TWI402258B - 陽離子化合物、色素化合物及其使用方法以及光資訊記錄媒體 - Google Patents

陽離子化合物、色素化合物及其使用方法以及光資訊記錄媒體 Download PDF

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TWI402258B
TWI402258B TW095141627A TW95141627A TWI402258B TW I402258 B TWI402258 B TW I402258B TW 095141627 A TW095141627 A TW 095141627A TW 95141627 A TW95141627 A TW 95141627A TW I402258 B TWI402258 B TW I402258B
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Taiwan
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group
dye
cation
independently represent
compound
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TW095141627A
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TW200728287A (en
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Kazumi Nii
Tatsuo Mikami
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Fujifilm Corp
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/02Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/04Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
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Description

陽離子化合物、色素化合物及其使用方法以及光資訊記錄媒體
本發明是關於一種新型陽離子化合物(cation compound),其可提供適當之色素化合物作為光資訊記錄媒體的記錄層用色素。而且,本發明是關於一種含有上述陽離子化合物的色素化合物及其使用方法、以及一種含有上述色素化合物作為記錄層用色素的光資訊記錄媒體。上述色素化合物適於用作使用可見雷射光來記錄資訊的可錄式數位多功能光碟(digital versatile disc)(DVD-R)等熱致模式(heat mode)資訊記錄媒體的記錄層用色素。
利用雷射光只能一次性記錄資訊的資訊記錄媒體(光碟)已知有可錄式CD(所謂CD-R)。該可錄式CD與先前CD的製作相比,具有可以合理之價格並迅速提供少量CD的優點,隨著個人電腦(personal computer)的普及,其需求亦亦已增大。CD-R型資訊記錄媒體的代表性構造是將於透明的圓盤狀基板上含有有機色素的記錄層、含有金等金屬的反射層、以及樹脂製保護層,按照上述順序進行層積者,要將資訊記錄至光碟上,可藉由照射近紅外區域之雷射光(通常為780 nm附近波長的雷射光),使記錄層局部性熱變形而進行。另一方面,資訊之讀取(再生)通常可藉由照射與記錄用雷射光相同波長的雷射光,檢測記錄層產生熱變形的部位(記錄部分)與未變形的部位(未記錄部分)的反射率差異而進行。近年來,伴隨個人電腦之高性能化及網際網路之高速化,圖像資訊(尤其是動畫等)變得可操作,更加需要大容量之資訊記錄媒體。作為記錄密度更高的資訊記錄媒體,市售有,為提高記錄密度而以短波長之雷射光將其更加縮小的,稱為可錄式數位多功能光碟(所謂DVD-R)的光碟。上述光碟可製成如下構造:於形成有軌道間距(track pitch)較CD-R之1.6 μm更窄的0.8 μm預刻溝槽(pregroove)的,直徑120 mm或直徑80 mm之透明圓盤狀基板上設置含有色素的記錄層,且通常於該記錄層上進而設置反射層而製成碟片(disk),將兩片該碟片以黏著劑貼合而成的構造;或以該記錄層為內側之方式將該碟片與大致相同尺寸的圓盤狀保護基板以黏著劑進行貼合而成的構造。並且DVD-R可藉由照射可見雷射光(通常為600 nm~700 nm範圍之波長的雷射光),而進行記錄及再生,並可進行較CD-R型光碟更高密度的記錄。又,亦市售有稱為DVD+R的與DVD-R規格類似的光碟。可錄式DVD之資訊記錄媒體與現有CD-R型相比,可記錄數倍之資訊量,因此不僅期望其具有高記錄靈敏度(sensitivity),且因須要快速處理大量資訊,故更期望其即使對於高速記錄的錯誤發生率亦少。而且含有色素之記錄層通常對熱、或光之經時穩定性低,因此期待開發即使經過長時間,對熱、或光亦可維持穩定性能的記錄層。
又,期望可錄式DVD亦與CD-R同樣縮短記錄時間,即記錄速度之高速化,並期望進一步提高可錄式DVD記錄媒體之靈敏度,及改善伴隨寫入雷射之高能量化的寫入精度下降(顫動(jitter)之惡化)。
日本專利特開昭63-209995號公報[專利文獻1]中,揭示有一種於基板上設置有含有氧喏色素(oxonol dye)之記錄層的CD-R型資訊記錄媒體。揭示有一種於分子內以鹽之形式導入有銨的氧喏色素化合物,藉由使用該色素化合物,可長期維持穩定之記錄再生特性。又,日本專利特開平10-109475號公報[專利文獻2]中,揭示有聯吡啶(bipyridinium)作為以鹽之形式而被導入的銨可有效提高耐光性。此處揭示有,色素並不限定於氧喏,各種色素皆有效。又,日本專利特開平10-297103號公報[專利文獻3]中,揭示具有耐紫羅鹼(viologen)性的氧喏色素為有效。又,日本專利特開2000-52658號公報[專利文獻4]、日本專利特開2002-249674號公報[專利文獻5]中,揭示有一種可提供顯示高耐光性及耐久性、且記錄特性良好之光資訊記錄媒體的氧喏色素化合物。又,日本專利特開2002-59652號[專利文獻6]中,揭示有一種混合2種靈敏度不同之色素的技術,其中有關於氧喏色素之揭示。日本專利特開2004-188968號公報[專利文獻7]中揭示有一種特定結構之雙型氧喏色素。
近年來,開發有具有雙層記錄面之DVD-RDL(Double Layer)媒體,其可利用單層媒體(4.7GB)之約1.8倍的單面8.5GB之容量,並與單層型DVD-R同樣正對縮短記錄時間進行研究。DVD-RDL媒體層積有雙層色素層,因此就靈敏度、反射率、顫動等方面而言,期望開發出對構成各層之色素所要求的物性與單層型媒體中所使用之色素相比,更加嚴格且更高性能的色素。
進而,對光資訊記錄媒體之記錄層用色素,除上述物性以外,亦謀求製備色素塗佈液時之溶解性、塗佈液之溶解經時穩定性、使用高濃度塗佈溶液時之塗佈性(塗佈膜平滑性)等製造適應性優異。
於上述情況下,本發明之目的在於提供一種新型色素,其可提供顯示優異靈敏度、顫動及反射率之光資訊記錄媒體,而且具有優異之製造適應性,尤其用作DVD-R媒體用色素時顯示出優異特性。
本發明人等為實現上述目的而不斷進行積極研討,結果發現,若利用由一分子中具有大於等於3個陽離子部分之新型陽離子化合物及陰離子所形成之色素化合物,則可獲得具有優異靈敏度、顫動、反射率之光資訊記錄媒體,而且上述色素化合物不僅製備色素塗佈液時之溶解性、塗佈液之溶解經時穩定性優異,而且塗佈高濃度塗佈溶液時可實現良好的塗佈面狀態,從而完成本發明。
即,作為達成上述目之方法的本發明是關於一種以下述通式(I)所表示之陽離子化合物:
[通式(I)中,Ar1 及Ar2 分別獨立表示可具有取代基之芳基或者芳香族雜環基,L1 表示單鍵或2價連結基(linking group),Ar1 、Ar2 及L1 之至少一個具有大於等於一個鎓陽離子;R3 及R4 分別獨立表示取代基,亦可與所取代之苯環(substituted benzene ring)成環;m3及m4分別獨立表示在0~4範圍內的整數,當m3、m4為2~4範圍的整數時,多個存在的R3 、R4 可分別相同亦可不同]。
上述通式(I)中,Ar1 可以下式表示:
Ar2 可以下式表示:
[上述中,R1 及R2 分別獨立表示取代基,亦可與所取代之苯環成環;m1及m2中一個表示在0~5範圍內的整數,另一個表示在1~5範圍內的整數,m1、m2為在2~5範圍內的整數時,多個存在的R1 、R2 可分別相同亦可不同]。
再者,上述通式(I)中,R1 及R3 之至少一個可表示具有氮陽離子的取代基,L1 可為單鍵。上述氮陽離子可為四(tetra)取代氮陽離子或含氮原子之芳香族雜環陽離子,上述含氮原子的芳香族雜環陽離子可為吡啶陽離子(pyridinium cation)、咪唑(imidazolium)陽離子、噻唑(thiazolium)陽離子、噁唑啉(oxazolium)陽離子或亞胺(iminium)陽離子。
進而,通式(I)中,L1 可以下式表示:
[上述式中,R5 及R6 分別獨立表示取代基;m5及m6分別獨立表示在0~4範圍內的整數,m5、m6為在2~4範圍內的整數時,多個存在之R5 、R6 可分別相同亦可不同;La 表示2價連結基]。
又,以上述通式(I)所表示之化合物可為以下述通式(IV)所表示之化合物:
[通式(IV)中,R5 1 及R5 2 分別獨立表示氫原子或烷基;R5 3 、R5 4 、R5 5 、R5 6 、R5 7 及R5 8 分別獨立表示氫原子、烷基、芳基、或芳香族雜環基,R5 5 與R5 6 、R5 7 與R5 8 亦可連結形成5或6員環(5 or 6-membered ring),R5 1 、R5 2 、R5 3 、R5 4 、R5 5 、R5 6 、R5 7 及R5 8 亦可分別進而具有取代基]。
本發明之其他態樣是關於一種色素化合物,其含有上述本發明之陽離子化合物以及可中和上述陽離子化合物之電荷之量的陰離子。於此色素化合物中,上述陰離子可為陰離子性色素,上述陰離子性色素可為氧喏色素,上述氧喏色素可以下述通式(V)表示:
[通式(V)中,Za2 5 及Za2 6 分別獨立表示形成酸性核(acidic nucleus)的原子群;Ma2 7 、Ma2 8 及Ma2 9 分別獨立表示取代或未取代之亞甲基;Ka2 3 表示在0~3範圍內的整數,Ka2 3 為2或3時,多個存在的Ma2 7 、Ma2 8 可分別相同亦可不同]。
進而,上述氧喏色素可以下述通式(VI)表示
[通式(VI)中,Za2 1 、Za2 2 、Za2 3 及Za2 4 分別獨立表示形成酸性核的原子群;Ma2 1 、Ma2 2 、Ma2 3 、Ma2 4 、Ma2 5 及Ma2 6 分別獨立表示取代或未取代之亞甲基;L表示不與兩個鍵形成π共軛系之2價連結基;Ka2 1 及Ka2 2 分別獨立表示在0~3範圍內的整數,Ka2 1 、Ka2 2 為2或3時,多個存在的Ma2 1 、Ma2 2 、Ma2 5 、及Ma2 6 可分別相同亦可不同]。
另外,本發明是關於一種光資訊記錄媒體,其於基板上具有記錄層,且上述記錄層含有上述本發明之色素化合物。這種光資訊記錄媒體可為可錄式光資訊記錄媒體,或者DVD-R型光資訊記錄媒體。
進而,本發明關是於一種將上述之本發明之色素化合物用作光資訊記錄媒體的記錄層用色素的方法。於該方法中,上述光資訊記錄媒體可為可錄式光資訊記錄媒體,或者DVD-R型光資訊記錄媒體。
根據本發明,可提供顯示優異靈敏度、顫動及反射率的光資訊記錄媒體。進而,本發明之色素化合物可形成,製備色素塗佈液時之溶解性、塗佈液之溶解經時穩定性優異,且於塗佈高濃度塗佈溶液以形成記錄層時亦具有良好塗佈面狀態的記錄層。
[陽離子化合物]
本發明之陽離子化合物是以下述通式(I)所表示之陽離子化合物。
本發明之陽離子化合物於一分子中具有大於等於3個陽離子部分,與陰離子部位一同形成可用作光資訊記錄媒體之記錄層用色素的色素化合物。以下,詳細說明本發明之陽離子化合物。
通式(I)
通式(I)中,Ar1 及Ar2 分別獨立表示可具有取代基之芳基或者芳香族雜環基,Ar1 及Ar2 之至少一個具有大於等於一個鎓陽離子。Ar1 、Ar2 所表示之芳基較佳的是碳數6~30,更佳的是碳數6~20,最佳的是碳數6~12,其例如可列舉:苯基、對甲基苯基(p-methylphenyl)、萘基、鄰胺苯甲基(anthranil)等。
Ar1 、Ar2 所表示之芳香族雜環基較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,上述芳香族雜環基中所含之雜原子(heteroatom)例如可列舉氮原子、氧原子、硫原子。上述芳香族雜環基之具體例可列舉:吡咯基(pyrrole)、吡唑基(pyrazole)、咪唑基(imidazole)、吡啶基(pyridine)、呋喃基(furan)、噻吩基(thiophene)、噁唑基(oxazole)、噻唑基(thiazole)及該等芳香族雜環基之苯環縮環物或雜環縮環物等。Ar1 、Ar2 最佳是苯基。
於至少Ar1 和Ar2 中有一個具有鎓陽離子之情形時,其鎓陽離子亦可包含在Ar1 、Ar2 之取代基上。或者,上述鎓陽離子亦可為Ar1 、Ar2 所表示之芳香族雜環基之雜原子進而被取代所生成的鎓陽離子。鎓陽離子並無特別限定,較佳的是表示銨陽離子(ammonium cation)、氧鎓(oxonium)陽離子、鏻(phosphonium)離子、鋶(sulfonium)陽離子、硒(selenonium)離子、錪(iodonium)陽離子,最佳的是表示銨陽離子。此處,銨陽離子表示於氮原子上具有正電荷之陽離子基,較佳的是表示四取代氮陽離子(取代基為以下所說明之烷基、芳基、芳香族雜環基)、吡啶陽離子、咪唑陽離子、噻唑陽離子、噁唑啉陽離子、亞胺陽離子等。
Ar1 、Ar2 亦可進而具有取代基。上述取代基例如可列舉:烷基(alkyl)(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~10,例如可列舉甲基、乙基、異丙基、第三丁基、正辛基、正癸基、正十六烷基、環丙基、環戊基、環己基等)、烯基(alkenyl)(較佳的是碳數2~30,更佳的是碳數2~20,最佳的是碳數2~10,例如可列舉乙烯基、烯丙基、2-丁烯基、3-戊烯基等)、炔基(alkynyl)(較佳的是碳數2~30,更佳的是碳數2~20,最佳的是碳數2~10,例如可列舉炔丙基(propargyl)、3-戊炔基等)、芳基(aryl)(較佳的是碳數6~30,更佳的是碳數6~20,最佳的是碳數6~12,例如可列舉苯基、對甲基苯基、萘基、鄰胺苯甲基等)、胺基(amino)(較佳的是碳數0~30,更佳的是碳數0~20,最佳的是碳數0~10,例如可列舉胺基、甲胺基、二甲胺基、二乙胺基、二苄胺基、二苯胺基、二甲苯胺基等)、烷氧基(alkoxy)(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~10,例如可列舉甲氧基、乙氧基、丁氧基、2-乙基己氧基等)、芳氧基(aryloxy)(較佳的是碳數6~30,更佳的是碳數6~20,最佳的是碳數6~12,例如可列舉苯氧基、1-萘氧基、2-萘氧基等)、芳香族雜環氧基(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如可列舉吡啶氧基(pyridyloxy)、吡嗪氧基(pyraziloxy)、嘧啶氧基(pyrimidyloxy)、喹啉氧基(quinolyloxy)等)、醯基(acyl)(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如乙醯基、苯甲醯基、甲醯基、三甲基乙醯(pivaloyl)等)、烷氧羰基(alkoxy carbonyl)(較佳的是碳數2~30,更佳的是碳數2~20,最佳的是碳數2~12,例如甲氧羰基、乙氧羰基等)、芳氧羰基(aryloxy carbonyl)(較佳的是碳數7~30,更佳的是碳數7~20,最佳的是碳數7~12,例如可列舉苯氧羰基等)、醯氧基(acyloxy)(較佳的是碳數2~30,更佳的是碳數2~20,最佳的是碳數2~10,例如可列舉乙醯氧基、苯甲醯氧基等)、醯胺基(acylamino)(較佳的是碳數2~30,更佳的是碳數2~20,最佳的是碳數2~10,例如可列舉乙醯胺基、苯甲醯胺基等)、烷氧醯胺基(alkoxy carbonyl amino)(較佳的是碳數2~30,更佳的是碳數2~20,最佳的是碳數2~12,例如可列舉甲氧醯胺基等)、芳氧醯胺基(aryloxy carbonyl amino)(較佳的是碳數7~30,更佳的是碳數7~20,最佳的是碳數7~12,例如可列舉苯氧醯胺基等)、磺醯胺基(sulfonylamino)(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如可列舉甲磺醯胺基、苯磺醯胺基等)、胺磺醯基(sulfamoyl)(較佳的是碳數0~30,更佳的是碳數0~20,最佳的是碳數0~12,例如胺磺醯基、甲胺磺醯基、二甲胺磺醯基、苯胺磺醯基等)、胺甲醯基(carbamoyl)(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如可列舉胺甲醯基、甲胺甲醯基、二甲胺甲醯基、苯胺甲醯基等)、烷硫基(alkylthio)(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如可列舉甲硫基、乙硫基等)、芳硫基(arylthio)(較佳的是碳數6~30,更佳的是碳數6~20,最佳的是碳數6~12,例如可列舉苯硫基等)、芳香族雜環硫基(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如可列舉吡啶硫基、2-苯並咪唑硫基(2-benzimidazolylthio)、2-苯並噁唑硫基(2-benzoxazolylthio)、2-苯並噻唑硫基(2-benzthiazolylthio)等)、磺醯基(sulfonyl)(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如可列舉甲磺醯基、甲苯磺醯基等)、亞磺醯基(sulfinyl)(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如可列舉甲亞磺醯基、苯亞磺醯基等)、脲基(ureido)(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如脲基、甲脲基、苯脲基等)、磷酸醯胺基(較佳的是碳數1~30,更佳的是碳數1~20,最佳的是碳數1~12,例如可列舉二乙基磷酸醯胺基、苯基磷酸醯胺基等)、羥基(hydroxy)、巰基(mercapto)、鹵素原子(例如氟原子、氯原子、溴原子、碘原子)、氰基(cyano)、磺基(sulfo)、羧基(carboxyl)、硝基(nitro)、羥肟酸基(hydroxamic group)、亞磺基(亞磺酸基)、肼基(hydrazino)、亞胺基(imino)、芳香族雜環基(較佳的是碳數1~30,更佳的是碳數1~12,雜原子例如可列舉氮原子、氧原子、硫原子,具體可列舉例如咪唑基、吡啶基、喹啉基、呋喃基(furyl)、噻吩基(thienyl)、哌啶基(piperidyl)、嗎啉基(morpholino)、苯並噁唑基、苯並咪唑基、苯並噻唑基、咔唑基(carbazolyl)、氮雜基(azepinyl)等)、矽烷基(silyl)(較佳的是碳數3~40,更佳的是碳數3~30,最佳的是碳數3~24,例如可列舉三甲基矽烷基、三苯基矽烷基等)等。該等取代基亦可進一步被取代。
R3 、R4 分別獨立表示取代基。R3 、R4 所表示之取代基的例子,較好可列舉上述之Ar1 、Ar2 之取代基的例子,更佳的是烷基、芳基、雜環基、胺基、烷氧基、醯基、醯氧基、醯胺基,最佳的是烷基、芳基、烷氧基、醯基。又,R3 、R4 所表示之取代基之間亦可進行鍵結。即,左右之吡啶環亦可以R3 與R4 鍵結的連結基進行鍵結。另外,R3 、R4 亦可分別與所取代之苯環成環。
m3、m4分別獨立表示在0~4範圍內的整數。m3、m4分別較佳的是0~2,更佳的是0~1。m3、m4為在2~4範圍內的整數時,多個存在之R3 、R4 可分別相同亦可不同。
L1 表示單鍵或2價連結基。2價連結基較佳的是於兩末端具有吡啶鎓基者。關於L1 所表示之2價連結基,如以下對通式(III)中之連結基所述。
通式(I)中之陽離子數較佳的是大於等於3個、小於等於1000,更佳的是大於等於3個、小於等於10,最佳的是大於等於4、小於等於6。
本發明之陽離子化合物的較好態樣可列舉:於通式(I)中,Ar1 以下式表示:
Ar2 以下式表示:
如此所得到之陽離子化合物,即以下述通式(II)所表示之陽離子化合物。
更好態樣可列舉如下陽離子化合物:於通式(II)中,L1 為單鍵,R1 及R2 之至少一個表示具有氮陽離子之取代基。
又,本發明之陽離子化合物的更佳的其他態樣亦可列舉如下化合物:於通式(II)中,L1
R1 及R2 分別獨立表示取代基,亦可與該取代基所取代的苯環成環的化合物,即以下述通式(III)所表示之陽離子化合物。
本發明之陽離子化合物的更佳的其他態樣可列舉以下述通式(IV)所表示之陽離子化合物。
以下依序詳細說明通式(II)、(III)、(IV)。
通式(II)
於通式(II)中,R1 及R2 分別獨立表示取代基。上述取代基的例子,除上述R3 、R4 之取代基說明中所揭示者以外,可列舉含有氮陽離子之取代基。此處,所謂「氮陽離子」表示含有大於等於一個氮原子且所含之氮原子的至少一個具有正電荷的陽離子。
上述氮陽離子,較佳可列舉四取代氮陽離子(取代基表示,作為Ar1 、Ar2 之取代基例而加以說明的烷基、芳基、芳香族雜環基)、含氮原子之芳香族雜環陽離子。
四取代氮陽離子的更好之其他態樣可列舉如下:
上述中,Ra 、Rb 、Rc 、Rd 及Re 分別獨立表示作為Ar1 、Ar2 之取代基例而加以說明的烷基、芳基或芳香族雜環基。
含氮原子之芳香族雜環陽離子,可列舉吡啶陽離子、咪唑陽離子、噻唑陽離子、噁唑啉陽離子或亞胺陽離子,具體可列舉如下:
於上述中,X1 表示O、N、S或CR(R表示氫原子或取代基),較佳的是N。Rf 、Rg 及Rh 分別獨立表示氫原子或取代基,Rg 及Rh 亦可分別與雜環中所含之N一同成環,X1 表示CR時,X1 與Rf 或Rh 亦可連結成環。X2 、X3 以及X4 分別獨立表示N或CR'(R'表示氫原子或取代基),Ri 及Rj 分別獨立表示氫原子或取代基,Ri 及Rj 亦可分別與雜環中所含之N一同成環,X2 表示CR'時,X2 與Ri 亦可連結成環,X4 表示CR'時,X4 與Rj 亦可連結成環。上述取代基是先前作為Ar1 、Ar2 之取代基例而加以說明之烷基、芳基或芳香族雜環基。
上述含氮原子之芳香族雜環陽離子之具體例可列舉,於下述含氮原子之芳香族雜環中至少有一個氮被取代者,
上述具體例中較好者可列舉於吡啶、1,3-噁唑、1,3-噻唑、咪唑或苯並咪唑中至少有一個氮被取代者。
L1 為單鍵時,較佳的是R1 、R2 之至少一個表示具有上述氮陽離子之取代基,更佳的是二者皆表示具有氮陽離子之取代基。R1 、R2 亦可分別與所取代之苯環成環。
m1及m2中一個表示0~5、較佳的是在0~2範圍內的整數,另一個表示1~5、較佳的是在1~2範圍內的整數。m1、m2為在2~5範圍內的整數時,多個存在之R1 、R2 可相同亦可不同。
於通式(II)中,R3 、R4 、L1 、m3、m4分別與通式(I)中之定義相同,其詳情如上所述。通式(II)中之陽離子數與通式(I)相同,較佳的是大於等於3個、小於等於1000,更佳的是大於等於3個、小於等於10,最佳的是大於等於4、小於等於6。
通式(III)
通式(III)中,R1 、R2 、R3 、R4 與通式(I)及(II)中之定義相同,R5 及R6 分別獨立表示取代基。以R5 、R6 所表示之取代基的較好例等之詳情如上述R3 、R4 之取代基的說明中所揭示。於通式(III)中,以Rl 、R2 、R3 、R4 、R5 、R6 所表示之取代基的最佳的例子可列舉:烷基、芳基、烷氧基、芳氧基、醯基、烷氧羰基、醯胺基、胺磺醯基、脲基等。
於通式(III)中,m5及m6分別獨立表示在0~4範圍內的整數,較佳的是表示在0~2範圍內的整數,最佳的是0。m5、m6為在2~4範圍內的整數時,多個存在之R5 、R6 可分別相同亦可不同。
於通式(III)中,m1、m2、m3、m4與通式(I)及(II)中之定義相同。於通式(III)中,m1及m2更佳的是表示在0~~2範圍內的整數,m3、m4較佳的是表示在0~4範圍內的整數,更佳的是表示在0~2範圍內的整數,最佳的是0。
於通式(III)中,L1 表示2價連結基,較佳的是單鍵、氧原子、硫原子、氮原子、亞甲基、伸苯基、羰基、胺苯磺基、醯胺基及含有該等連結基之組合的基,最佳的是下述連結基。
通式(III)中之陽離子數與通式(I)、通式(II)相同,較佳的是大於等於3個、小於等於1000,更佳的是大於等於3個、小於等於10,最佳的是大於等於4、小於等於6。
通式(IV)
於通式(IV)中,R5 1 及R5 2 分別獨立表示氫原子或烷基,R5 3 、R5 4 、R5 5 、R5 6 、R5 7 及R5 8 分別獨立表示氫原子、烷基、芳基、或芳香族雜環基,R5 5 與R5 6 、R5 7 與R5 8 亦可連結形成5或6員環。所形成之環,可列舉脂肪族環、苯環、芳香族雜環等。以R5 1 、R5 2 、R5 3 、R5 4 、R5 5 、R5 6 、R5 7 、R5 8 所表示之烷基、芳基、芳香族雜環基可列舉以上述取代基之例子中所表示者,亦可進而具有取代基R5 1 、R5 2 較佳的是取代或未取代之烷基(例如甲基、苯基),更佳的是二者為相同烷基。R5 3 、R5 4 、R5 5 、R5 6 、R5 7 、R5 8 均為氫原子之情形時,或R5 3 、R5 4 為氫原子且R5 5 與R5 6 、R5 7 與R5 8 連結形成苯環之情形時較好。
以下列舉本發明之陽離子化合物的較佳的具體例,但本發明並不限定於下述具體例。
本發明之陽離子化合物如日本專利特開2003-128654號公報中所揭示,可藉由將於吡啶化合物之氮上取代有二硝基苯或雜芳基者,以苯胺或雜芳胺進行取代而合成。進而,具有大於等於3個陽離子基的本發明之陽離子化合物可使用已具有陽離子基者作為上述苯胺或雜芳胺而進行合成,或者可藉由將聯吡啶化合物之氮上的芳基或雜芳基之取代基加以鎓化而進行合成。
又,所獲得之化合物亦可以習知方法進行精製。再者,可利用NMR等習知的分析方法確認已獲得的本發明之陽離子化合物。
[色素化合物]
本發明之色素化合物含有本發明之陽離子化合物以及可中和上述陽離子化合物之電荷的量的陰離子。上述色素化合物較佳的是上述陽離子化合物與上述陰離子成鹽而形成的化合物。本發明之色素化合物於色素膜中之最大吸收波長較佳的是大於等於500 nm、不足720 nm,更佳的是大於等於550 nm、不足600 nm,最好的是大於等於565 nm、不足590 nm。
上述陰離子若為可中和本發明之陽離子化合物之電荷而形成鹽的陰離子,則可為無機陰離子或有機陰離子之任一者,例如可列舉:鹵素離子(Cl 、Br 、I 等)、磺酸鹽離子(CH3 SO3 、CF3 SO3 、CF3 (CF2 )7 SO3 、對甲苯磺酸鹽離子、萘-1,5-二磺酸鹽離子等)、硫酸根離子(CH3 SO4 等)、ClO4 、BF4 、SbF6 、及磷酸根離子(PF6 等)、金屬錯合物離子(例如, 等)、陰離子色素(例如氧喏色素、陰離子性解離性基(OH基、NH基、COOH基、SO3 H基等)所解離之陰離子性色素部分(較佳的是偶氮基、偶氮甲基色素,二苯乙烯(stilbene)色素))。上述陰離子較佳的是陰離子性色素,更佳的是氧喏色素。所謂氧喏色素,是以下述通式(A)所表示之化合物,若最大吸收波長大於等於350 nm、不足720 nm,則結構並無特別限定。較佳的是亞甲基數為5~7且具有鏈狀酸性核或環狀酸性核的色素。
R:氫或取代基,n:大於等於0之整數
於通式(A)中,n較佳的是在1~4範圍內的整數。R所表示之取代基例可列舉作為Ar1 、Ar2 之取代基的例子而加以說明者,更佳的是碳數1~20之烷基(例如甲基、乙基、異丙基)、鹵素原子(例如氯、溴、碘、氟)、碳數1~20之烷氧基(例如甲氧基、乙氧基、異丙氧基)、碳數6~26之芳基(例如苯基、2-萘基)、碳數0~20之雜環基(例如2-吡啶基、3-吡啶基)、碳數6~20之芳氧基(例如苯氧基、1-萘氧基、2-萘氧基)、碳數1~20之醯胺基(例如乙醯胺基、苯甲醯胺基)、碳數1~20胺甲醯基(例如N,N-二甲基胺甲醯基)、磺基、羥基、羧基、碳數1~20之烷硫基(例如甲硫基)、氰基等,多個R之間亦可連結成環。上述陰離子更佳的是以下述通式(V)所表示之具有環狀酸性核的氧喏色素: 最佳的是以下述通式(VI)所表示之氧喏色素: 以下依序詳細說明通式(V)、(VI)。
通式(V)
於通式(V)中,Za2 5 及Za2 6 分別獨立表示形成酸性核的原子群,其例揭示於James編The Theory of the Photographic Process,第4版,麥克米倫出版公司,1977年,第198頁。具體可分別列舉可被取代之吡唑-5-酮、吡唑啶-3,5-二酮(pyrazolidine-3,5-dione)、咪唑啉-5-酮、乙內醯脲(hydantoin)、2或4-硫代乙內醯脲、2-胺基噁唑烷-4-酮、2-噁唑啉-5-酮、2-硫代噁唑啉-2,4-二酮、異繞丹寧、繞丹寧(rhodanine)、噻吩-3-酮、噻吩-3-酮-1,1-二氧化物、3,3-二氧[1,3]氧硫雜環戊烷-5-酮、吲哚啉-2-酮、吲哚啉-3-酮、2-氧基吲唑(2-oxoindazolium)、5,7-二氧-6,7-二氫噻唑並[3,2-a]嘧啶、3,4-二氫異喹啉-4-酮、1,3-二噁烷-4,6-二酮(例如丙二酸環亞異丙酯(Meldrum's acid)等)、巴比妥酸(barbituric acid)、2-硫代巴比妥酸、香豆素-2,4-二酮(coumarin-2,4-dion)、吲唑-2-酮(indazoline-2-one)、吡啶並[1,2-a]嘧啶-1,3-二酮、吡唑並[15-b]喹唑酮(pyrazolo[15-b]quinazolone)、吡唑並吡啶酮(pyrazolopyridone)、5或6員之碳環(例如己烷-1,3-二酮、戊烷-1,3-二酮、茚烷-1,3-二酮)等核,較佳的是吡唑-5-酮、吡唑啶-3,5-二酮、巴比妥酸、2-硫代巴比妥酸、1,3-二噁烷-4,6-二酮、或者3,3-二氧[1,3]氧硫雜環戊烷-5-酮、茚二酮(indane dione)、吡唑啉酮(pyrazolone)、吡唑啉二酮、二氧化苯並噻吩酮。Za2 5 、Za2 6 最好的是分別為可取代之1,3-二噁烷-4,6-二酮。取代酸性核之取代基可列舉如下基作為例子:鹵素原子、烷基(包括環烷基、二環烷基)、烯基(包括環烯基、二環烯基)、炔基、芳基、雜環基、氰基、羥基、硝基、羧基、烷氧基、芳氧基、矽烷氧基、雜環氧基、醯氧基、胺甲醯氧基、烷氧基羰氧基、芳氧基羰氧基、胺基(包括烷胺基、芳胺基)、醯胺基、胺基羰基胺基、烷氧基羰基胺基、芳氧羰基胺基、胺磺醯基胺基、烷基及芳基磺醯胺基、巰基、烷硫基、芳硫基、雜環硫基、胺磺醯基、磺基、烷基及芳基亞磺醯基、烷基及芳基磺醯基、醯基、芳氧基羰基、烷氧羰基、胺甲醯基、芳基及雜環偶氮基、醯亞胺基、膦基、氧膦基、磷氧基、氧膦基胺基、或矽烷基。其中,較佳的是碳數1~20之取代或未取代之烷基、或者碳數6~20之取代或未取代之芳基。
酸性核(acidic nucleus)較佳的是未取代者、或者被碳數1~20之取代或未取代之烷基取代者、被碳數6~20之取代或未取代之芳基取代者。
Ma2 7 、Ma2 8 及Ma2 9 分別獨立表示取代或未取代之亞甲基。取代基較好可列舉:碳數1~20之烷基(例如甲基、乙基、異丙基)、鹵素原子(例如氯、溴、碘、氟)、碳數1~20之烷氧基(例如甲氧基、乙氧基、異丙氧基)、碳數6~26之芳基(例如苯基、2-萘基)、碳數0~20之雜環基(例如2-吡啶基、3-吡啶基)、碳數6~20之芳氧基(例如苯氧基、1-萘氧基、2-萘氧基)、碳數1~20之醯胺基(例如乙醯胺基、苯甲醯胺基)、碳數1~20之胺甲醯基(例如N,N-二甲基胺甲醯基)、磺基、羥基、羧基、碳數1~20之烷硫基(例如甲硫基)、氰基等。又,可與其他亞甲基鍵結形成環狀結構,亦可與以Za2 7 ~Za2 9 所表示之原子團鍵結形成環狀結構。
較佳的是,Ma2 7 、Ma2 8 及Ma2 9 分別獨立為未取代之亞甲基,或者被乙基、甲基或苯基取代之亞甲基中的任一者。最好的是未取代之亞甲基。
於通式(V)中,Ka2 3 表示在0~3範圍內的整數。Ka2 3 為2或3時,多個存在之Ma2 7 、Ma2 8 可相同亦可不同。Ka2 3 較佳的是2。
本發明之陽離子化合物與以通式(V)所表示之陰離子性色素部位中,形成鹽之色素為中性,色素化合物中之陽離子數與陰離子數相同,陽離子數及陰離子數分別較佳的是3~10,最佳的是4~6。
於通式(V)中,較佳的是Za2 5 及Za2 6 分別獨立為未取代、或者被碳數1~20之取代或未取代之烷基所取代、或者被碳數6~20之取代或未取代之芳基取代的吡唑-5-酮、吡唑啶-3,5-二酮、巴比妥酸、2-硫代巴比妥酸、1,3-二噁烷-4,6-二酮、3,3-二氧[1,3]氧硫雜環戊烷-5-酮,Ma2 7 、Ma2 8 及Ma2 9 分別獨立表示未取代之亞甲基,或者被乙基、甲基、或苯基取代的亞甲基中的任一者,Ka2 3 為2。最佳的是,Za2 5 及Za2 6 分別獨立表示未取代、或者被碳數1~20之取代或未取代之烷基取代、或者被碳數6~20之取代或未取代之芳基取代的1,3-二噁烷-4,6-二酮,Ma2 7 、Ma2 8 、Ma2 9 為未取代之亞甲基,Ka2 3 為2。
通式(VI)
於通式(VI)中,Za2 1 、Za2 2 、Za2 3 及Za2 4 分別獨立表示形成酸性核的原子群。酸性核與通式(V)之Za2 5 、Za2 6 所形成者相同,其具體例亦相同。Za2 1 、Za2 2 、Za2 3 及Za2 4 所形成之酸性核,較佳的是吡唑-5-酮、吡唑啶-3,5-二酮、巴比妥酸、2-硫代巴比妥酸、1,3-二噁烷-4,6-二酮、或者3,3-二氧[1,3]氧硫雜環戊烷-5-酮、茚二酮、吡唑啉酮、吡唑啉二酮、苯並噻吩酮二氧化物。其中,最好的是1,3-二噁烷-4,6-二酮。
Ma2 1 、Ma2 2 、Ma2 3 、Ma2 4 、Ma2 5 及Ma2 6 分別獨立表示取代或未取代之亞甲基,其與通式(V)之Ma2 7 、Ma2 8 、Ma2 9 相同,具體例及較好例亦相同。Ma2 1 、Ma2 2 、Ma2 3 、Ma2 4 、Ma2 5 、Ma2 6 較佳的是未取代之亞甲基。
Ka2 1 及Ka2 2 分別獨立表示在0~3範圍內的整數,其與通式(V)之Ka2 3 相同。Ka2 3 為2或3時,多個存在之Ma2 1 、Ma2 2 、Ma2 5 、Ma2 6 可分別相同亦可不同。
L為不與兩個鍵共同形成π共軛體系之2價連結基。對於2價連結基,除這種連結基鍵結所形成之發色基(chromophore)之間不形成π共軛體系以外,並無特別限定,較佳的是表示將伸烷基(碳數1~20,例如亞甲基、伸乙基、伸丙基、伸丁基、伸戊基)、伸芳基(碳數6~26,例如伸苯基、伸萘基)、伸烯基(碳數2~20,例如伸乙烯基、伸丙烯基)、伸炔基(碳數2~20,例如伸乙炔基、伸丙炔基)、-CO-N-(R1 0 1 )-、-CO-O-,-SO2 -N(R1 0 2 )-、-SO2 -O-、-N(R1 0 3 )-CO-N(R1 0 4 )-、-SO2 -、-SO-、-S-、-O-、-CO-、-N(R1 0 5 )-、伸雜環基(碳數1~26,例如6-氯-1,3,5-三嗪-2,4-二基、嘧啶-2,4-二基)中一個或更多個加以組合而構成之碳數0~100、較佳的是1~20之連結基。上述R1 0 1 、R1 0 2 、R1 0 3 、R1 0 4 、R1 0 5 分別獨立表示氫原子、取代或未取代之烷基、及取代或未取代之芳基中的任一者。又,以L所表示之連結基可於此等連接基所連結之兩個發色基之間存在一個以上的多個,亦可多個(較佳的是兩個)連結基鍵結成環。
L分別較佳的是兩個伸烷基(較佳的是伸乙基)鍵結而形成者。其中,更佳的是形成5或6員環(較佳的是環己烷)之情形。
以下列舉上述氧喏色素之較好具體例,但本發明並不限定於此。
通常之氧喏色素可藉由適合之活性亞甲基化合物與亞甲基源(用以將亞甲基導入亞甲基染料的化合物)的縮合反應而合成。此種化合物之詳情可參照:日本專利特公昭39-22069號、日本專利特公昭43-3504號、日本專利特公昭52-38056號、日本專利特公昭54-38129號、日本專利特公昭55-10059號、日本專利特公昭58-35544號、日本專利特開昭49-99620號、日本專利特開昭52-92716號、日本專利特開昭59-16834號、日本專利特開昭63-316853號、日本專利特開昭64-40827號公報、以及英國專利第1133986號、美國專利第3247127號、美國專利第4042397號、美國專利第4181225號、美國專利第5213956號、美國專利第5260179號各說明書。
雙型氧喏色素之合成法揭示於歐洲專利EP1424691A2中。
其次,列舉本發明之陽離子化合物與陰離子性色素成鹽而形成的色素化合物的較好具體例,但本發明並不限定於該等。
除上述氧喏色素以外,上述陰離子性色素還可使用具有解離性基(羥基、胺基等)作為發色基的解離性之偶氮色素、偶氮甲基色素,或者除亞甲基色素及發色團以外,取代有解離性基的偶氮色素、偶氮甲基色素、亞甲基色素、醌系色素、二芳基及三芳基甲烷系色素、鈦菁(phthalocyanine)系色素、靛藍(indigo)色素、縮合環系色素、苯乙烯系色素、螺吡喃(spiropyran)及螺噁嗪(spirooxazine)衍生物、二芳基乙烯衍生物、角鯊烯鎓(squalilium)及克酮鎓(croconium)衍生物等。具體結構例可列舉大河原信.松岡賢.平嶋恆亮.北尾悌次郎著(講談社)「機能性色素」所揭示之色素等。
本發明之色素化合物可藉由將本發明之陽離子化合物之鹽(鹽酸鹽等)進行陰離子交換而容易地獲得。此外,所獲得之色素化合物亦可以習知的方法精製。再者,可利用NMR等習知的分析方法確認已獲得本發明之色素化合物。
本發明之色素化合物在製備色素塗佈液時之溶解性、塗佈液之溶解經時穩定性、使用高濃度塗佈溶液時之塗佈性(塗佈膜平滑性)優異,因此,可藉由使用本發明之色素化合物作為光資訊記錄媒體之記錄層用色素,而改善製造適應性。
再者,本發明之色素化合物的記錄特性優異,因此,可藉由將其用作光資訊記錄媒體之記錄層用色素,而獲得記錄靈敏度及寫入精度優異的光資訊記錄媒體。將本發明之色素化合物用作記錄層用色素之使用方法的詳情,如以下對本發明之光資訊記錄媒體所述。
[光資訊記錄媒體]
本發明之光資訊記錄媒體於基板上具有記錄層,且於上述記錄層上含有本發明之色素化合物。
上述記錄層可僅含一種本發明之色素化合物,亦可組合含有兩種以上。其含有率較佳的是1~100%,更佳的是5~100%,最佳的是10~100%。
上述記錄層中除本發明之色素化合物以外的成分可為有機物、無機物之任一者,其具體例可列舉本發明之色素化合物以外的色素。所併用之色素較佳的是有機色素,具體為偶氮色素、花青(cyanine)色素、氧喏色素、吡咯甲川(pyrromethene)色素、鈦菁色素,更具體為本發明之色素化合物以外的氧喏色素,進而具體為日本專利特開平10-297103號公報、日本專利特開2000-108520號公報,日本專利特開2002-59652號公報,日本專利特開2002-249674暑公報,日本專利特開2003-39831號公報、及日本專利特開2004-188968號公報中所揭示之氧喏色素。併用本發明之色素化合物與其他色素作為記錄材料之情形時,就提高記錄特性及製造適應性之觀點而言,較佳的是以記錄層中總色素成分中的本發明之色素化合物的比例為60~100wt%、其他色素的比例為0~40wt%的方式進行混合。
本發明之光資訊記錄媒體若為於記錄層中含有本發明之色素化合物者,則並無特別限定,但較佳的是可錄式光記錄媒體。將本發明之光資訊記錄媒體應用為CD-R之情形時,較佳的是於形成有軌道間距為1.4~1.8 μm之預刻溝槽的厚度為12±0.2 mm的透明圓盤狀基板上,依序具有含有本發明之色素化合物的記錄層、光反射層及保護層的結構。
又,本發明之光資訊記錄媒體亦可為可錄式DVD。可錄式DVD存在具有單層記錄層者及具有兩層記錄層者,本發明可為任一態樣。又,可錄式DVD有DVD-R及DVD+R兩種,本發明可適用於任一態樣。
具有單層記錄層之可錄式DVD可採用於一對基板之間具有記錄層之層機構(例如依序具有基板、記錄層及保護基板(隔板(dummy board)))。除此以外,較佳的是適當形成反射層、保護層等。具有如此層結構之可錄式DVD的一個例子如圖1所示。
又,具有單層記錄層之DVD-R型光資訊記錄媒體之較好態樣可列舉以下光資訊記錄媒體。
即如下光資訊記錄媒體,其於形成有軌道間距為0.6~0.9 μm之預刻溝槽的厚度為0.6±0.1 mm的透明圓盤狀基板上,將設置含有本發明之色素化合物的記錄層及光反射層而成的層積體與,與該層積體之圓盤狀基板形狀相同之透明圓盤狀保護基板,以記錄層為內側之方式進行接合,並構成厚度為1.2±0.2 mm者。再者,上述DVD-R型光資訊記錄媒體亦可製成於光反射層上進而設置有保護層的結構。
上述單層記錄層中所使用的本發明之色素化合物,較佳的是於通式(III)~(IV)所表示之陽離子部分組合有以通式(VI)所表示之氧喏色素者。
另一方面,具有兩層記錄層之可錄式DVD可採取於相對之一對基板間具有兩層以上之記錄層的結構(例如依序具有第一基板、第一記錄層、第二記錄層、第二基板)。將具有兩層記錄層之可錄式DVD的一個例子示於圖2。
圖2所示之可錄式DVD具有如下結構:具有第一記錄層22之第一基板14與具有第二記錄層28之第二基板18經由中間層20而貼合。又,於第一記錄層22上設置反射層24,於中間層20與第二記錄層28之間設置障壁層(barrier layer)30,於第二記錄層28與第二基板18之間設置反射層26。再者,因自第一基板側照射雷射光,故形成於第一層記錄層上的反射層24變為半透明。
於圖2所示之可錄式DVD中,在對第一記錄層22記錄資訊時,於自第一基板14之端面14a面向第一記錄層22之方向上照射記錄用的雷射光32,使雷射光32成像於第一記錄層22上,以形成資訊(訊坑(pit))。此時,資訊可記錄在與第一預刻溝槽12之溝槽34對應之部分。
另一方面,對第二記錄層28記錄資訊時,於自第一基板14之端面14a面向第二記錄層28之方向上照射記錄用的雷射光,使雷射光32成像於第二記錄層28上,以記錄資訊(訊坑)。此時,資訊可記錄在第二記錄層28中之與第二預刻溝槽16之平面(land)36對應的部分。
再者,中間層20之作用在於防止第一記錄層22中所記錄之資訊與第二記錄層28中所記錄之資訊相互干擾,可藉由介入中間層20,而於第一記錄層22及第二記錄層28中獲得良好的記錄再生信號。
如上述可進行單面兩層記錄之可錄式DVD中,第一記錄層與第二記錄層因與入射光源之距離、及必需之熱分解特性不同,故較佳的是考慮應答特性等之後再選擇各層中所使用之記錄材料。使用於接近雷射光源之記錄層(圖2中之第一記錄層22)中的色素化合物中較好之色素,可為於上述具有單層記錄層之可錄式DVD的較好例子中所列舉的化合物。
另一方面,使用於遠離雷射光源之記錄層(圖2中之第二記錄層28)的色素化合物較佳的是於以通式(III)所表示之陽離子部分中組合有通式(VI)所表示之氧喏色素者。
又,具有兩層記錄層之DVD-R型光資訊記錄媒體的較好態樣,可列舉以下光資訊記錄媒體。
即如下光資訊記錄媒體:於形成有軌道間距為0.6~0.9 μm之預刻溝槽的厚度為0.6±0.1 mm之透明圓盤狀基板上,將設有含有本發明之色素化合物的記錄層及光反射層而成的兩片之層積體,分別以記錄層為內側之方式進行接合,並構成厚度為1.2±0.2 mm者。
本發明之光資訊記錄媒體例如可利用如以下所述之方法進行製造。基板(包括保護基板)可自先前用作資訊記錄媒體之基板的各種材料中任意選擇。基板材料例如可列舉:玻璃,聚碳酸酯,聚甲基丙烯酸甲酯等丙烯酸系樹脂,聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂,環氧樹脂,非晶質聚烯烴及聚酯等,還可根據需要併用該等而使用。再者,該等材料可用作膜狀或具有剛性之基板。上述材料中,就耐濕性、尺寸穩定性等方面而言,較佳的是聚碳酸酯。
以改善平面性、提高黏著力及防止記錄層變質等為目的,亦可於設有記錄層之側的基板表面設置下塗層。下塗層之材料例如可列舉:聚甲基丙烯酸甲酯、丙烯酸.甲基丙烯酸共聚物、苯乙烯.馬來酸酐共聚物、聚乙烯醇、N-羥甲基丙烯醯胺、苯乙烯.乙烯基甲苯共聚物、氯磺化聚乙烯、硝化纖維素(nitrocellulose)、聚氯乙烯、氣化聚烯烴、聚酯、聚醯亞胺、乙酸乙烯酯.氯乙烯共聚物、乙烯.乙酸乙烯酯共聚物、聚乙烯、聚丙烯、聚碳酸酯等高分子物質,以及矽烷偶合劑等表面重組劑。下塗層可藉由於將上述物質溶解或分散於適當溶劑中製備塗佈液後,再利用旋塗法(spin coat)、浸塗法(dip coat)、擠壓塗佈(extrusion coat)等塗佈法將該塗佈液塗佈於基板表面而形成。
另外,於基板(或者下塗層)上,形成表示追蹤(tracking)用溝槽或者位址(address)信號等資訊的凹凸(預刻溝槽)。較佳的是,在將聚碳酸酯等樹脂材料射出成形或擠出成形時,直接將該預刻溝槽以上述軌道間距形成於基板上。又,亦可藉由設置預刻溝槽層來形成預刻溝槽。預刻溝槽層之材料可使用丙烯酸之單酯、二酯、三酯及四酯中至少一種之單體(或者寡聚物(oligomer))與光聚合引發劑之混合物。預刻溝槽層之形成例如可藉由首先於精密製造之母模(壓模(stamper))上塗佈含有上述丙烯酸酯及聚合引發劑之混合液,接著在該塗佈液層上放置基板後,隔著基板或母模照射紫外線,以使塗佈層硬化並使基板與塗佈層固定。繼而,藉由自母模剝離基板而獲得預刻溝槽層。
於形成基板(或者下塗層)上之預刻溝槽的表面上,可設置含有本發明之色素化合物的記錄層。於記錄層上可進而含有用以提高耐光性之各種防退色劑。防退色劑之代表例可列舉:日本專利特開平3-224793號公報中所揭示的以通式(III)、(IV)或(V)所表示之金屬錯合物、二亞胺鹽、銨鹽,以及日本專利特開平2-300287號公報及日本專利特開平2-300288號公報中所揭示的亞硝基化合物,日本專利特開平10-151861號公報中所揭示的TCNQ(7,7,8,8-四氰對醌二甲烷,7,7,8,8-tetracyanoquino dimethane)衍生物。
可藉由如下方法形成記錄層:將本發明之色素化合物,進而根據需要之驟冷劑、黏合劑等溶解於溶劑中,以製備塗佈液,繼而將該塗佈液塗佈於基板表面而形成塗膜後,進行乾燥。用於色素記錄層形成之塗佈液之溶劑可列舉:乙酸丁酯、乳酸乙酯、乙酸賽璐蘇等酯,甲基乙基酮、環己酮、甲基異丁基酮等酮,二氯甲烷、1,2-二氯乙烷、氯仿等氯代烴,二甲基甲醯胺等醯胺,環己烷等烴,四氫呋喃、乙醚、二噁烷等醚,乙醇、正丙醇、異丙醇、正丁醇、二丙酮醇等醇,2,2,3,3-四氟丙醇等氟系溶劑,乙二醇單甲醚、乙二醇單乙醚、丙二醇單甲醚等二醇醚類等。上述溶劑可根據所使用之化合物的溶解性而單獨使用,或者組合二種以上使用。於塗佈液中,亦可根據目的進而添加抗氧化劑、紫外線吸收劑、可塑劑、潤滑劑等各種添加劑。
黏合劑的例子例如可列舉:明膠(gelatin)、纖維素衍生物、葡聚糖(dextran)、松香(rosin)、橡膠等天然有機高分子物質,以及聚乙烯、聚丙烯、聚苯乙烯、聚異丁烯等烴系樹脂,聚氯乙烯、聚氯亞乙烯、聚氯乙烯.聚乙酸乙烯酯共聚物等乙烯系樹脂,聚丙烯酸甲酯、聚甲基丙烯酸甲酯等丙烯酸系樹脂,聚乙烯醇、氯化聚乙烯、環氧樹脂、丁醛樹脂、橡膠衍生物、苯酚.甲醛樹脂等熱固性樹脂之初期縮合物等合成有機高分子。於併用黏合劑作為記錄層之材料時,黏合劑之使用量相對於色素之合計量,通常在0.01~50倍量之範圍內,較佳的是在0.1~5倍量之範圍內。以如此方式製備之塗佈液的色素濃度通常在0.01~10wt%之範圍內,較佳的是在0.1~5wt%之範圍內。
塗佈方法可列舉噴塗(spray)法、旋塗法、浸塗法、輥塗(roll coat)法、層板塗佈(plate coat)法、刮刀輥(doctor roll)法、絲網印刷(screen print)法等。記錄層可為單層,亦可為多層。記錄層之層厚度通常在20~500 nm之範圍內,較佳的是在50~300 nm之範圍內。
通常於提高資訊再生時的反射率為目的下可在上述記錄層上設置反射層。作為反射層之材料的光反射性物質為對雷射光之反射率高的物質,其例可列舉:Mg、Se、Y、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Co、Ni、Ru、Rh、Pd、Ir、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Si、Ge、Te、Pb、Po、Sn、Bi等金屬以及亞金屬(semimetal)或不銹鋼(stainless steel)。這些中較佳者為Cr、Ni、Pt、Cu、Ag、Au、Al及不銹鋼,尤其好者為Ag。該等物質可單獨使用,或者組合二種以上使用,或用作合金。反射層例如可藉由將上述反射性物質進行蒸鍍(evaporation)、濺鍍(sputtering)或者離子電鍍(ionplating),而形成於記錄層上。反射層之層厚度通常在10~300 nm之範圍內,較佳的是50~200 nm之範圍。
於以物理及化學方法保護記錄層等之目的下,亦可在反射層上設置保護層。為了提高基盤之並未設置記錄層側的耐損傷性、耐濕性,亦可設置該保護層。使用於保護層之材料例如可列舉:SiO、SiO2 、MgF2 、SnO2 、Si3 N4 等無機物質,熱塑性樹脂、熱固性樹脂、紫外線硬化性樹脂等有機物質。保護層例如可藉由將經塑膠之擠出加工而獲得的薄膜層壓於黏接層、反射層上及/或基板上而形成。或者亦可藉由真空蒸鍍(Vacuum evaporation)、濺鍍、塗佈等方法進行設置,又,於熱塑性樹脂、熱固性樹脂之情形時,亦可藉由溶解於該等之適當溶劑中而製備塗佈液後,塗佈該塗佈液,並乾燥而形成。於紫外線硬化性樹脂之情形時,可藉由直接或者溶解於適當溶劑中而製備塗佈液後,塗佈該塗佈液,接著照射紫外光使其硬化而形成。該等塗佈液中,還可根據目的進而添加抗靜電劑、抗氧化劑、紫外線吸收劑等各種添加劑。保護層之層厚度通常在0.1~10.0 μm之範圍內。藉由以上步驟,可製作於基板上設置有記錄層及反射層,並且根據需要設置有保護層的層積體。以如上所述之方式製作兩片層積體,將該等以各個記錄層為內側之方式,以黏合劑進行貼合,藉此可製造具有兩個記錄層之光資訊記錄媒體。又藉由將所獲得之層積體、及與該層積體之基板尺寸大致相同的圓盤狀保護基板,以該記錄層為內側之方式,以黏接劑進行貼合,可製造具有單層記錄層之光資訊記錄媒體。
上述黏接層之材料可列舉:熱塑性樹脂(thermoplastic resin)、熱固性樹脂(thermoset resin)、電子束硬化性樹脂(electron beam curable resin)、紫外線硬化性樹脂(ultraviolet curing resin)、感壓性雙面膠(pressure-sensitive two-sided tape)等,或SiO2 等無機材料等。此外,可單獨或混合使用該等材料,不僅是一層,亦可製成多層膜而使用。如此之黏接層可利用旋塗法或澆鑄(cast)法、濺鍍法而形成。黏接層之厚度較佳的是5~100 μm,更佳的是10~70 μm。
對本發明之光資訊記錄媒體記錄資訊之方法例如可以如下方式進行。首先,一邊使資訊記錄媒體以恆定線速度(constant linear velocity)或恆定角速度(constant angular velocity)進行旋轉,一邊自基板側照射半導體雷射光等記錄用雷射光。一般認為,由於照射該光,於記錄層與反射層之界面會形成空洞(空洞是伴隨記錄層或反射層之變形、或者兩層之變形而形成),使基板隆起變形,或者因記錄層上產生變色、締合狀態(association state)變化等而造成折射率變化,藉此以記錄資訊。記錄光可使用具有,CD-R型時為770~790 nm、DVD-R型時為600 nm~700 nm(較佳的是620~680 nm,更佳的是630~660 nm)範圍之發射波長的半導體雷射光束。如上述所記錄之資訊的再生,可藉由一邊使資訊記錄媒體以與上述相同之恆定線速度進行旋轉,一邊自基板側照射具有與記錄時相同之波長的半導體雷射光,再檢測其反射光而進行。
[實施例]
以下根據實施例進一步說明本發明。但,本發明並不限定於實施例中所示之態樣。
[實施例1] 色素化合物D-1之合成 (1)化合物例V-1之對甲苯磺酸鹽的合成
根據如下反應流程,於300 ml異丙醇中添加3 g氯化銨及30 g還原鐵,進行30分鐘加熱回流。繼而於加熱回流下,緩緩添加25.8 g的4-硝基苯基-1-咪唑。進而加熱回流2小時後,以熱過濾除去不溶成分。將所獲得之異丙醇溶液加以濃縮乾涸,之後將其以矽膠管柱層析法(silica gel column chromatography)進行精製,從而獲得16.0 g中間體A。接著,於20 ml二甲基甲醯胺中添加2.07 g中間體A及3.36 g的DNPV(1,1'-雙(2,4-二硝基苯基)[4,4']-二氯聯吡啶)後,於90℃下加熱攪拌2小時。
反應完畢後,放置冷卻,並放置一晚。濾取所析出之結晶,以二甲基甲醯胺清洗後,進行減壓乾燥,獲得3.0 g中間體B。接著於2.0 g中間體B中添加20 ml對甲苯磺酸甲酯,於120℃下加熱攪拌6小時。放置冷卻後,添加30 ml乙酸乙酯,攪拌30分鐘。濾取析出結晶,加以乾燥,從而獲得2.75 g的V-1之對甲苯磺酸鹽。
1 H-NMRData(d6 -DMSO):9.99(s,2H),9.74(d,4H),9.10(d,4H),8,46(s,2H),8.28(dd,8H),8,05(s,2H),7.48(d,8H),7.12(d,8H),4.03(s,6H),2.30(s,12H)
(2)色素化合物之合成(鹽形成)
將上述所獲得的0.58 g的V-1之對甲苯磺酸鹽加熱完全溶解於30 ml甲醇中,然後於其中添加1.24 g下述色素原料,於60℃下攪拌30分鐘。
繼而於放置冷卻後,於室溫下攪拌2小時,濾取析出結晶,以甲醇清洗。乾燥後,獲得色素化合物D-1(吸收λmax=561.6 nm,ε=6.13×105 /2,2,3,3-四氟丙醇(TFP))。
1 H-NMRData(d6 -DMSO):9.94(s,2H),9.78(s,4H),9.15(d,4H),8.44(s,2H),8.25(dd,8H),8.05(s,2H),(7.70~7.47(m,12H),7.20~7.08(m,8H),4.00(s,6H),1.98(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
[實施例2] 色素化合物D-2之合成 (1)化合物例V-2之Br 、Cl 之混合鹽的合成
根據如下反應流程,藉由使中間體B與溴甲苯反應,而合成化合物例V-2之Br 、Cl 之混合鹽。
1H-NMRData(d6 -DMSO):10.82(s,2H),9.80(d,4H),9.17(d,4H),8.53(s,2H),8.32(dd,8H),8.15(s,2H),7.60(d,4H),7.50~7.42(m,6H),5.60(s,4H)
(2)色素化合物之合成(鹽形成)
藉由進行與實施例1同樣之操作,與下述色素原料進行反應,而獲得色素化合物D-2(吸收λmax=561.7 nm,ε=6.08×105 /TFP)。
1 H-NMRData(d6 -DMSO):10.16(s,2H),9.78(d,4H),9.13(d,4H),8.50(s,2H),8.27(dd,8H),8.12(s,2H),(7.70~7.41(m,22H),7.20~7.09(m,8H),5.55(s,4H),1.98(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
[實施例3] 色素化合物D-3之合成 (1)化合物例V-3之對甲苯磺酸鹽的合成
根據如下反應流程進行合成。首先,於50 ml均三甲苯中添加3.23 g苯並咪唑及17.3 g碳酸銣(rubidium carbonate)、56 mg乙酸鈀(palladium carbonate)、三-第三丁基膦,並於100℃下進行攪拌,然後於其中緩緩添加6.23 g的1-碘基-4-硝基苯。加熱回流8小時後,放置冷卻,然後添加乙酸乙酯及水,以乙酸乙酯進行萃取。濃縮萃取液後,以管柱層析法進行精製,獲得2.41 g中間體C。接著,進行與實施例1相同之操作,以合成中間體D、中間體E,然後藉由使該等與對甲苯磺酸甲酯反應而合成化合物例V-3之對甲苯磺酸鹽。
1H-NMRData(d6 -DMSO):10.30(s,2H),9.81(d,4H),9.17(d,4H),8.39(d,4H),8.29(d,4H),8.22(d,2H),7.92~7.78(m,8H),7.49(d,2H),7.45(d,8H),7.10(d,8H),4.25(s,6H),2.28(s,12H)
(2)色素化合物之合成(成鹽)
藉由進行與實施例1同樣之操作,與下述色素原料進行反應而獲得色素化合物D-3(吸收λmax=562.0 nm,ε=5.76×105 /TFP)。
1 H-NMRData(d6 -DMSO):10.30(s,2H),9.83(d,4H),9.19(d,4H),8.38(d,4H),8.28(d,4H),8.21(d,2H),7.91~7.80(m,6H),7.70~7.45(m,12H),7.20~7.08(m,8H),4.25(s,6H),1.98(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
[實施例4] 色素化合物D-4之合成 (1)化合物例V-4之Br 、Cl 之混合鹽的合成
根據如下反應流程,藉由使中間體E與溴甲苯反應,而合成化合物例V-4之Br 、Cl 之混合鹽。
1 H-NMRData(d6 -DMSO):10.68(s,2H),9.88(d,4H),9.23(d,4H),8.40(dd,4H),8.13~8.10(m,2H),7.95~7.91(m,2H),7.83~7.77(m,4H),7.71(d,4H),7.50~7.40(m,6H),5.96(s,4H)
(2)色素化合物之合成(成鹽)
藉由進行與實施例1同樣之操作,與下述色素原料進行反應,而獲得色素化合物D-4(吸收λmax=562.0 nm,ε=6.05×105 /TFP)。
1 H-NMRData(d6 -DMSO):10.53(s,2H),9.84(d.4H),9.19(d,4H),8.38(dd,4H),8.12~8.09(m,2H),7.93~7.90(m,2H),7.80~7.77(m,4H),7.70~7.40(m,22H),7.20~7.08(m,8H),5.93(s,4H),1.98(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
[實施例5] 色素化合物D-53之合成 (1)化合物例V-31之鹽酸鹽的合成
根據如下流程進行合成。
(i)中間體F之合成將15 g的4,4'-聯吡啶基溶解於100 ml丙酮中,然後於其中添加13.2 g的1-氯-2,4-二硝基苯,於室溫下攪拌15分鐘,接著加熱回流15小時。反應結束後,放置冷卻至室溫,接著以減壓過濾來濾取析出結晶。最後將所獲得之結晶以丙酮清洗後,進行乾燥,從而獲得18.8 g中間體F。
(ii)中間體G之合成將14.4 g中間體F懸濁於100 ml乙腈中,然後於其中添加4.6 g苯胺,加熱回流7小時。反應結束後,放冷至室溫,濾去析出結晶後,以乙腈清洗,然後乾燥。於所獲得之粗結晶中添加20 ml甲醇使其加熱完全溶解,然後於其中添加200 ml乙酸乙酯,於室溫下攪拌1小時,濾取所獲得之結晶,從而獲得10.4 g中間體G。
(iii)中間體H之合成於3 g中間體G及7 g的1-氯-2,4-二硝基苯中添加5 ml的N-甲基吡咯烷酮,於外溫110℃之油浴(oil bath)中加熱9小時。反應完畢後,放置冷卻至室溫,濾取析出結晶,然後以N-甲基吡咯烷酮清洗,進而以乙酸乙酯清洗,並加以乾燥,從而獲得3.7 g中間體H。
(iv)化合物例V-31鹽酸鹽之合成將2.4 g中間體G懸濁於30 ml二甲基甲醯胺中,然後於其中添加0.4 g的4,4'-二胺基二苯醚,於100℃下加熱攪拌6小時。反應完畢後,放置冷卻至室溫,濾取析出結晶,然後以二甲基甲醯胺清洗,進而以乙酸乙酯清洗,並加以乾燥,從而獲得1.16 g化合物例V-31鹽酸鹽。
化合物例V-31鹽酸鹽的1 H-NMR Data(CD3 OD):9.62~9.56(m,8H),8.97~8.83(m,8H),8.10~8.06(m,4H),7.97~7.94(m,4H),7.83~7.80(m,6H),7.57~7.53(m,4H)
(2)色素化合物D-53之合成(成鹽)
將上述中所獲得之V-31之鹽酸鹽1.0g加熱溶解於30 ml甲醇中,然後於其中添加3.1 g實施例1中揭示之色素原料,於60℃下攪拌30分鐘。接著放置冷卻後,於室溫下攪拌2小時,濾取析出結晶,然後以甲醇清洗,並加以乾燥,從而獲得1.8 g化合物D-53(吸收λmax=561.8 nm、ε=6.07×105 /2,2,3,3-四氟丙醇(TFP))。
化合物例D-53的1 H-NMR資料(d6 -DMSO):9.70(s(br),8H),9.08(s(br),8H),8.08(s(br),4H),7.98(s(br),4H),7.81(s(br),6H),(7.70~7.46(m,16H),7.20~7.08(m,8H),1.99(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
[實施例6] 色素化合物之合成
可藉由與上述相同之方法合成化合物例V-27~V-30、V-32~V-72的鹽酸鹽,並將所獲得之鹽酸鹽的陰離子進行陰離子交換,而合成具有各種陰離子之化合物。如上述實施例中所述,與色素原料進行反應而合成具有將氧喏色素作為相反陰離子的化合物。以下記錄若干化合物之NMR鑑定數據。
化合物例V-41鹽酸鹽的1 H-NMR Data(CD3 OD):9.58~9.55(m,8H),8.94~8.91(m,8H),7.96~7.94(m,4H),7.83~7.78(m,8H),7.73~7.70(m,4H),7.52(t,1H),7.47(d,2H),7.06~7.02(m,3H)
色素化合物D-63的1 H-NMR Data(d6 -DMSO):9.70(s(br),8H),9.07(s(br),8H),7.95(s(br),4H),7.80(s(br),8H),(7.70~7.45(m,19H),7.20~7.07(m,8H),7.02~6.98(m,3H),1.98(s,16H),1.81~1.75(m,8H),1.5(s,12H),1.47~1.33(m,8H),0.88(t,12H)
化合物例V-51鹽酸鹽的1 H-NMR Data(CD3 OD):9.64(dd,8H),8.98(dd,8H),8.53(d,2H),8.38(d,2H),8.18(d,2H),8.07(d,4H),7.97(t,2H),7.77(d,4H),7.57(d,4H),7.40(t,4H),7.20(t,2H)
色素化合物D-73的1 H-NMR Data(d6 -DMSO):10.53(s,2H),9.77(d(br),8H),9.12(s(br),8H),8.51(s(br),2H),8.39(s(br),2H),8.09(m(br),6H),7.80(d,4H),7.70~7.47(m,18H),7.42(t,4H),7.20~7.09(m,8H),1.98(s,16H),1.80~1,76(m,8H),1.52(s,12H),1.43~1.35(m,8H),0.89(t,12H)
化合物例V-54鹽酸鹽的1 H-NMR資料(CD3 OD):9.68~9.55(m,8H),9.00~8.92(m,8H),8.42(d,2H),8.28(d,2H),8.17(d,2H),8.00(d,2H),7.71(t,2H),7.54(s,2H),7.48(d,2H),7.38(d,2H),3.97(s,6H)
色素化合物D-76之1 H-NMR Data(d6 -DMSO):10.98(s,1H),9.73(s(br),8H),9.09(s(br),8H),8.41(s(br),2H),8.20(s(br),4H),8.02(s(br),2H),7.71~7.47(m,18H),7.39(s(br),2H),7.20~7.09(m,8H),3.93(s,6H),1.99(s,16H),1.82~1.77(m,8H),1.53(s,12H),1.47~1.35(m,8H),0.89(t,12H)
化合物例V-57鹽酸鹽的1 H-NMR Data(CD3 OD):9.68~9.57(m,8H),9.00~8.92(m,8H),8.42(d,2H),8.29(d,2H),8.17(d,2H),8.02~7.93(m,6H),7.83~7.80(m,6H)
色素化合物D-79的1 H-NMR Data(d6 -DMSO):10.98(s,1H),9.72(s(br),8H),9.10(s(br),8H),8.41(s(br),2H),8.20(s(br),4H),7.99(s(br),6H),7.82(s(br),6H),7.71~7.47(m,12H),7.21~7.08(m,8H),1.99(s,16H),1.82~1.77(m,8H),1.53(s,12H),1.47~1.35(m,8H),0.89(t,12H)
評價方法 (1)旋轉塗佈適應性之評價
將表3所揭示的色素(0.3 g)溶解於10 ml的2,2,3,3-四氟丙醇(TFP)中,然後將其旋塗於聚碳酸酯基板上,以目測觀察塗佈條紋。將結果示於表3。
(2)溶解經時穩定性試驗
將如表3所揭示之色素製成5.0 wt%之2,2,3,3-四氟丙醇溶液,於20℃下放置1週。以目測確認結晶析出之情況。將結果示於表3。
◎:完全未看到結晶析出。
○:未看到結晶析出。
△:略微看到結晶析出。
×:結晶析出較多。
(3)色素膜折射率測定
以橢圓偏光法(ellipsometry)測定將色素溶液(表3所示之各色素10 mg/l ml,TFP)塗佈於玻璃基板而獲得者的折射率。將結果示於表3。
由表3之結果表明,本發明之色素化合物難以形成塗佈條紋,且溶解經時穩定性優異。又,本發明之色素化合物具有高折射率。使用本發明之其他色素化合物時亦可同樣觀察到該傾向。
光資訊記錄媒體之製作
利用射出成形,將聚碳酸酯樹脂成形於具有螺旋狀組(深130 nm,寬310 nm,軌道間距0.74 μm)的厚度為0.6 mm、直徑為120 mm之基板上。製備於100 ml之2,2,3,3-四氟丙醇中溶解有1.25 g比較化合物A的塗佈液,利用旋塗法,於上述基板之組所形成之面上塗佈該塗佈液,以形成色素層。
接著,於色素塗佈面上濺鍍銀而形成膜厚度約為150 nm之反射層後,使用紫外線硬化樹脂(Daicure Clear SD640,大日本油墨化學工業製)作為黏著劑,將其與厚度為0.6 mm之隔板貼合,以製作DVD-R光碟。
光資訊記錄媒體之評價
使用DDU1000及多信號發生器(multi-signal generator)(Pulstec Industrial,Co.,Ltd製,雷射波長=660 nm,開口率=0.60),以傳輸率1倍速(11.08 Mbps)、8倍速(88.64 Mbps)、10倍速(110.8 Mbps)記錄8-16調變信號。
所使用之記錄策略如表4所示。1倍速記錄、10倍速記錄以1種,8倍速記錄以脈波寬度(pulse-width)大為不同之兩種進行記錄。
記錄功率根據各個媒體,設定為顫動最小之記錄功率。其後,使用與記錄雷射波長相同之雷射進行再生,測定靈敏度及顫動。將結果示於表5。成功設定了良好的記錄策略。
接著,進行與表4、表5同樣之操作,藉由比較化合物A設定為12x之記錄策略,繼而除使用表6所示之各色素代替比較化合物以外,以與上述同樣之方式製作DVD-R光碟。使用該等光碟,以12X進行記錄再生試驗。將結果示於表6。
如表6所示,使用實施例中所合成之色素化合物作為記錄層用色素的DVD-R光碟,在靈敏度及顫動方面優異。又,如表3所示,上述DVD-R光碟亦顯示出高反射率。該反射率是於DL媒體中可達到充分之記錄特性的水準。又,如表3所示,實施例中所合成之色素化合物具有優異之製造適應性,
[產業上之可利用性]
本發明之光資訊記錄媒體適於用作DVD-R型光資訊記錄媒體。
12...第一預刻溝槽
14...第一基板
14a...端面
16...第二預刻溝槽
18...第二基板
20...中間層
22...第一記錄層
24、26...反射層
28...第二記錄層
30...障壁層
32...雷射光
34...溝槽
36...平面
圖1是具有單層記錄層之可錄式DVD的概略剖面圖。
圖2是具有兩層記錄層之可錄式DVD的概略剖面圖。

Claims (18)

  1. 一種陽離子化合物,其是以下述通式(I)所表示者: 通式(I)中,Ar2 獨立表示可具有取代基的芳基或芳香族雜環基,L1 表示單鍵或2價連結基,Ar1 、Ar2 及L1 之至少一個具有大於等於一個的鎓陽離子;R3 及R4 分別獨立表示取代基,亦可與所取代之苯環成環;m3及m4分別獨立表示在0~4範圍內的整數,m3、m4為在2~4範圍內的整數時,多個存在之R3 、R4 可分別相同亦可不同;通式(I)中,Ar1 以下式表示: Ar2 以下式表示: 上述R1 及R2 分別獨立表示取代基,亦可與所取代之 苯環成環;m1及m2中一個表示在0~5範圍內的整數,另一個表示在1~5範圍內的整數,m1、m2為在2~5範圍內的整數時,多個存在之R1 、R2 可分別相同亦可不同。
  2. 如申請專利範圍第1項所述之陽離子化合物,其中上述通式(I)中,R1 及R2 的至少一個表示具有氮陽離子之取代基。
  3. 如申請專利範圍第2項所述之陽離子化合物,其中上述通式(I)中,L1 為單鍵。
  4. 如申請專利範圍第2項或第3項所述之陽離子化合物,其中上述氮陽離子為四取代氮陽離子或含氮原子之芳香族雜環陽離子。
  5. 如申請專利範圍第4項所述之陽離子化合物,其中上述含氮原子之芳香族雜環陽離子為吡啶陽離子、咪唑陽離子、噻唑陽離子、噁唑啉陽離子或亞胺陽離子。
  6. 一種陽離子化合物,其是以下述通式(I)所表示者: 通式(I)中,Ar1 及Ar2 分別獨立表示可具有取代基的芳基或芳香族雜環基,Ar1 、Ar2 及L1 之至少一個具有大於等於一個的鎓陽離子;R3 及R4 分別獨立表示取代基,亦可與所取代之苯環成環;m3及m4分別獨立表示在0~4範圍 內的整數,m3、m4為在2~4範圍內的整數時,多個存在之R3 、R4 可分別相同亦可不同;L1 以下式表示: 上述R5 及R6 分別獨立表示取代基;m5及m6分別獨立表示在0~4範圍內的整數,m5、m6為在2~4範圍內的整數時,多個存在之R5 、R6 可分別相同亦可不同;La 表示2價連結基。
  7. 一種陽離子化合物,其是以下述通式(IV)所表示之化合物 於通式(IV)中,R51 及R52 分別獨立表示氫原子或烷基;R53 、R54 、R55 、R56 、R57 及R58 分別獨立表示氫原子、烷基、芳基、或芳香族雜環基,R55 與R56 、R57 與R58 亦可連結形成5或6員環,R51 、R52 、R53 、R54 、R55 、R56 、R57 及R58 亦可分別更包括有取代基。
  8. 一種色素化合物,包括:申請專利範圍第1項至第7項中任一項所述之陽離子化合物;以及可中和上述陽離子化合物之電荷之量的陰離子。
  9. 如申請專利範圍第8項所述之色素化合物,其中上述陰離子為陰離子性色素。
  10. 如申請專利範圍第9項所述之色素化合物,其中上述陰離子性色素為氧喏(oxonol)色素。
  11. 如申請專利範圍第10項所述之色素化合物,其中上述氧喏色素可以下述通式(V)表示 於通式(V)中,Za25 及Za26 分別獨立表示形成酸性核的原子群;Ma27 、Ma28 及Ma29 分別獨立表示取代或未取代之亞甲基;Ka23 表示在0~3範圍內的整數,Ka23 為2或3時,多個存在之Ma27 、Ma28 可分別相同亦可不同。
  12. 如申請專利範圍第10項所述之色素化合物,其中上述氧喏色素可以下述通式(VI)表示:[化7] 於通式(VI)中,Za21 、Za22 、Za23 及Za24 分別獨立表示形成酸性核的原子群;Ma21 、Ma22 、Ma23 、Ma24 、Ma25 及Ma26 分別獨立表示取代或未取代之亞甲基;L表不會與兩個鍵形成π共軛體系的2價連結基;Ka21 及Ka22 分別獨立表示在0~3範圍內的整數,Ka21 、Ka22 為2或3時,多個存在之Ma21 、Ma22 、Ma25 、及Ma26 可分別相同亦可不同。
  13. 一種光資訊記錄媒體,包括:於一基板上具有一記錄層,其特徵在於:上述記錄層包括申請專利範圍第8項至第12項中任一項所述之色素化合物。
  14. 如申請專利範圍第13項所述之光資訊記錄媒體,其為可錄式光資訊記錄媒體。
  15. 如申請專利範圍第14項所述之光資訊記錄媒體,其為DVD-R型光資訊記錄媒體。
  16. 一種使用色素化合物之方法,包括將申請專利範圍第8項至第12項中任一項所述之色素化合物用作光資訊記錄媒體之記錄層用色素。
  17. 如申請專利範圍第16項所述之使用色素化合物之方法,其中上述光資訊記錄媒體為可錄式光資訊記錄媒體。
  18. 如申請專利範圍第19項所述之使用色素化合物之方法,其中上述光資訊記錄媒體為DVD-R型光資訊記錄媒體。
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