1233937 玖、發明說明 (發明δ兌明應敘明：發明所屬之技術領域、先前技術、內容、實 施方式及圖式簡單說明） 發明所屬之技Μ 本發明是有關於一種資訊儲存媒體，且特別是有關於 一種資訊儲存媒體用花青TCNQ錯合物色素。 先前技術 有鑑於時代的進步’資訊的流通量也大幅的增加，而 大里資訊的流通，則需要〜個儲存密度更高、更小型化， 而製作成Φ更低_雜||。由腿性肺關並不能滿 足上述之需求’因此磁性儲存媒體已逐漸由光學資訊儲存 媒體取代。有機色素（Organic Dye)由於具有光敏感性，而 廣泛的應用於光學資訊儲存媒體。而且，有機色素目前也 被積極的硏究，並應用在各種產業。舉例來說，有機色素 之應用包括非線性光學元件、光碟資料之記錄與顯示、光 阻、熱/光/電感測與指示劑、能量之轉換與儲存、醫療與 生物等。 目則吊使用之有機色素包括花青（Cyanine)色素、偶氮 (Αζο)色素、靛類色素等’其中較適合作爲高密度光學資 訊儲存媒體之有機色素包括花青色素。1856年，Greville Williams首先合成出具花青結構的花青藍色素（Cyanine blue)(K. Venkataraman(ed.)，The Chemistry of Synthetic Dyes, Vol. Π，p· 1143-1186，Academic Press，New York， 1952·)。其後’ 1875年’ V〇gei發現williams所合成的花 8 10435twf.doc 1233937 青藍具有特殊的感光性質（sensitizing pr〇perties);因而使 這類織布印染用色素，也可以廣泛的應用於電子工業之具 有附加價値的資訊儲存媒體中。花青色素隨結構的不同， 而可涵蓋UV/Visible/IR等感光範圍。因此，花青色素 也可作爲目前半導體製程上之光阻層及電子工業上之光學 資訊儲存媒體。 1967年，〗· H_ Lupinski等人首先合成出花青TCNQ 錯合物色素（cyanine TCNQ complex)(Tetracyanoquino_ dimethan Derivatives of Cyanine Dyes, V〇l. 3，ρ·241 〜250, Molecular Crystals，Great Britain，1967);於 1981 年 Law 等人首度將花青色素（3,3f-diethyl-12-acetyl-thiatetracyanine perchlorate)應用於光碟製作上（Κ· Y. Law， Ρ· S. Vincett，and G· Ε· Johnson，Appl· Phys· Lett” 39, 718(1981))。選擇此類有機色素的主要原因是爲配合使用 近紅外光雷射讀寫頭。其製造的方法是將花青色素與PVAc 相混，再利用旋轉塗佈（spin coating)的方法製作成光碟片。 隨花青色素在光學記錄材料的應用成功，爾後即不斷地有 不同的花青結構被用來作此用途的開發，如，美國專利第 5,019,476 號案、第 5,292,615 號案、第 5,328,802 號案、 第 5,332,608 號案、第 5,424，171 號案、第 5,455,094 號案 與第5,579，150號案等。 然而，含有聚甲炔(p〇lymethine)這類結構的有機化合 物皆有著光安定性不佳的問題，尤其是以短波長之雷射光 對光學資訊儲存媒體進行記錄/再生時，會造成資料儲存 9 10435twf.doc 1233937 穩定度、反射率、感光性變差。由於一般花青色素正屬於 此類化合物’因此也有著同樣的問題。所以，必需要開發 出新型具光安定性的花青色素。1999年日本Fujifilm公司 Shinichi Morishima 等人嘗試以摻混（doping)的方式（Shin-ichi Morishima et al·，Jpn. J. Appl. Phys. Vol. 38(1999)， PP.1634-1637)，在色素中加入中性的TCNQ衍生物 (derivative)來增進色素的耐光性，但由於TCNQ對一般有 機溶劑溶解度不佳，使得其摻混在色素配方的含量受到限 制，因而限制其安定效果。1233937 发明, description of the invention (invention delta should be stated: the technical field to which the invention belongs, the prior art, the content, the embodiments and the drawings are briefly explained) the invention belongs to the technology M. The invention relates to an information storage medium, and particularly It is a cyanine TCNQ complex pigment for information storage media. In the prior art, in view of the advancement of the times, the amount of information circulation has also increased significantly, while the circulation of information in Dali requires ~ higher storage density and smaller size, and it is made into a lower Φ_mis ||. Legged lungs do not meet the above requirements', so magnetic storage media have gradually been replaced by optical information storage media. Organic Dye is widely used in optical information storage media due to its light sensitivity. Moreover, organic pigments are currently being actively investigated and applied in various industries. For example, the application of organic pigments includes non-linear optical elements, recording and display of optical disc data, photoresistance, thermal / optical / inductive measurement and indicators, energy conversion and storage, medical and biological, etc. The organic pigments currently used include cyanine pigments, azo pigments, indigo pigments, etc. Among them, the organic pigments that are more suitable as high-density optical information storage media include cyanine pigments. In 1856, Greville Williams first synthesized a cyanine blue (Cyanine blue) (K. Venkataraman (ed.), The Chemistry of Synthetic Dyes, Vol. Π, p. 1143-1186, Academic Press, New York , 1952 ·). Later '1875' Vogei discovered that the flower 8 synthesized by williams 8 10435twf.doc 1233937 Cyan has special sensitizing properties; therefore, this kind of textile printing and dyeing can also be widely used Electronic industry information storage media with additional cost. Depending on the structure, the cyanine pigment can cover UV, Visible, and IR. Therefore, cyanine pigment can also be used as a photoresist layer in the current semiconductor manufacturing process and an optical information storage medium in the electronics industry. In 1967, H. Lupinski et al. First synthesized a cyanine TCNQ complex (Tetracyanoquino_ dimethan Derivatives of Cyanine Dyes, V〇l. 3, ρ · 241 ~ 250, Molecular Crystals, Great Britain, 1967); Law et al. First applied cyanine pigments (3,3f-diethyl-12-acetyl-thiatetracyanine perchlorate) to optical disc production in 1981 (K · Y. Law, P · S. Vincett, and G · E. Johnson, Appl. Phys. Lett "39, 718 (1981)). The main reason for choosing this type of organic pigment is to use a near-infrared laser read-write head. The manufacturing method is to combine cyanine pigment with PVAc Mix and then use spin coating to make optical discs. With the successful application of cyanine pigments in optical recording materials, different cyanine structures have been used for this purpose. For example, US Patent Nos. 5,019,476, 5,292,615, 5,328,802, 5,332,608, 5,424,171, 5,455,094, and 5,579,150, etc. However, they contain polymethyne. (p〇 lymethine) organic compounds with such structures have problems with poor light stability, especially when recording / reproducing optical information storage media with short-wavelength laser light, which can cause data storage 9 10435twf.doc 1233937 stability, reflection The photosensitivity and photosensitivity become worse. Since general cyanine pigments belong to this type of compound, they also have the same problem. Therefore, it is necessary to develop a new type of light-stabilizing cyanine pigments. In 1999, Fujifilm company Shinichi Morishima and others Try to doping (Shin-ichi Morishima et al., Jpn. J. Appl. Phys. Vol. 38 (1999), PP.1634-1637), adding neutral TCNQ derivatives to the pigment (derivative) to improve the light resistance of pigments, but because TCNQ has poor solubility in general organic solvents, its content in pigment formulations is limited, which limits its stabilization effect.
發明內A 爲了解決上述之問題點，本發明之一目的爲提供一種 資訊儲存媒體用花青TCNQ錯合物色素，此種色素在短波 長（200〜400nm)及近紅外光區（800〜1000am)對光具高吸 收度，可抵抗紫外光(UV)及單態氧對色素的破壞。 本發明之一目的爲提供一種資訊儲存媒體用花青 TCNQ錯合物色素，此種色素具有高氧化電位（Oxidation potential)，可以防止染料被氧化。 本發明之一目的爲提供一種資訊儲存媒體用花青 TCNQ錯合物色素，此種色素在波長範圍300〜800nm可 調變之主吸收位置，且具有高螢光量子效率。 本發明之一目的爲提供一種資訊儲存媒體用花青 TCNQ錯合物色素，不須添加任何光安定劑，此花青TCNQ 錯合物色素即具有極佳之光安定性（耐光效果：3000W Xe lamp 照射 1200min，CNR^45dB，光碟在波長 635nm 之 10435twf.doc 1233937Invention A In order to solve the above-mentioned problems, an object of the present invention is to provide a cyanine TCNQ complex pigment for information storage media. The pigment has a short wavelength (200 to 400 nm) and a near infrared light region (800 to 1000 am). ) Has a high absorption of light, can resist ultraviolet light (UV) and singlet oxygen damage to the pigment. An object of the present invention is to provide a cyanine TCNQ complex pigment for an information storage medium. The pigment has a high oxidation potential and can prevent the dye from being oxidized. An object of the present invention is to provide a cyanine TCNQ complex pigment for an information storage medium. The pigment has a main absorption position that can be adjusted in a wavelength range of 300 to 800 nm and has high fluorescence quantum efficiency. An object of the present invention is to provide a cyanine TCNQ complex pigment for information storage media without adding any light stabilizer. This cyanine TCNQ complex pigment has excellent light stability (lightfast effect: 3000W Xe lamp Illumination for 1200min, CNR ^ 45dB, CD-ROM at a wavelength of 635nm, 10435twf.doc 1233937
其中Q及Q'係選自單苯環及雙苯環芳香族之其中之一種； h及R2係選自烷基、芳基酯基團、烷氧基、烷硫基與院 氧硫基所組成之群組；η爲0、1或2之整數；TCNQ、係 爲 7,7’，8,8、四氰基奎諾二甲烷（7,7’，8,8、 tetracyanoquinodimethane)及其衍生物；及 m 表不 1 或 2 之整數。反射層設置於螢光反射層上。第二基板設置於反 射層上。 反射層之材質爲金、銀、鋁、銅、鉻及其合金等所組 成之族群。用於溶解該花青TCNQ錯合物色素（I)之有機溶 劑爲2,2,3,3-四氟丙醇、醇類（alcohol)、酮類（ketone)、醚 類（ether)、氯仿（chloroform)、二氯甲院（dichloromethane) 或二甲基甲醯胺（dimethylformamide，DMF)。螢光記錄層 組成至少包括花青TCNQ錯合物色素、高分子樹脂、界面 貼合膠，但不含光安定劑。 爲讓本發明之上述目的、特徵、和優點能更明顯易懂， 下文特舉較佳實施例，並配合所附圖式，作詳細說明如下： 實施方式 10435twf.doc 12 1233937 於本發明實施例中係以花青色素爲實例作說明。本發 明所揭露的花青TCNQ錯合物色素之製造方法，首先是合 成取代基團甲基（4-碘甲基）苯甲酸酯（methyl(4-iodomethyl)benzoate)。此取代基團 methyl(4-iodomethyl)benzoate 可由 4-氯甲基苯甲醯氯（4- chloromethyl benzoyl chloride)與甲醇在含有D比 0定（pyridine) 的苯溶劑中，於4(TC〜6(TC之溫度下，反應數小時，然後 再以碘化鈉置換氯而得。然後，將此取代基團Hiethyl(4- iodomethyl)benzoate 與 2,3,3-trimethyl-4,5-benzo-3H-indole 置於苯中一起加熱至80°C〜l〇〇°C之溫度，反應3〜8小時 後即可得到 1-(4’-methoxy- carbonyl)-benzyl-2,3,3-trimethyl-4,5-benzo-3H-indolium iodide。接著，合成 1-butanyl-2,3,3-trimethyl indolenine，將 iodidebutane 和 2,3,3-trimethyl indolenine 置於苯中，力口熱至 80°C 〜l〇〇°C 之溫度，反應3〜8小時後即可得l-butanyl-2,3,3-trimethyl indolenine。然後，將 l-(4’-methoxycarbonyl)-benzyl-2,3,3-trimethyl-4,5- benzo-3H-indolium iodide 與 N，N'-Diphenylformamidine置於醋酸酐中，力□熱至10(TC〜120 t：之溫度，反應1〜3小時後即可得到化合物(A)。之後， 再將 l-butanyl-2,3,3-trimethyl indolenine、化合物（A)和醋 酸鈉置於醋酸酐中一起加熱至100〜120°c之溫度下，反應 1〜3小時，然後再以LiTCNQ ( LiTCNQ之合成主要參照 L. R. Melby et al., J. Am. Chem. Soc., 84, 1962, 3374)置 換碘即可得到化合物（B)2-[：Hl，3Dihydr〇-l，l-dimethyl-3- 10435twf.doc 14 1233937 (4f-m ethoxy c arbo ny 1)-benzyl-2H-benze[e]indol-2-yli dene]-l-propenyl]l，l-dimethyl-3butyl-lH indolium TCNQ。 以上述方法合成的新型花青TCNQ錯合物色素（I)皆可 溶解於醇類（如：甲醇、乙醇、異丙醇等）、酮類（如：丙酮、 甲基乙基酮（MEK)等）、醚類（如：乙醚、四氫呋喃 (tetrahydrofuran)等）或氯仿、二氯甲院、DMF等有機溶劑 中，因此可利用噴佈、滾壓塗佈、含浸或旋轉塗佈等施工 法，將本發明的新型花青TCNQ錯合物色素（I)塗佈於基板 上，以形成含花青TCNQ錯合物色素（I)的薄膜。本發明主 要是將TCNQ分子鍵結在花青色素上形成一穩定錯合物 (complex)，因花青TCNQ錯合物比一般花青鹵素、花青 C104、花青PF6錯合物具有較高的氧化電位，也就是說 TCNQ具有較佳之抑制單態氧攻擊花青色素主體之效果， 可提高花青色素對光的穩定性，以解決花青色素須加光安 定劑之困擾。 此外，本發明的新型花青TCNQ錯合物色素除可用作 光學記錄媒體材料外，亦可將其應用於銀鹽相片、複寫及 印刷用之增感劑。 以下’即以實驗例1至實驗例3說明本發明的新型花 青TCNQ錯合物色素（Π )、（Π )、（IV)之製備方法，並以實 驗例4說明使用本發明的新型花青TCnQ錯合物色素製備 之資料儲存媒體。 〔實驗例1〕 10435twf.doc 製備合成 2-[3-(l，3Dihydi*o-l，l-dimethyl-3(4L niethoxycarbonyl)-benzyl)-2H-benze[e]indol-2-ylidene]-l-prope-nyl]-l，l-dimethyl-3-butyl-ΙΗ-indolium TCNQ(簡稱： SL-TCNQ)之SL花青TCNQ錯合物色素，其結構式如第2 圖之花青TCNQ錯合物色素（Π)，其製備方法包括下列所 述之步驟： (a) methyl(4-iodomethyl)benzoate (簡稱：MIB)之製備 方法，MIB之結構式如第3圖所示·· 取 1.89g 的 4-chloromethylbenzoyl chloride(TCI 化藥) 及〇.32g甲醇以25ml苯溶解之，接著加入0.79lg的 pyridine，並加熱至45之溫度、反應1〜3小時，經過濾、 濃縮產物後可得到白色固體。 將此白色固體溶於丙酮中並加入1.5Og的峨化鈉，保 持反應溫度爲40°C、反應3〜5小時。過濾產物，並以： 氯甲烷和水萃取後，蒸乾產物可得淡黃色固體。淡黃色_ 體之產率90%，熔點(m.p.)爲67°C。 (b) 1 麵butyl-2,3,3-trimethyl indoleninium iodide (簡稱 BII)之製備方法，BII化合物之結構式如第4圖所示： 取 iodidebutane (TCI 化藥）2.76g 及 2,3,3-trimethyi indolenine (TCI 化藥）2.38 g 以苯爲溶劑，在 80°C -85°C 之 溫度下加熱4小時。反應完後，減壓濃縮產物，並以乙酸 乙酯作再結晶可得淡黃色產物。此淡黃色產物之產率胃 85%，熔點（m.p·)爲 102°C。 10435twf.doc 16 1233937 (c) i-(4f-meth〇xycarb〇nyl) benzyl - 2, 3, 3 - trimethyl-4, 5- benzo-3H indoleninium iodide (簡稱：MBTI)之製備方 法，MBTI化合物之結構式如第5圖所示： 耳又 MIB 2.76g 及 2，3,3-trimethyl-4,5-benzo-3H-indole (TCI化藥）1.75 g以苯爲溶劑’在80°C-9〇°C之溫度下，反 應4〜8小時。反應完後’減壓濃縮產物’並以甲醇作再 結晶可得淡灰色產物。此淡灰色產物之產率爲75% ’熔點 (m.p.)爲 120T：。 (d) 中間產物（A)之製備方法，中間產物（A)之結構式 如第6圖所示： 耳又 6.16 g l-(4’-methoxycarbonyl)benzyl-2,3,3-tri-methyl-4,5-benzo-3H-indoleninium iodide 及 1.12g N，N'-Di-phenylformamidine 在20ml之醋酸酐中反應，加熱至 100°C〜120°C之溫度，反應2小時，冷卻後加入至1.41 g之 過氯酸鈉水溶液中便有固體產生，以二氯甲烷溶解之並用 水洗數次，濃縮產物後，再用乙醇作再結晶，可得中間產 物(A)。此中間產物(A)之產率爲70%。 (e) 2-[3-( 1,3 Dihydro-151 -dimethyl-3(4f-methoxycarbonyl) - benzyl)-2H-benze[e]indol-2-ylidene]-1 -propenyl]-l，l-dimethyl-3butyl-lH indolium TCNQ (Π)之製 備方法，花青TCNQ錯合物色素（Π)之結構式如第2圖所 示： 取 0.02mole 的 1-(4’-methoxycarbonyl)2,3,3· trimethyl-4,5-benzo-3H-indole 及 O.Olmole 的 ethyl 17 10435twf.doc 1233937 orthoformate (TCI化藥）置於雙頸瓶中，以pyridine溶解之， 並保持反應溫度於ll〇°C〜12CTC之溫度，攪拌1〜3小時， 待反應完後，將反應溶液卻後倒入加有1.24 g之LiTCNQ 水溶液中即有固體產生。之後，再用甲醇作再結晶，可得 日首紅色結晶（K )。日苜紅色結晶（ΙΠ )之產率爲70%，溶點（m_p.) 爲190°C。第7圖所繪示爲花青TCNQ錯合物色素（Π)之 UV/Visible/IR吸收光譜分析圖，花青TCNQ錯合物色 素（Π )之最大吸收波長爲Xmax(EtOH)= 568 nm。第8圖及 第9圖則分別爲繪示花青TCNQ錯合物色素（Π)之紅外線 光譜(IR)分析圖及熱重量分析圖（10°C / min)。 〔實驗例2〕 製備合成 l-(4’-methoxycarbonyl) benzyl -3,3-trimethyl-3,3-dimethyl-1 ,-(45-methoxylcarbonyl)benzyl- 3’，3-dimethyllindo-2,2’麵trimethineTCNQ(簡稱：S-TCNQ) 之S花青TCNQ錯合物色素，其結構式如第10圖之花青 TCNQ錯合物色素（瓜），其製備方法包括下列所述之步驟： (a)首先合成取代基 Methyl(4-iodomethyl)benzoate (MIB)，取 0.01mole(1.8904g)的 4_Chloromethyl benzoyl chloride(TCI 化藥）及 0.01mole(0.3204g)Methanol 以苯溶解 之，接著加入 0.01mole(0.7910g)pyridine，並加熱至 40°C 之溫度，反應3小時，經過濾、濃縮產物後可得白色固體。 接著，將白色固體溶於丙酮中並加入1.5g的碘化鈉後，加 熱至4(TC之溫度，攪拌3小時，產物經過濾、以二氯甲烷 與水萃取、濃縮後可得淡黃色產物。 18 10435twf.doc 1233937 (b) 1-(4 ’ 疆methoxy carbonyl )bezy 1-2，3,3-trimethyl- 4,5-benzo-3H-indole 之製備方法： 取 O.Olmole 的 Methyl(4-iodomethyl)benzoate (MIB) 與 O.Olmole 的 2,3,3-trimethyl-4,5-benzo-3H-indole (TCI 化 藥）以MEK爲溶劑，並加熱至80°C之溫度，反應3小時， 待反應完後，過濾濃縮、並以乙酸乙酯作再結晶可得白色 結晶物。 (c) 1 - (4’-methoxy carbonyl )-benzy 1-3，3-trimethyl -3,3-di methyl -1 ,-(4,-methoxylcarbonyl)benzyl-3 \3-dimethyllindo -2,2’-trimethine TCNQ 之製備方法： 取 0.02mole 的 l-(4’-methoxycarbonyl)2,3,3-trimethyl-4,5-benzo-3H-indole 及 O.Olmole 的 ethyl orthoformate (TCI 化藥）以pyridine溶解之，並加熱至ll〇°C〜120°C之溫度， 反應1〜3小時。將反應溶液卻後倒入加有1.24 g之 LiTCNQ水溶液即有固體產生，之後再用甲醇作再結晶， 可得暗紅色結晶（ΙΠ)。暗紅色結晶（1Π)之產率爲73%，熔 點（m.p·)爲178°C。第11圖所繪示爲花青TCNQ錯合物色 素（m)之UV/Visible/IR吸收光譜分析圖，其最大吸收 波長爲Xmax(EtOH)=551nm。第12圖及第13圖則分別爲 繪示花青TCNQ錯合物色素（ΙΠ)之紅外線光譜(IR)分析圖 及熱重量分析圖（10°C / min)。 〔實施例3〕 製備合成 l-(4"-methoxycarbonyl)-benzyl-3,3-di-methyl -1 ,-(4ff-methoxycarbonyl)-benzyl-3',3f-dimethyllindo- 19 10435twf.doc 1233937 2,2’-pentamethiiie TCNQ之花青TCNQ錯合物色素，其結 構式如第14圖所示之花青TCNQ錯合物色素（IV)，其製 備方法包括下列所述之步驟： (a) 首先合成取代基 methyl(4-iodomethyl)benzoate， 然後合成 1-(4’_methoxycarbonyl)benzyl，2,3,3-trimethyl indoleninium iodide，最後再與 3-anilinoacrylaldehyde anil 反應而得結構（IV)的色素。 (b) methyl(4-iodomethyl)benzoate(簡稱：MIB)之製備 方法，MIB之結構式如第3圖所示： 取 1.89g 的 4-chloromethylbenzoyl chloride (TCI 化藥） 及0.32g甲醇以25ml苯溶解之，接著加入0.791g的 pyridine，並加(熱至40°C之溫度、反應3小時，經過濾、 濃縮產物後可得白色固體。將此白色固體溶於丙酮中並加 入1.50g的碘化鈉，加熱至40°C之溫度、反應3小時，過 濾產物，並以二氯甲烷和水萃取後，蒸乾產物可得淡黃色 固體。淡黃色固體之產率90%，熔點（m.p.)爲67°C。 (c) 1-(4f-methoxycarbonyl) benzyl - 2, 3, 3- trimethyl -4，5- benzo-3H indoleninium iodide (簡稱：MBTI)之製備方 法，MBTI化合物之結構式如第5圖所示： 取 0.276g methyl(4-iodomethyl)benzoate 及 1.752 g 2,3,3-trimethyl indolenine ( TCI 化藥）以苯爲溶劑，在 80°C -85°C之溫度下，反應6小時。反應完後，減壓濃縮產物， 以乙酸乙酯作再結晶可得淡黃色產物。此淡黃色產物之產 率爲 71%，熔點（m.p.)爲 109t：。 10435twf.doc 20 1233937 (d) 1-(4M-methoxycarbonyl) benzyl - 3, 3 - dimethyl-Γ-(4’’-methoxycarbonyl)benzyl-3’，3’-dimethyllindo-2， 2f- pentamethineTCNQ(DI)的製備方法： 取 6.16 g l-(4'-methoxycarbonyl)benzyl-2,3,3-tri-methyl-indoleninium iodide、2.85 g 3-anilinoacrylaldehyde anil (TCI化藥）與1.64 g酢酸鈉在20 ml酢酸酐中反應， 加熱至l〇〇°C之溫度，反應2小時。使結果反應混合物冷 卻後，加入1.41 g之LiTCNQ水溶液中以使固體產生， 以二氯甲烷溶解之並用水洗數次，濃縮、再用乙醇作再結 晶，可得暗綠色結晶。此暗綠色結晶之產率爲70%，熔點 (m.p.)爲201°C。第15圖所繪示爲該花青TCNQ錯合物色 素（IV)之UV/Visible/IR吸收光譜分析圖，其最大吸收 波長爲Xmax (EtOH)= 649 rnn。第16圖與第17圖分別爲 繪示花青TCNQ錯合物色素（IV)之紅外線光譜(IR)分析圖 及熱重量分析圖（l〇°C / min)。 〔實驗例4〕 可錄式光碟片的製作： 花青TCNQ錯合物色素(I)，例如是花青TCNQ錯合物 色素（ΙΠ)與TCNQ錯合物色素（IV)以20 : 1之比例溶解於 例如是 2,2,3,3 -四氟丙醇（2,2,3,3-tetrafluoropropanol)之溶 劑中，以形成均勻的溶液。然後以旋轉塗佈之方式將上述 花青TCNQ錯合物色素塗佈於空白基板上。舉例來說，整 個旋轉塗佈製程如下：塗佈工程：30〜500 rpm，2〜10秒； 甩開工程：1000〜3000 rpm，10〜30秒；烘乾工程：2000 10435twf.doc 1233937 〜5000 rpm，10〜30秒。塗佈於空白基板上的花青TCNQ 錯合物色素層之厚度較佳爲500A〜2000A。接著，於花青 TCNQ錯合物色素層上鍍上一層金、銀、鋁、銅、鉻或其 合金作爲反射層。反射層之厚度較佳爲500A〜1000A。之 後，於已鍍上反射層及記錄層的基板上利用習知的方法例 如是旋轉塗佈法、網印法及熱融膠法等貼合另一片爲空白 基板，而成爲一片高密度可錄式光碟片。 舉例來說，以本發明之花青TCNQ錯合物色素（Π)、 花青TCNQ錯合物色素（瓜）與花青TCNQ錯合物色素（IV) 分別製作資訊儲存媒體時，花青TCNQ錯合物色素（Π)、 花青TCNQ錯合物色素（瓜）與花青TCNQ錯合物色素（IV) 之重量百分比爲0.5%〜20%，較佳爲2%〜10%。然而， 花青TCNQ錯合物色素（Π)相對於全部溶液（包括花青 TCNQ錯合物色素（Π )、花青TCNQ錯合物色素（IV)及溶 劑）的重量百分比爲0.5%〜10%，較佳爲1%〜5%。 舉例來說，以本發明之花青TCNQ錯合物色素（Π)與 花青TCNQ錯合物色素（IV)之混合物製作資訊儲存媒體 時，花青TCNQ錯合物色素（IV)相對於花青TCNQ錯合物 色素（Π )之重量百分比爲0.5%〜20%，較佳爲2%〜10%。 然而，花青TCNQ錯合物色素（Π )相對於全部溶液(包括花 青TCNQ錯合物色素（Π )、花青TCNQ錯合物色素（IV)及 溶劑）的重量百分比爲0.5%〜10%，較佳爲1 %〜5%。 舉例來說，以本發明之花青TCNQ錯合物色素（m)與 花青TCNQ錯合物色素（IV)之混合物製作資訊儲存媒體 10435twf.doc 22 1233937 時，花青TCNQ錯合物色素（IV)相對於花青TCNQ錯合物 色素（m )的重量百分比爲0.5%〜20%，較佳爲2%〜10%。 然而’花青TCNQ錯合物色素（ΙΠ)相對於全部溶液（包括花 青TCNQ錯合物色素（瓜）、花青TCNQ錯合物色素（IV)及 溶劑）的重量百分比爲0.5%〜10%，較佳爲1%〜5%。 以本發明之花青TCNQ錯合物色素（I)製作資訊儲存媒 體時，其中用於溶解花青TCNQ錯合物色素（I)之有機溶劑 可選自下列化合物其中之一 ·· 2,2,3,3-四氟丙醇、醇類 (alcohol)、嗣類（ketone)、醚類(ether)、氯仿（chloroform)、 二氯甲院（dichloromethane)、DMF(dimethylformamide) 〇 第18圖所繪示爲花青TCNQ錯合物色素（m)與花青 TCNQ錯合物色素（IV)混合塗佈於空白基板之UV/Visible /IR吸收光譜分析圖。 如第18圖所示，此類化合物在最大波長λ = 200nm〜 400mn紫外光區及800nm〜lOOOnrn近紅外光區都有不錯 的吸收，可將太陽光中具有破壞化學鍵結能力之短波長光 源（波長小於400nm)，透過電荷轉移及放射蛮光的方式， 將能量轉移掉。另外，本發明之花青TCNQ錯合物色素具 有比一般花青色素具有較高之氧化電位，亦即TCNQ具有 較佳之抑制單態氧攻擊花青色素主體之效果。所以，在不 添加任何泛用之光安定劑的情況下，色素即具有優越的光 安定性。Wherein Q and Q 'are selected from one of monophenyl ring and biphenyl ring aromatics; h and R2 are selected from alkyl, aryl ester groups, alkoxy, alkylthio, and oxothio groups. A group consisting of; η is an integer of 0, 1 or 2; TCNQ is 7,7 ', 8,8, tetracyanoquinodimethane (7,7', 8,8, tetracyanoquinodimethane) and its derivatives And m represents an integer of 1 or 2. The reflective layer is disposed on the fluorescent reflective layer. The second substrate is disposed on the reflective layer. The material of the reflective layer is a group consisting of gold, silver, aluminum, copper, chromium and its alloys. The organic solvents used to dissolve the cyanine TCNQ complex pigment (I) are 2,2,3,3-tetrafluoropropanol, alcohols, ketones, ethers, chloroform (Chloroform), dichloromethane, or dimethylformamide (DMF). The composition of the fluorescent recording layer includes at least a cyanine TCNQ complex pigment, a polymer resin, and an interface adhesive, but does not contain a light stabilizer. In order to make the above-mentioned objects, features, and advantages of the present invention more comprehensible, the following exemplifies preferred embodiments and the accompanying drawings to describe them in detail as follows: Embodiment 10435twf.doc 12 1233937 In the embodiment of the present invention The middle line uses cyanine pigment as an example. The method for producing the cyanine TCNQ complex pigment disclosed in the present invention firstly synthesizes a substituent group methyl (4-iodomethyl) benzoate. The substitution group methyl (4-iodomethyl) benzoate can be obtained by using 4-chloromethyl benzoyl chloride and methanol in a benzene solvent containing pyridine at 4 (TC ~ 6 (At TC, react for several hours, and then replace the chlorine with sodium iodide. Then, this substitution group Hiethyl (4- iodomethyl) benzoate and 2,3,3-trimethyl-4,5-benzo- 3H-indole is placed in benzene and heated to 80 ° C ~ 100 ° C. After 3 ~ 8 hours of reaction, 1- (4'-methoxy-carbonyl) -benzyl-2,3,3- trimethyl-4,5-benzo-3H-indolium iodide. Then, synthesize 1-butanyl-2,3,3-trimethyl indolenine, put iodidebutane and 2,3,3-trimethyl indolenine in benzene, and heat to 80 ° C ~ 100 ° C, l-butanyl-2,3,3-trimethyl indolenine can be obtained after 3 ~ 8 hours of reaction. Then, l- (4'-methoxycarbonyl) -benzyl-2,3 , 3-trimethyl-4,5-benzo-3H-indolium iodide and N, N'-Diphenylformamidine are placed in acetic anhydride and heated to a temperature of 10 (TC ~ 120 t: temperature, after 1 to 3 hours of reaction) Compound (A) is obtained. After that, l-butanyl-2,3,3-trimethyl indolenine, compound (A) and sodium acetate are heated together in acetic anhydride to a temperature of 100 ~ 120 ° c, and reacted for 1 ~ 3 hours, and then LiTCNQ (LiTCNQ of The synthesis mainly refers to LR Melby et al., J. Am. Chem. Soc., 84, 1962, 3374), and the compound (B) 2-[: Hl, 3Dihydr0-1, l-dimethyl-3- can be obtained by replacing iodine. 10435twf.doc 14 1233937 (4f-m ethoxy c arbo ny 1) -benzyl-2H-benze [e] indol-2-yli dene] -l-propenyl] l, l-dimethyl-3butyl-lH indolium TCNQ. The new cyanine TCNQ complex pigment (I) synthesized by the above methods can be dissolved in alcohols (such as methanol, ethanol, isopropanol, etc.) and ketones (such as acetone, methyl ethyl ketone (MEK)). Etc.), ethers (such as: ether, tetrahydrofuran, etc.) or organic solvents such as chloroform, dichloromethane, DMF, etc., therefore, construction methods such as spraying, roll coating, impregnation or spin coating can be used. The novel cyanine TCNQ complex pigment (I) of the present invention is coated on a substrate to form a thin film containing the cyanine TCNQ complex pigment (I). The present invention mainly combines TCNQ molecules with cyanine pigments to form a stable complex. The cyanine TCNQ complex is higher than the general cyanine halogen, cyanine C104, and cyanine PF6 complexes. The oxidation potential of TCNQ has a better effect of inhibiting singlet oxygen from attacking the main body of cyanine pigment, and can improve the stability of cyanine pigment to light, so as to solve the problem that cyanine pigment must be added with light stabilizer. In addition, the novel cyanine TCNQ complex pigment of the present invention can be used as an optical recording medium material, and it can also be used as a sensitizer for silver salt photographs, copying and printing. In the following, the preparation methods of the new cyanine TCNQ complex pigments (Π), (Π), and (IV) of the present invention will be described in Experimental Examples 1 to 3, and Experimental Example 4 will be used to explain the use of the novel flowers of the present invention. A data storage medium for the preparation of blue TCnQ complex pigments. [Experimental Example 1] 10435twf.doc Preparation and synthesis of 2- [3- (l, 3Dihydi * ol, l-dimethyl-3 (4L niethoxycarbonyl) -benzyl) -2H-benze [e] indol-2-ylidene] -l- prope-nyl] -l, l-dimethyl-3-butyl-ΙΗ-indolium TCNQ (abbreviation: SL-TCNQ) is an SL cyanine TCNQ complex pigment with a structural formula as shown in Figure 2 Pigment (Π), the preparation method includes the following steps: (a) The preparation method of methyl (4-iodomethyl) benzoate (abbreviation: MIB), the structural formula of MIB is shown in Figure 3 ... Take 1.89g of 4-chloromethylbenzoyl chloride (TCI chemical) and 0.32 g of methanol were dissolved in 25 ml of benzene, and then 0.79 lg of pyridine was added, and heated to a temperature of 45 for 1 to 3 hours. After filtering and concentrating the product, a white solid was obtained . This white solid was dissolved in acetone and 1.50 g of sodium arsenide was added, and the reaction temperature was maintained at 40 ° C for 3 to 5 hours. The product was filtered and extracted with: methyl chloride and water, and the product was evaporated to give a pale yellow solid. The yield of light yellow body was 90%, and the melting point (m.p.) was 67 ° C. (b) A method for preparing 1-sided butyl-2,3,3-trimethyl indoleninium iodide (BII for short). The structural formula of the BII compound is shown in Figure 4: Take 2.76 g of iodidebutane (TCI chemical) and 2,3, 3-trimethyi indolenine (TCI chemical) 2.38 g of benzene as a solvent, heated at a temperature of 80 ° C -85 ° C for 4 hours. After the reaction, the product was concentrated under reduced pressure and recrystallized from ethyl acetate to obtain a pale yellow product. The yield of this pale yellow product was 85% stomach and the melting point (m.p.) was 102 ° C. 10435twf.doc 16 1233937 (c) i- (4f-meth〇xycarb〇nyl) benzyl-2, 3, 3-trimethyl-4, 5- benzo-3H indoleninium iodide (abbreviation: MBTI) The structural formula is shown in Figure 5: Ear and MIB 2.76g and 2,3,3-trimethyl-4,5-benzo-3H-indole (TCI chemical medicine) 1.75 g with benzene as a solvent at 80 ° C-9 The reaction was performed at a temperature of 0 ° C for 4 to 8 hours. After the reaction, the product was 'concentrated under reduced pressure' and recrystallized from methanol to obtain a pale gray product. The yield of this pale gray product was 75%. The melting point (m.p.) was 120T :. (d) Preparation method of intermediate product (A), the structural formula of intermediate product (A) is shown in Fig. 6: 6.16 g l- (4'-methoxycarbonyl) benzyl-2,3,3-tri-methyl -4,5-benzo-3H-indoleninium iodide and 1.12 g of N, N'-Di-phenylformamidine are reacted in 20 ml of acetic anhydride, heated to a temperature of 100 ° C ~ 120 ° C, and reacted for 2 hours. After cooling, add to A solid was produced in 1.41 g of an aqueous sodium perchlorate solution, which was dissolved in dichloromethane and washed several times with water. After concentrating the product, ethanol was used for recrystallization to obtain an intermediate product (A). The yield of this intermediate product (A) was 70%. (e) 2- [3- (1,3 Dihydro-151 -dimethyl-3 (4f-methoxycarbonyl)-benzyl) -2H-benze [e] indol-2-ylidene] -1 -propenyl] -l, l- Preparation method of dimethyl-3butyl-lH indolium TCNQ (Π), the structural formula of cyanine TCNQ complex pigment (Π) is shown in Figure 2: Take 0.02mole of 1- (4'-methoxycarbonyl) 2,3, 3. · trimethyl-4,5-benzo-3H-indole and ethyl 17 10435twf.doc 1233937 orthoformate (TCI chemical) of O. Olmole were placed in a double-necked flask, and dissolved in pyridine, and the reaction temperature was maintained at 110 ° At a temperature of C ~ 12CTC, stir for 1 ~ 3 hours. After the reaction is completed, pour the reaction solution into a 1.24 g LiTCNQ aqueous solution and a solid will be produced. After that, methanol was used for recrystallization to obtain Japanese first red crystals (K). The yield of Japanese red clover (II) was 70%, and the melting point (m_p.) Was 190 ° C. Figure 7 shows the UV / Visible / IR absorption spectrum of the cyanine TCNQ complex pigment (Π). The maximum absorption wavelength of the cyanine TCNQ complex pigment (Π) is Xmax (EtOH) = 568 nm . Figures 8 and 9 are the infrared spectrum (IR) analysis chart and thermogravimetric analysis chart (10 ° C / min) of the cyanine TCNQ complex pigment (Π), respectively. [Experimental Example 2] Preparation and synthesis of l- (4'-methoxycarbonyl) benzyl -3,3-trimethyl-3,3-dimethyl-1,-(45-methoxylcarbonyl) benzyl- 3 ', 3-dimethyllindo-2,2' The tricyanine TCNQ complex pigment of trimethineTCNQ (abbreviation: S-TCNQ) has the structural formula as shown in figure 10 of the cyanine TCNQ complex pigment (melon). The preparation method includes the following steps: (a ) First synthesize the substituent Methyl (4-iodomethyl) benzoate (MIB), take 0.01mole (1.8904g) of 4_Chloromethyl benzoyl chloride (TCI chemical) and 0.01mole (0.3204g) Methanol to dissolve it in benzene, then add 0.01mole ( 0.7910g) pyridine, heated to a temperature of 40 ° C, and reacted for 3 hours. After filtering and concentrating the product, a white solid was obtained. Next, the white solid was dissolved in acetone and 1.5 g of sodium iodide was added, followed by heating to 4 ° C. and stirring for 3 hours. The product was filtered, extracted with dichloromethane and water, and concentrated to obtain a light yellow product. 18 10435twf.doc 1233937 (b) 1- (4 'Xinjiang methoxy carbonyl) bezy 1-2,3,3-trimethyl- 4,5-benzo-3H-indole Preparation method: Take M.O. -iodomethyl) benzoate (MIB) and 2,3,3-trimethyl-4,5-benzo-3H-indole (TCI chemical) of O. Olmol use MEK as a solvent and heat to 80 ° C to react 3 After the reaction was completed, it was filtered and concentrated, and recrystallized with ethyl acetate to obtain white crystals. (C) 1-(4'-methoxy carbonyl) -benzy 1-3,3-trimethyl -3,3- di methyl -1,-(4, -methoxylcarbonyl) benzyl-3 \ 3-dimethyllindo -2,2'-trimethine TCNQ Preparation method: Take 0.02mole of l- (4'-methoxycarbonyl) 2,3,3-trimethyl -4,5-benzo-3H-indole and ethyl orthoformate (TCI chemical) of O. Olmole are dissolved in pyridine and heated to a temperature of 110 ° C to 120 ° C for 1 to 3 hours. The reaction solution is But then poured into Canada There is 1.24 g of LiTCNQ aqueous solution to produce solids, and then use methanol for recrystallization to obtain dark red crystals (ΙΠ). The yield of dark red crystals (1Π) is 73%, and the melting point (mp ·) is 178 ° C. Figure 11 shows the UV / Visible / IR absorption spectrum of the cyanine TCNQ complex pigment (m). Its maximum absorption wavelength is Xmax (EtOH) = 551nm. Figures 12 and 13 are respectively In order to show the infrared spectrum (IR) analysis chart and thermogravimetric analysis chart (10 ° C / min) of the cyanine TCNQ complex pigment (III). [Example 3] Preparation and synthesis of l- (4 " -methoxycarbonyl)- benzyl-3,3-di-methyl -1,-(4ff-methoxycarbonyl) -benzyl-3 ', 3f-dimethyllindo- 19 10435twf.doc 1233937 2,2'-pentamethiiie TCNQ cyanine TCNQ complex pigment, which The cyanine TCNQ complex pigment (IV), whose structural formula is shown in Figure 14, includes the following steps: (a) Firstly synthesize the substituent methyl (4-iodomethyl) benzoate, and then synthesize 1- ( 4'_methoxycarbonyl) benzyl, 2,3,3-trimethyl indoleninium iodide, and finally reacted with 3-anilinoacrylaldehyde anil to obtain the structure (IV) Su. (b) Preparation method of methyl (4-iodomethyl) benzoate (abbreviation: MIB). The structural formula of MIB is shown in Figure 3. Take 1.89g of 4-chloromethylbenzoyl chloride (TCI chemical) and 0.32g of methanol in 25ml of benzene. After dissolving, 0.791 g of pyridine was added, and heated to a temperature of 40 ° C for 3 hours. After filtering and concentrating the product, a white solid was obtained. This white solid was dissolved in acetone and 1.50 g of iodine was added. Sodium chloride, heated to a temperature of 40 ° C, reacted for 3 hours, filtered the product, and extracted with dichloromethane and water, and evaporated to dryness to obtain a pale yellow solid. The yield of the pale yellow solid was 90%, melting point (mp) It is 67 ° C. (C) 1- (4f-methoxycarbonyl) benzyl-2, 3, 3- trimethyl -4,5-benzo-3H indoleninium iodide (abbreviation: MBTI). Figure 5 shows: Take 0.276g of methyl (4-iodomethyl) benzoate and 1.752g of 2,3,3-trimethyl indolenine (TCI chemical) with benzene as the solvent and react at a temperature of 80 ° C -85 ° C. 6 After the reaction was completed, the product was concentrated under reduced pressure and recrystallized from ethyl acetate to obtain a pale yellow product. The yield of the color product was 71%, and the melting point (mp) was 109 t: 10435twf.doc 20 1233937 (d) 1- (4M-methoxycarbonyl) benzyl-3, 3-dimethyl-Γ- (4 ''-methoxycarbonyl) benzyl -3 ', 3'-dimethyllindo-2, 2f- pentamethineTCNQ (DI): 6.16 g of l- (4'-methoxycarbonyl) benzyl-2,3,3-tri-methyl-indoleninium iodide, 2.85 g 3 -anilinoacrylaldehyde anil (TCI) is reacted with 1.64 g of sodium gallate in 20 ml of gallic anhydride, heated to 100 ° C for 2 hours. After the resulting reaction mixture is cooled, 1.41 g of a LiTCNQ aqueous solution is added to The solid was generated, dissolved in dichloromethane and washed with water several times, concentrated, and then recrystallized with ethanol to obtain dark green crystals. The yield of this dark green crystals was 70%, and the melting point (mp) was 201 ° C. Figure 15 shows the UV / Visible / IR absorption spectrum analysis of the cyanine TCNQ complex pigment (IV). The maximum absorption wavelength is Xmax (EtOH) = 649 rnn. Figures 16 and 17 show the infrared spectrum (IR) analysis chart and thermogravimetric analysis chart (10 ° C / min) of the cyanine TCNQ complex pigment (IV), respectively. [Experimental Example 4] Production of recordable optical discs: cyanine TCNQ complex pigment (I), for example, cyanine TCNQ complex pigment (IΠ) and TCNQ complex pigment (IV) The ratio is dissolved in a solvent such as 2,2,3,3-tetrafluoropropanol (2,2,3,3-tetrafluoropropanol) to form a uniform solution. Then, the above cyanine TCNQ complex pigment was applied on a blank substrate by spin coating. For example, the entire spin coating process is as follows: coating process: 30 ~ 500 rpm, 2 ~ 10 seconds; throw-off process: 1000 ~ 3000 rpm, 10 ~ 30 seconds; drying process: 2000 10435twf.doc 1233937 ~ 5000 rpm, 10 ~ 30 seconds. The thickness of the cyanine TCNQ complex pigment layer applied on the blank substrate is preferably 500A to 2000A. Next, the cyanine TCNQ complex pigment layer is plated with a layer of gold, silver, aluminum, copper, chromium, or an alloy thereof as a reflective layer. The thickness of the reflective layer is preferably 500A to 1000A. After that, on a substrate that has been coated with a reflective layer and a recording layer, another blank substrate is bonded to the substrate by a conventional method such as spin coating method, screen printing method, and hot-melt adhesive method, thereby becoming a high-density recordable substrate. Discs. For example, when an cyanine TCNQ complex pigment (Π), a cyanine TCNQ complex pigment (melon), and a cyanine TCNQ complex pigment (IV) are separately used to create an information storage medium, The weight percentage of the complex pigment (Π), the cyanine TCNQ complex pigment (melon), and the cyanine TCNQ complex pigment (IV) is 0.5% to 20%, preferably 2% to 10%. However, the weight percentage of the cyanine TCNQ complex pigment (Π) to all the solutions (including the cyanine TCNQ complex pigment (Π), the cyanine TCNQ complex pigment (IV), and the solvent) is 0.5% to 10% by weight. %, Preferably 1% to 5%. For example, when a mixture of the cyanine TCNQ complex pigment (Π) and the cyanine TCNQ complex pigment (IV) of the present invention is used to make an information storage medium, the cyanine TCNQ complex pigment (IV) is The weight percentage of the blue TCNQ complex pigment (Π) is 0.5% to 20%, preferably 2% to 10%. However, the weight percentage of the cyanine TCNQ complex pigment (Π) to all solutions (including the cyanine TCNQ complex pigment (Π), the cyanine TCNQ complex pigment (IV), and the solvent) is 0.5% to 10% by weight. %, Preferably 1% to 5%. For example, when the information storage medium 10435twf.doc 22 1233937 is prepared from a mixture of the cyanine TCNQ complex pigment (m) and the cyanine TCNQ complex pigment (IV) of the present invention ( IV) The weight percentage of the cyanine TCNQ complex pigment (m) is 0.5% to 20%, preferably 2% to 10%. However, the weight percentage of 'cyanine TCNQ complex pigment (III) to all solutions (including cyanine TCNQ complex pigment (melon), cyanine TCNQ complex pigment (IV), and solvent) is 0.5% to 10% by weight %, Preferably 1% to 5%. When using the cyanine TCNQ complex pigment (I) of the present invention to make an information storage medium, the organic solvent used to dissolve the cyanine TCNQ complex pigment (I) may be selected from one of the following compounds ... 2,2 3,3-tetrafluoropropanol, alcohol, ketone, ether, chloroform, dichloromethane, DMF (dimethylformamide). Figure 18 A UV / Visible / IR absorption spectrum analysis diagram of a cyanine TCNQ complex pigment (m) and a cyanine TCNQ complex pigment (IV) mixed and coated on a blank substrate is shown. As shown in Figure 18, these compounds have good absorption in the maximum wavelength λ = 200nm ~ 400mn ultraviolet light region and 800nm ~ 100Onrn near-infrared light region, which can be a short-wavelength light source that has the ability to destroy chemical bonding in sunlight The wavelength is less than 400nm), and the energy is transferred by means of charge transfer and irradiated light. In addition, the cyanine TCNQ complex pigment of the present invention has a higher oxidation potential than ordinary cyanine pigments, that is, TCNQ has a better effect of inhibiting singlet oxygen from attacking the cyanine pigment main body. Therefore, without adding any light stabilizer for general use, the pigment has superior light stability.
第19圖所繪示爲在花青TCNQ錯合物色素（瓜）與花 青TCNQ錯合物色素（IV)上形成光碟片之銀反射層的UV 10435twf.doc 23 1233937 / Visible/IR反射光譜分析圖。此結構的高密度可錄式 光碟片測其反射率對波長的光譜在λ = 635nm附近反射率 皆可達60%以上。 第20圖所繪示爲使用本發明之花青TCNQ錯合物色 素⑴所製作之光碟片的耐光測試實驗之碟片讀寫測試分 析。 第21圖所繪示爲使用花青TCNQ錯合物色素（瓜）與 花青TCNQ錯合物色素（IV)所製作之光碟片的耐光測試實 驗之反射率光譜圖。在第21圖中，本發明的花青TCNQ 錯合物色素可成功的應用於高密度光碟片儲存系統中，並 且在不需要光安定劑下仍擁有極佳之耐光性。 第22圖所繪示爲使用本發明之花青TCNQ錯合物色 素製作之資訊儲存媒體時，該花青TCNQ錯合物色素 (IH)551nm之激發光源所得之螢光光譜。其中該營光記錄 層組成至少包含花青TCNQ錯合物色素（瓜）、高分子樹脂、 界面貼合膠，但不含光安定劑。 本發明之花青TCNQ錯合物色素，在波長爲200nm〜 400nm之紫外光區及800nm〜lOOOnm之近紅外光區都有 不錯的吸收。可將太陽光中具有破壞化學鍵結能力之短波 長光源（波長小於400nm)，透過電荷轉移及放射螢光的方 式’將能量轉移掉。另外，因花青TCNQ錯合物色素比一 般花青鹵素、花青C104、花青？？6錯合物具有較高的氧化 電位，也就是說TCNQ具有較佳之抑制單態氧攻擊花青色 24 10435twf.doc 1233937 素主體之效果’可提高花青色素對光的穩定性，以解決花 青色素須加光安定劑之困擾。 綜上所述，雖然本發明已以較佳實施例揭露如上，然 其並非用以限定本發明，任何熟習此技藝者，在不脫離本 發明之精神和範圍內’當可作各種之更動與潤飾，因此本 發明之保護範圍當視後附之申請專利範圍所界定者爲準。 式簡單說1 第1圖爲繪示本發明花青TCNQ錯合物色素（I)之基本 結構式； 第2圖爲繪示本發明之花青TCNQ錯合物色素（Π )之 結構式； 第3圖爲繪示本發明實驗例中簡稱MIB化合物之結 構式； 第4圖爲繪示本發明實驗例中簡稱BII化合物之結構 式； 第5圖爲繪示本發明合成例中簡稱MBTI化合物之結 構式； 第6圖爲繪示本發明實驗例中反應中間體（A)之結構 式·， 第7圖爲繪示本發明之花青TCNQ錯合物色素（Π )之 UV/Visible/IR吸收光譜分析圖； 第8圖爲繪示本發明之花青TCNQ錯合物色素（Π )之 紅外線光譜(IR)分析圖； 第9圖爲繪示本發明之花青TCNQ錯合物色素（Π )之 10435twf.doc 25 1233937 熱重量分析圖（l〇°C/min); 第10圖爲繪示本發明之花青TCNQ錯合物色素（m) 之結構式； 第11圖爲繪示本發明之花青TCNQ錯合物色素（m )之 UV/Visible/IR吸收光譜分析圖； 第12圖爲繪示本發明之花青TCNQ錯合物色素（m) 之紅外線光譜(IR)分析圖； 第13圖爲繪示本發明之花青TCNQ錯合物色素（m) 之熱重量分析圖（l〇°C/min); 第14圖爲繪示本發明之花青TCNQ錯合物色素（IV) 之結構式； 第15圖爲繪示本發明之花青TCNQ錯合物色素（IV) 之UV/Visible/IR吸收光譜分析圖； 第16圖爲繪示本發明之花青TCNQ錯合物色素（IV) 之紅外線光譜（IR)分析圖； 第17圖爲繪示本發明之花青TCNQ錯合物色素（IV) 之熱重量分析圖（l〇t/min); 第18圖爲繪示本發明之花青TCNQ錯合物色素（瓜） 與花青TCNQ錯合物色素（IV)混合塗佈於空白基板之UV /Visible/IR吸收光譜分析圖； 第19圖爲繪示本發明之花青TCNQ錯合物色素（ΙΠ) 與花青TCNQ錯合物色素（IV)之製作光碟片以銀反射層之 UV/Visible/IR反射光譜分析圖； 第20圖爲繪示本發明之花青TCNQ錯合物色素（ΙΠ) 10435twf.doc 26 1233937 與花青TCNQ錯合物色素（IV)之製作光碟片之耐光測試實 驗之碟片讀寫測試分析； 第21圖爲繪示本發明之花青TCNQ錯合物色素（m) 與花青TCNQ錯合物色素（IV)之製作光碟片之耐光測試實 驗之反射率光譜圖；以及 第22圖爲繪示本發明之花青TCNQ錯合物色素 (m)551nm之激發光源所得之螢光光譜。 10435twf.doc 27Figure 19 shows the UV reflection spectrum of the silver reflective layer of the optical disc formed on the cyanine TCNQ complex pigment (melon) and the cyanine TCNQ complex pigment (IV). 10435twf.doc 23 1233937 / Visible / IR reflection spectrum diagram. The high-density recordable optical disc of this structure has a reflectance-to-wavelength spectrum measured in the vicinity of λ = 635nm, and the reflectance can reach more than 60%. Figure 20 shows the analysis of the disk read-write test of the light resistance test experiment of the optical disc made using the cyanine TCNQ complex cyanine of the present invention. Figure 21 shows the reflectance spectrum of a lightfastness test experiment on an optical disc made using cyanine TCNQ complex pigment (melon) and cyanine TCNQ complex pigment (IV). In Figure 21, the cyanine TCNQ complex pigment of the present invention can be successfully applied to a high-density optical disc storage system, and has excellent light resistance without the need for a light stabilizer. FIG. 22 shows the fluorescence spectrum obtained by using the cyanine TCNQ complex pigment (IH) 551 nm excitation light source when using the information storage medium made of the cyanine TCNQ complex pigment of the present invention. The composition of the Yingguang recording layer includes at least a cyanine TCNQ complex pigment (melon), a polymer resin, and an interface adhesive, but does not contain a light stabilizer. The cyanine TCNQ complex pigment of the present invention has good absorption in the ultraviolet light region with a wavelength of 200 nm to 400 nm and the near infrared light region with a wavelength of 800 nm to 100 nm. A short-wavelength light source (wavelength less than 400nm) in sunlight that has the ability to destroy chemical bonds can be transferred by charge transfer and radiate fluorescence 'to transfer energy away. In addition, because the pigment of cyanine TCNQ complex is more than ordinary cyanine halogen, cyanine C104, cyanine? ? The 6 complex has a higher oxidation potential, which means that TCNQ has a better ability to inhibit singlet oxygen from attacking cyanine 24 10435twf.doc 1233937 The effect of the prime body 'can improve the stability of cyanine pigments to light to solve cyanine Pigments must be troubled with light stabilizers. In summary, although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Retouching, so the scope of protection of the present invention shall be determined by the scope of the attached patent application. Brief description of the formula 1 Figure 1 shows the basic structural formula of the cyanine TCNQ complex pigment (I) of the present invention; Figure 2 shows the structural formula of the cyanine TCNQ complex pigment (Π) of the present invention; Figure 3 shows the structural formula of the abbreviated MIB compound in the experimental examples of the invention; Figure 4 shows the structural formula of the BII compound in the experimental examples of the invention; Figure 5 shows the MBTI compound of the synthetic examples of the invention Figure 6 shows the structural formula of the reaction intermediate (A) in the experimental example of the present invention. Figure 7 shows the UV / Visible / of the cyanine TCNQ complex pigment (Π) of the present invention. IR absorption spectrum analysis diagram; FIG. 8 is an infrared spectrum (IR) analysis diagram showing the cyanine TCNQ complex pigment (Π) of the present invention; FIG. 9 is a diagram showing the cyanine TCNQ complex pigment of the present invention (Π) of 10435twf.doc 25 1233937 thermogravimetric analysis chart (10 ° C / min); FIG. 10 is a structural formula showing the cyanine TCNQ complex pigment (m) of the present invention; FIG. 11 is a drawing Shows the UV / Visible / IR absorption spectrum analysis chart of the cyanine TCNQ complex pigment (m) of the present invention; FIG. 12 shows the cyanine TCNQ of the present invention The infrared spectrum (IR) analysis chart of the complex pigment (m); Figure 13 is a thermogravimetric analysis chart (10 ° C / min) showing the cyanine TCNQ complex pigment (m) of the present invention; Figure 14 is a structural formula showing the cyanine TCNQ complex pigment (IV) of the present invention; Figure 15 is a UV / Visible / IR absorption spectrum analysis showing the cyanine TCNQ complex pigment (IV) of the present invention FIG. 16 is an infrared spectrum (IR) analysis chart showing the cyanine TCNQ complex pigment (IV) of the present invention; FIG. 17 is a view showing the cyanine TCNQ complex pigment (IV) of the present invention; Thermogravimetric analysis chart (10t / min); Figure 18 shows the UV coating of the cyanine TCNQ complex pigment (melon) and the cyanine TCNQ complex pigment (IV) mixed on a blank substrate of the present invention. / Visible / IR absorption spectrum analysis chart; FIG. 19 is a drawing showing a cyanine TCNQ complex pigment (III) and cyanine TCNQ complex pigment (IV) of the present invention Visible / IR reflection spectrum analysis chart; Figure 20 shows the production light of the cyanine TCNQ complex pigment (IV) 10435twf.doc 26 1233937 and the cyanine TCNQ complex pigment (IV) of the present invention Analysis of disc read-write test of light-fastness test experiment of discs; Figure 21 shows the light-fastness of optical discs in which the cyanine TCNQ complex pigment (m) and cyanine TCNQ complex pigment (IV) of the present invention are shown The reflectance spectrum of the test experiment; and FIG. 22 is a fluorescent spectrum obtained by the excitation light source of the cyanine TCNQ complex pigment (m) 551 nm of the present invention. 10435twf.doc 27