Ar1 is a divalent aromatic group which may have a substituent, Ar2 is a divalent aromatic group which may have a substituent, and A is an azo group The fluorenyl group, p is an integer of 0 to 5, and when p is 2 or more, Ar2 in the plural may be the same or different; 4 322866 201141818 In the above formula (III), when the above formula (11) is an aldehyde group, γ Is an amine group, γ is an aldehyde group when X is an amine group, Ar is a divalent aromatic group which may have a substituent, A is an azo sulfhydryl group, m is hydrazine or 1, R and R 2 are independently a hydrogen atom, carbon a number of 1 to 2 alkyl or a halogen atom, Z is a divalent group having an oxygen atom, a sulfur atom or a cycloalkyl group, i is 0 or 1, and h and j are independently an integer from 〇 to 12 (only 'z When an oxygen atom or a sulfur atom is 'h and j are 1 or more at the same time, k is an integer of 1 to 1 ,, and when h is 2 or more, the plural of the plural may be the same or different, and when j is 2 or more, the plural exists. R2 may be the same or different. When k is 2 or more, the plural (_(CHRl)h_(z)i_(CHR2) wide) may be the same or different, q is 0 or 1, and R3 is carbon number 1 to 20 alkyl, (-(CHRVUKC HR2) wide) k-(〇)q-R3 indicates that the carbon number in the structure is 2 to 512). 9. The method for producing an azomethine oligomer according to claim 8, wherein the aromatic ring-containing compound is at least one compound selected from the group consisting of compounds represented by the following formula: 5 322866 201141818 x X 6 322866 2011418186 322866 201141818 XX XX XX 322866 201141818322866 201141818 8 322866 201141818 ’ （於上述式，x為醛基或胺基）。 10.如申請專利範圍第8項或第9項所述之偶氮曱川寡聚物 之製造方法，其中，該烴化合物為至少一種選自由下述 式表示之化合物所成組群之化合物：8 322866 201141818 ' (in the above formula, x is an aldehyde group or an amine group). 10. The method for producing an azochuanchuan oligomer according to the above-mentioned item, wherein the hydrocarbon compound is at least one compound selected from the group consisting of compounds represented by the following formula: YY (於上述式，Y為胺基或醛基，t為5至11之整數）。 9 322866 201141818 四、指定代表圖·· (一) 本案指定代表圖為：第（）圖。 (二) 本代表圖之元件符號簡單說明： 本案無圖式 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： R1-—A-Ar——A——R2 322866(In the above formula, Y is an amino group or an aldehyde group, and t is an integer of 5 to 11). 9 322866 201141818 IV. Designation of Representative Representatives (1) The representative representative of the case is: (). (2) A brief description of the symbol of the representative figure: There is no drawing in this case. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R1--A-Ar——A——R2 322866
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