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TWI301973B - Optical-information recording method - Google Patents

Optical-information recording method Download PDF

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Publication number
TWI301973B
TWI301973B TW093136410A TW93136410A TWI301973B TW I301973 B TWI301973 B TW I301973B TW 093136410 A TW093136410 A TW 093136410A TW 93136410 A TW93136410 A TW 93136410A TW I301973 B TWI301973 B TW I301973B
Authority
TW
Taiwan
Prior art keywords
group
substituted
unsubstituted
recording
information recording
Prior art date
Application number
TW093136410A
Other languages
English (en)
Other versions
TW200523920A (en
Inventor
Hisashi Mikoshiba
Michihiro Shibata
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of TW200523920A publication Critical patent/TW200523920A/zh
Application granted granted Critical
Publication of TWI301973B publication Critical patent/TWI301973B/zh

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Classifications

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    • G11B7/00Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
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  • Optical Record Carriers And Manufacture Thereof (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Description

1301973 九、發明說明: 【發明所屬之技術領域】 本發明係關於一種利用高能量密度之雷射光而可進行 資訊之寫入(記錄)或讀取(再生)的熱模式型資訊記錄 媒體與資訊記錄方法。本發明特別關於一種適合於利用可 見雷射光而記錄資訊的重寫型多樣化數位光碟(DVD-R) 般之熱模式型資訊記錄媒體。 【先前技術】 習知之資訊記錄媒體(光碟)係藉由雷射光而僅可進行 一次資訊之記錄。該資訊記錄媒體也稱爲重寫型CD (所謂 CD-R),相較於習知CD之製作,具有以合適的價格且可 迅速提供少量CD之優點,隨著最近個人電腦之普及,其 需求量大增。CD-R型資訊記錄媒體的代表性構造係於透明 碟狀基板上依序疊層由有機色素而成的記錄層、由金等之 金屬層而成的反射層、甚至樹脂製之保護層。 然後,藉由照射近紅外線領域之雷射光(通常7 8 0nm 附近波長之雷射光),使記錄層局部發熱變形而進行對光 碟之資訊記錄。另一方面,通常藉由照射與記錄用雷射光 相同波長的雷射光,檢測記錄層之已發熱變形的部位(記 錄部分)與未變形的部位(未記錄部分)之反射率的差異 而進行資訊之讀取(再生)。 近年來,一直在尋求更高記錄密度之資訊記錄媒體。爲 了提高記錄密度,集中縮小所照射之雷射光徑爲有效的’ 另外,理論上得知,因爲波長短的雷射光,越能夠集中縮 -6- 1301973 小,有利於高密度化。因而,積極開發使用較習用之7 8 Onm 更短波長之雷射光而進行記錄再生的光碟,例如,所謂重 寫型多樣化數位光碟(所謂DVD-R)已上市。此光碟之軌 距較CD-R之1 .6 // m爲窄,於已形成0.8 // m預溝槽的直 徑1 2 0 m m或直徑8 0 m m之透明碟狀基板上,利用黏結劑, 使兩片由色素而成的記錄層,然後通常於該記錄層上進一 步設置反射層與保護層而成的光碟予以貼合,或是使該記 錄層位於內側,並使約略相同於該光碟大小之碟狀保護基 板成爲相貼合的構造般之進行製造。然後,DVD-R係藉由 照射可見雷射光(通常600〜700nm範圍波長之雷射光), 進行記錄與再生,便可能較CD-R型光碟進行更高密度之 記錄。 相較於習知之CD-R型,由於DVD-R型之資訊記錄媒 體能夠記錄數倍之資訊量,當然具有高的記錄感度,尤其 必須迅速進行大量資訊之處理,期望對於高速記錄之錯誤 發生率要少。另外,由色素而成的記錄層,一般而言,由 於對熱或光的經時安定性較差,期望開發即使經歷長期 間,也能夠維持對於熱或光穩定性能的記錄層。 於日本公開專利特開昭6 3 -2 0999 5號公報【專利文獻1】 中,揭示一種CD-R型資訊記錄媒體,其於基板上設置氧 雜菁(Oxonol)色素而成的記錄層。藉由使用此色素化合 物,經歷長期間也能夠維持穩定的記錄再生特性。而且, 於此公報中,揭示一種氧雜菁色素,以分子內鹽的型式導 入銨。另外,於日本公開專利特開2000- 5 26 5 8號公報【專 利文獻2】、日本公開專利特開2002-249674號公報【專利 1301973 文獻3】中,揭示一種氧雜菁色素,其顯示高的耐光性與 耐久性,提出良好記錄特性之光資訊記錄媒體。然而,於 此公報中,揭示一種含有氧雜菁色素之光資訊記錄媒體, 但並未記載相當於DVD-R規格之8倍速以上高速的記錄再 生之特別優異的性能。 【專利文獻1】日本公開專利特開昭6 3 - 2 0 9 9 9 5號公報 【專利文獻2】日本公開專利特開2 0 0 0 - 5 2 6 5 8號公報 【專利文獻3】日本公開專利特開2 0 0 2 - 2 4 9 6 7 4號公報 【發明内容】 發明所欲解決之技術問題 本發明之發明人將揭示於該公報之各種氧雜菁色素化 合物使用於DVD-R型光資訊記錄媒體,針對其性能進行探 討。其結果,得知於記錄層中含有該色素化合物之DVD-R 型光資訊記錄媒體,於等倍速至4倍速之低速記錄發揮足 夠之性能,尤其於8倍速以上之高速記錄時,顯示特別優 異的記錄特性,特別是孔徑比方面更爲優異。亦即,本發 明之光資訊記錄媒體,發現一面維持1〜4倍速之低速記錄 下的良好記錄特性,另一方面,即使同時於8倍速以上之 高速記錄也顯示良好之記錄性能而完成了本發明。 本發明之目的一面維持1〜4倍速之低速記錄下的良好 記錄特性,另一方面,即使於8倍速以上之高速記錄,也 實現高的反射率與高的調變度。另外,提供一種於1〜1 6倍 速記錄之廣範圍記錄速度達成足夠低振動的光資訊記錄媒 體。本發明之另一目的在於提供一種對光、熱具有穩固性 之光資訊記錄媒體。 1301973 解決問題之技術手段 根據本發明之發明人鑽硏的結果,發現該目的可以藉由 下列之技術手段而達成。 (1 ) 一種光資訊記錄媒體,其包含··透明基板、含色 素而成之記錄層與反射層的熱模式重寫型光資訊記錄媒 體,其特徵爲:該記錄層之主成分爲有機色素,利用波長 6 0 0〜70011111之雷射,以線速度\^(111/3)對該記錄媒體進行 記錄時之最適記錄功率爲25mW以上(較宜爲30 mW以 上、更佳爲32mW以上、最好爲60mW以下)。彳日是,最 適記錄功率係於記錄8 - 1 6調變信號時,振動成爲最小的記 錄功率(Po),該Po係以下式表示。 i>〇 = PlxV(v73.5) -1,5P1xV(W3,5) 但是’ P 1係以線速度3 · 5 ( m / s )記錄時之最適記錄功率。 (2 )揭不於(1 )之光資訊記錄媒體,其中該有機色素 爲氧雜菁色素。
(3)揭不於(2)之光資訊記錄媒體,其中該氧雜菁色 素係下式通式(1 )所示之構造。
1301973 式中’ Za1與Za2表示形成各自獨立之酸性核的原子群。 Ma1、Ma2、Ma3表示各自獨立之取代或未取代的次甲基。 ka表示〇〜3之整數,ka爲2以上時,數個所存在之、 Ma2可以相同,也可以不同。 Q表示進行電何中和的離子,y表示電荷中和所需要之 數目。 (4 )揭示於(3 )之光資訊記錄媒體,其中該氧雜菁色 素之Q所示之離子係下式通式(2)所示之構造。 通式(2 )
19 R20 R11 R12
式中,R11、R12、R14、R15、R16、R17、R19 與 R2G 表示 各自獨立之氫原子或取代基。R13與R18表示各自獨立之取 代基。 (5 )揭示於(1 )〜(4 )中任一項之光資訊記錄媒體, 其中[1]於已形成軌距0.6〜〇.9//m預溝槽之直徑l2〇±3mm 或直徑80±3mm、厚度0.6±0.1mm透明碟狀基板之已設置 該預溝槽側之表面,將設置含色素之記錄層而成的二片層 壓物,使各自之記錄側向內接合而厚度成爲1.2±0.2mm’ -10- 1301973 或是[2]於由軌距 0.6〜0.9 /zm預溝槽所形成的直徑 120±3mm或直徑80±3mm、厚度〇.6±0.1mm透明碟狀基板 之已設置該預溝槽側之表面,使記錄層成爲內側,將設置 含色素之記錄層而成的層壓物與碟狀保護板予以接合的厚 度成爲 1.2±0.2mm。 (6 ) —種光資訊記錄媒方法,將波長600〜700 nm之雷 射,以線速度v ( m/s ),對透明基板上已設置至少含有機 色素之記錄層與反射層的光資訊記錄媒體進行最適記錄功 率爲25mW以上(較宜爲60mW以下)之記錄。該最適記 錄功率於記錄8 - 1 6調變信號時,振動成爲最小的記錄功率 (P〇 ),該Po係以下式表示。
Po = PI X ^(v / 3- 5) ~ 1.5P1 x ,](v / 3.5) 但是’ P 1係以線速度3 . 5( m/s )記錄時之最適記錄功率。 (7 ) —種光資訊記錄媒體’適用於揭示於(6 )之光資 δΛ δ己錄方法。 (8 )揭示於(7 )之光資訊記錄媒體,其中於揭示於(7 ) 之光貝訊記錄媒體中所含之有機色素爲氧雜菁色素。 (9 )揭示於(8 )之光資訊記錄媒體,其中該氧雜菁色 素係下式通式(1 )所示之構造。 通式(1 ) -11 - 1301973
式中’ Za1與Za2表示形成各自獨立之酸性核的原子群。 Ma1、Ma2、Ma3表示各自獨立之取代或未取代的次甲基。
ka表示0〜3之整數,ka. 2以上時,數個所存在之Mai、 M a2可以相同,也可以不同。 Q表示進行電荷中和的離子,y表示電荷中和所需要之 數目。 (10)揭示於(9)之光資訊記錄媒體,其中該氧雜菁 色素之Q所示之離子係下式通式(2)所示之構造。 通式(2 )
式中,R11、R12、R14、R15、R16、R17、R19 與 R2G 表示 各自獨立之氫原子或取代基。R13與R18表示各自獨立之取 代基。 -12 - 1301973 (1 1 )揭示於(7 )〜(1 0 )中任一項之光資訊記錄媒體, 其中[1]於已形成軌距0.6〜0.9 // m預溝槽之直徑120±3mm 或直徑80:t3mm、厚度〇.6±0.1mm透明碟狀基板之已設置 該預溝槽側之表面,將設置含色素之記錄層而成的二片層 壓物,使各自之記錄側向內接合而厚度成爲1.2 土 0.2mm, 或是[2]於由軌距 0.6〜0.9 μ m預溝槽所形成的直徑 120±3mm或直徑80±3mm、厚度0.6±0.1mm透明碟狀基板 之已設置該預溝槽側之表面,使記錄層成爲內側,將設置 含色素之記錄層而成的層壓物與碟狀保護板予以接合的厚 度成爲 l-2±〇.2mm。 【發明效果】 相較於低速記錄用比較色素,本發明能夠提供一種雙折 射率之實部η較大,虛部k約相等或較小之色素。也能夠 提供一種具有優異之低速〜高速記錄特性的光資訊記錄媒 am 體。 【發明之實施態樣】 以下,詳細說明本發明。 使用於本發明光資訊記錄媒體的有機色素較宜爲氧雜 菁色素。氧雜菁色素之具體例,可列舉:揭示於 F · Μ. Harmer 戶斤著之 Heterocyclic Compounds-Cyanine Dyes and Related Compounds、John& Wiley& Sons、New York、 London、1964 年發行。 氧雜菁色素之中,較宜爲下式通式(1)所示之構造。 通式(1 ) -13- 1301973
Za1 ka
Za4
Qy 通式(1 )中’ Za1與Za2袠示形成各自獨立之 酸性核的 原子群。
Za1與Za2之具體例係根據James所編之The Theory of the Photographic Process、第 4 版、MacmUan 公司、1977 年、第1 9 8頁所定義的。具體而言,可列舉:吡唑-5 _酮、 吡唑啉_3,5-二酮、咪唑啉酮、乙內醯脲、2或4•硫代乙 內醯脲、2 -亞胺基噚嗤啉-4 -酮、2 _噚唑啉—5 _酮、2 _硫代噚 唑啉- 2,4-一酮、異繞單寧、繞單寧、5,6員之碳環(例如, 印滿-1,3-二酮)、噻吩-3-酮、噻吩_3_酮“,卜二氧化物、 吲哚滿-2-酮、吲哚滿-3-酮、2_羰基吲哚滿鑰、5,7_二羰基 _6,7-二氫噻嗤[3,2_&]喃陡、31二氫異嗤啉I酮、 曙烷-4,6-二酮(例如,梅耳酸(Meidrum,s ^^))、巴比土 酸、2-硫巴比土酸、香豆素㈣ [^㈣淀-^-二酮^比嗤……唾啉酮^哩卩比陡嗣、 3·二氰基次甲基-3-苯基丙腈、梅耳酸(Meldrum,s μη)等 之環,較宜爲啦哩-5-酮、巴比土酸、2_硫巴比土酸、丨% —% 院-4,6 -二醒。
Ma1、Ma2、Ma3表示各自獨立之取代或未取代的次甲 基。取代Ma、〇取代基表示取代或無取代之院 基取代或無取代之丨兀氧基、取代或無取代之芳其 、 取代 _14- 1301973 或無取代之芳氧基、取代或無取代之雜環基、鹵素原子、 羧基、取代或無取代之烷氧羰基、氰基、取代或鈿取代之 醯基:取代或無取代之胺基甲醯基、胺基、取代胺基、磺 基、趣s、硝基、取代或無取代之硫醯胺基、耳又代或無取 代之!女羰胺基、取代或無取代之烷硫醯基、取代或無取代 之芳硫醯基、取代或無取代之磺醯基與取代或無取代之胺 磺醯基。取代基較宜爲取代或無取代之碳數i〜2〇的烷基、 取代或無取代之碳數2〜20的雜環基、取代或無取代之碳數 1〜20的烷氧基、取代或無取代之碳數6〜2〇的芳基與鹵素 原子;更佳爲取代或無取代之碳數丨〜…的烷基、取代或無 取代之碳數1〜ίο的烷氧基、取代或無取代之碳數2〜ι〇的 雜環基與鹵素原子;最好爲取代或無取代之碳數丨〜5的烷 基、取代或無取代之碳數i〜5的烷氧基、取代或無取代之 碳數2〜6的雜環基與鹵素原子。
Ma1、Ma2、M a3較宜爲無取代之次甲基、或是無取代之 碳數卜5的烷基、無取代之碳數丨〜5的烷氧基、取代或無 取代之碳數2〜6的雜環基與鹵素原子所取代之次甲基。 ka表示〇〜3之整數,更佳表示之整數。^爲2以 上時’數個所存在之Ma1、Ma2可以相同,也可以不同。 Q表示進行電荷中和的離子,y表示電荷中和所需要之 數目。 某化合物爲陽離子、陰離子或者是否具有淨離子電荷係 視其化合物之取代基而定。於通式(1 ),Q所示之陽離子 係對應於相對之色素分子的電荷,有可能表示陽離子,也 有可能表示陰離子’另外,色素分子無電荷之情形,q並 -15- 1301973 不存在。Q所示之離子並無特別之限制,可以爲由無機化 合物而成的離子,也可以爲由有機化合物而成的離子。另 外,Q所示之離子的電荷可以爲1價,也可以爲多價。Q 所示之陽離子,例如,可列舉:如鈉離子、鉀離子之金屬 離子、4級銨離子、鲜離子、磺酸鑰離子、鐵根離子、硒 鑰離子、碘離子等之鑰離子。另一方面,Q所示之陰離子, 例如,可列舉:如氯化物離子、溴化物離子、氟化物離子 之鹵素陰離子;如硫酸根離子、磷酸根離子、磷酸氫根離 子等之雜聚酸根離子、琥珀酸根離子、馬來酸根離子、富 馬酸根離子、芳香族二磺酸根離子之有機酸多價陰離子; 四氟化磺酸離子、六氟化磷酸離子。 Q所示之陽離子較宜爲鑰離子,更佳爲4級銨離子。4 級銨離子之中,尤以於日本公開專利第2000-5265 8號公報 之通式(1-4 )所示之4,4’-二吡啶鑰陽離子以及於日本公開 專利第2002-5 9652號公報所揭示之4,4’-二吡啶鑰陽離子 更爲理想。 通式(1)所示之色素之中,Q所示之離子較宜爲下列 通式(2 )所示之構造。 通式(2 ) -16- 1301973 r18
R11 r!2
R13 式中,R11、R12、R14、R15、Rl6、Rl7、汉19與 R2。表示 各自獨立之氫原子或取代基。R13與R18表免欠'
丨、食曰獨立之取 代基。取代基之例子,可列舉:鹵素原子、户宜/ ^ 阮基(包含環 烷基、雙環烷基)、烯基(環烯基、雙環燦基)、块其 芳基、雜環基、氰基、羥基、硝基、羧基、户&甘 ^ /兀氧基、芳氧 基、矽烷氧基、雜環氧基、醯氧基、胺基申赔每 氧基、烷氧 羰氧基、芳氧羰氧基、胺基(包含苯胺基)、酿胺其、月安 羰胺基、烷氧羰胺基、芳氧羰胺基、胺磺酸胺基、p其跑 芳基磺醯胺基、氫硫基、烷硫基、芳硫基、雜p # ’、 木田银硫基、胺
磺醯基、磺基、烷基與芳基亞磺醯基、烷基 土 /、方S硫醯基、 醯基、芳氧羰基、烷氧羰基、胺基甲醯基、;I的% 方基與雑環偶 氮基、醯亞胺基、膦基、磷醯基、磷醯氧_、憐驢胺其 矽烷基。 更詳言之,R11、R12、R14、R15、R16、R17、 19 ^ R 與 R2 ( 表示各自獨立之鹵素原子(例如,氯原子、湟g 俠貺于、碘原 子)、烷基[直鏈、分歧、環狀之取代或無取代的院基。此 等係烷基(較宜爲碳數1〜3 0之烷基,例如,φ基、乙基、 -17- 1301973 心丙基、異丙: 2-氰乙基、2-$ 取代或無取代 二烷基環己基 取代的雙環烷 氫原子的一價 [2,2,2]辛烷-3. 以下所說明之 表示如此槪念 取代或無取代 代或無取代的 香葉草基、油 無取代的環烯 原子的一價官 基)、雙環嫌 碳數5〜30之耳 個雙鍵之雙環 環[2,2,1]庚-2_ 基(較宜爲碳 基、丙炔基、 6〜3 0之取代或 基、w-氯苯基 或6員之取代 去除一個氫原 員的芳香族雜 基、卜丁基、卜辛基、二十烷基、2-氯乙基、 乙基環己基)、環烷基(較宜爲碳數3〜30之 的環烷基,例如,環己基、環戊基、4-〃-十 )、雙環烷基(較宜爲碳數5〜3 0之取代或無 基,亦即,從碳數5〜3 0之雙環院基除去一個 官能基。例如,雙環[1,2,2]庚烷-2-基、雙環 基),再者,也包含多環構造之三環構造等。 取代基中的烷基(例如,烷硫基之烷基)也 的烷基。]、烯基[表示直鏈、分歧、環狀之 的烯基。此等係烯基(較宜爲碳數2〜30之取 烯基,例如,乙烯基、烯丙基、異戊二烯基、 嫌基)、環烯基(較宜爲碳數3〜30之取代或 基,亦即,從碳數3〜3 0之環烯基除去一個氫 能基。例如,2 -環戊烯-1 -基、2 -環己烯-1 -基(包含取代或無取代之雙環烯基,較宜爲 又代或無取代的雙環烯基,亦即,除去具有一 烯基之一個氫原子的一價官能基。例如,雙 -綠-1 -基、雙環[2,2,2 ]辛· 2 -烯· 4 -基)。]、炔 數2〜3〇之取代或無取代的炔基,例如,乙炔 二甲基砂院基乙炔基)、芳基(較宜爲碳數 ,無取代的芳基,例如,苯基、;7 -甲苯基、萘 〇 -己癸醯胺基苯基)、雜環基(較宜爲從5 或無取代的芳香族或非芳香族之雜環化合物 :的一價官能基,更佳爲碳數3〜30之5或6 哀基。例如,2_呋喃基、2_噻吩基、厂嘧啶基、 -18- 1301973 2-苯并噻哩基)、氰基、經基、硝基、殘基、院氧基(, 宜爲碳數卜30之取代或無取代的院氧基,例如,甲氧 乙氧基、異丙氧基、^丁氧基、〃_辛氧基、2_甲氧基乙氧基")、 芳氧基(較宜爲碳數6〜3〇之取代或無取代的芳氧基,例 如,本氧基、2-甲基苯氧基、4•卜丁基苯氧基、3_硝基苯氧 基、2-四癸醯胺基苯氧基)、矽烷氧基(較宜爲碳數3〜〇 之矽烷氧基,例如,三甲基矽烷氧基、丁基矽烷氧基)、 雜環氧基(較宜爲碳數2〜3 0之取代或無取代的雜環氧綦、 1-苯基四唑-5-氧基、2-四氫吡喃氧基、醯氧基(較宜爲申 醯氧基、碳數2〜30之取代或無取代的烷羰氧基、碳數6〜3〇 之取代或無取代的芳滕氧基,例如,甲醯氧基、乙酿氧基、 一甲基乙醯興基硬爿曰酿氧基、苯酿氧基、p -甲氧基苯難^ 氧基)、胺基甲醯氧基(較宜爲碳數1〜3〇之取代或無取代 的胺基甲醯氧基’例如,N,N-二甲胺基甲醯氧基、n,n、= 乙胺基甲醯氧基、嗎啉代羰氧基、N,N-二_π_辛胺基锻氧 基、Ν-π-辛胺基甲醯氧基)、烷氧羰氧基(較宜爲碳數2〜3〇 之取代或無取代的烷氧羰氧基,例如,甲氧基鑛氧基、乙 氧基鐵氧基、卜丁氧基碳氧基、η-辛氧基鑛氧基)、芳氧其 羰氧基(較宜爲碳數7〜30之取代或無取代的芳氧鑛氧基, 例如,苯氧基羰氧基、;^甲氧基苯氧基羰氧基、十六酸 氧基苯氧基羰氧基)、胺基(較宜爲胺基、碳數iyO之取 代或無取代的烷胺基、碳數6〜3 0之取代或無取代的芳胺 基,例如,胺基、甲胺基、二甲胺基、苯胺基、N _甲基苯 胺基、二苯胺基)、醯胺基(較宜爲甲醯胺基、碳數卜3〇 之取代或無取代的院羰胺基、碳數6〜3 〇之取代或無取代的 -19- 1301973 方簾s女基,例如,甲醯胺基、乙醯胺基、三甲基乙酸 月桂醯胺基、本醯胺基、3,4,5-三- /2 -辛氧基苯基羰g 胺基羰胺基(較宜爲碳數1〜3〇之取代或無取代的 基’例如’胺基甲醯胺基、N,N -二甲胺基鑛胺基、 乙胺基羰胺基、嗎啉代羰胺基)、烷氧基羰胺基( 碳數2〜3 0之取代或無取代的烷氧基羰胺基,例如, 羰胺基、乙氧基羰胺基、ί-丁氧基羰胺基、吣十八烷 胺基、Ν -甲基甲氧基羰胺基)、芳氧基羰胺基(較 數7〜30之取代或無取代的芳氧基羰胺基,例如,苯 胺基、ρ -氯苯氧基羰胺基、辛氧基苯氧基羰胺 月女διι酿fee基(較且爲碳數〇〜3 〇之取代或無取代的胺 基,例如,胺磺醯胺基、N,N -二甲胺基磺醯胺基、 基胺基磺醯胺基)、烷基與芳基磺醯胺基(較宜爲碳 之取代或無取代的烷基磺醯胺基、碳數6〜30之取代 代的芳基磺醯胺基,例如,甲基磺醯胺基、丁基磺酸 苯基磺醯胺基、2,3, 5-三氯苯基磺醯胺基、;^甲基苯 胺基)、氫硫基、烷硫基(較宜爲碳數1〜3 〇之取代 代的烷硫基,例如,甲硫基、乙硫基、^十六烷硫 芳硫基(較宜爲碳數6〜30之取代或無取代的芳硫 如,苯硫基、P -氯苯硫基、m -甲氧基苯硫基)、雜 (較宜爲碳數2〜30之取代或無取代的雜環硫基,β 苯并噻唑硫基、1 -苯基四唑-5 ·基硫基)、胺磺醯基 爲碳數0〜3 0之取代或無取代的胺磺醯基,例如,Ν 磺醯基、Ν-(3-十二烷氧基丙基)胺磺醯基、Ν,Ν 胺磺醯基、Ν -乙醯基胺磺醯基、Ν -苯醯基胺磺醯基、 胺基、 ?基)、 胺羰胺 Ν,Ν-二 較宜爲 甲氧基 氧基羰 宜爲碳 氧基羰 基)、 磺醯胺 Ν · «-辛 數1〜30 或無取 !胺基、 基磺醯 ;或無取 基)、 基,例 ;環硫基 如,2 -丨(較宜 -乙基胺 •二甲基 N-( N,- -20- 1301973 苯基胺基甲酿基)胺磺醯基)、磺基、烷基與芳基胺磺醯 基(較宜爲碳數丨〜30之取代或無取代的烷基磺醯基、碳數 6〜3 0之取代或無取代的芳基磺醯基,例如,甲基磺醯基、 乙基礦釀基、苯基磺醯基、p甲基苯基磺醯基)、烷基與 方基礦釀基(較宜爲碳數丨〜3 〇之取代或無取代的烷基磺醯 基、碳數6〜30之取代或無取代的芳基磺醯基,例如,甲基 擴醯基、乙基磺醯基、苯基磺醯基、"甲基苯基磺醯基)、 酿基(較宜爲甲醯基、碳數2〜3〇之取代或無取代的烷基羰 基、碳數7〜30之取代或無取代的芳基羰基、利用碳數4〜3〇 之取代或無取代的碳原子與羰基鍵結的雜環羰基,例如, 乙醯基、二甲基乙醯基、2_氯乙醯基、硬脂醯基、苯醯基、 广^半氧基苯基羰基、2 -吡啶基羰基、2 -呋喃基羰基)、芳 氧基鑛基(較宜爲碳數7〜30之取代或無取代的芳氧基羰 基’例如’苯氧基羰基、氯苯氧基羰基、硝基苯氧基 鑛基、ρ-ί-丁基苯氧基羰基)、烷氧基羰基(較宜爲碳數 2〜3 0之取代或無取代的烷氧基羰基,例如,甲氧基羰基、 乙氧基鑛基、丁氧基羰基、^十八烷氧基羰基)、胺基甲 酸基(較宜爲碳數1〜3 〇之取代或無取代的胺基甲醯基,例 如,胺基甲醯基、Ν-甲基胺基甲醯基、Ν,Ν_二甲基胺基甲 醢基、Ν,Ν-二-心辛基胺基甲醯基、Ν-(甲基磺醯基)胺基 甲醯基)、芳基與雜環偶氮基(較宜爲碳數6〜30之取代或 無取代的芳偶氮基、碳數3〜3 〇之取代或無取代的雜環偶氮 基’例如,苯基偶氮、[氯苯基偶氮、5_乙硫基-153,4_噻 二Ρ坐-2-基偶氮)、亞胺基(較宜爲Ν_琥珀醯亞胺醯基、 Ν-鄰苯二甲醯亞胺基)、膦基(較宜爲碳數2〜3〇之取代或 -21 - 1301973 無取代的膦基,例如,二甲基膦基、二苯基膦基、甲基苯 氧基膦基)、磷醯基(較宜爲碳數2〜30之取代或無取代的 磷醯基,例如,磷醯基、二辛氧基磷醯基、二乙氧基磷醯 基)、磷醯氧基(較宜爲碳數2〜30之取代或無取代的磷酿 氧基,例如,二苯氧基磷醯氧基、二辛氧基磷醯氧基)、 磷酿胺基(較宜爲碳數2〜30之取代或無取代的磷酿胺基, 例如’二甲氧基磷醯胺基、二甲胺基磷醯胺基)、砂院基 (較宜爲碳數3〜3 0之取代或無取代的矽烷基,例如,三甲
基砂烷基、卜丁基二甲基矽烷基、苯基二甲基矽院基)。 於該官能基之中,具有氫原子之官能基,也可以去除此 氫原子,進一步利用該官能基進行取代。如此官能基之例 子’可列舉:烷基羰基胺基磺醯基、芳基羰基胺基磺醯基、 烷基磺醯基胺基羰基、芳基磺醯基胺基羰基。其例子可列 舉:甲基磺醯基胺基羰基、P-甲基苯基磺醯基胺基羰基、 乙醯基胺基磺醯基、苯醯基胺基磺醯基。 R1 與R表不各自獨立之取代或無取代的烷基、 代或無取代之雜環基。其中,更 。再者,以取代芳基爲最好。R13 的取代基,較宜爲羥基、取代或 取代之烷基與鹵素原子。 ^的最佳構造係下式之通式(3 )
R12、R14、R15、 氨原子。R 1 3 取代或無取代之芳基、取 佳爲取代或無取代之芳基 與R18爲取代芳基之情形 無取代之芳基、取代或無 Μ本:發明之氧雜菁色 所示之構造。 R17、R19與r2〇較宜全部爲 通式(3 ) -22- 1301973
1/2 通式(3)中,R^R2、!^與R4表示各自猸4 曰獨乂之取代或 無取代之烷基、取代或無取代之芳基、取代或無取代之雜 環基。R1、R2、R3與R4也可以相互鍵結而形成環構造。$ R2、r22、r23、r24、r25、r26、r27、r28、π 二3。 表示各自獨立之氫原子或取代基。R21、R22、R23、r24、 25
r26、r27、r28、R”與r3Q之中,相鄰接的二個取代基也可 以相互鍵結而形成環構造。 取代基之例子,可列舉:該通式(2 )之R 1 1、R i 2、R i 4、 R15、Rl6、r17、r19與r2G所述之取代基。 R21、R22、、R24、R25、r26、r27、r28、r” 與 r3〇 較宜爲各自獨立之氫原子、羥基、氰基、鹵素原子、取代 或無取代之芳基、取代或無取代之烷基。 R2l、R”、R23、R24、R25、r26、r27、r28、r29 與 r3〇
的較佳例係R2 3、R28爲羥基,並且R2 2、R27爲取代或無取 代之苯基,再者’更佳的例子,其他爲氫原子。 以下,雖然列舉本發明之通式(1)(包含通式(3)) 所示之化合物的較佳具體例,但是,本發明並非受此等化 合物所限定。 -23- 1301973
-24 1301973
-25- 1301973 色素
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28- 1301973
一般之氧雜菁色素能夠藉由相符的亞甲基化合物與次 甲基源(爲了將次甲基導入次甲基染料所用之化合物)之 縮合反應而進行合成。針對此種化合物之詳細說明,可以 參照於日本公告專利特公昭39_22069、特公昭43-3 5 04、 特公昭52-38056、特公昭54-38129、特公昭55-10059、特 公昭58-35544號、特公昭49-99620、特公昭52-92716、特 公昭59-16834、特公昭63-316853、特公昭64-40827號公 報,以及英國專利第1 1 3 3 9 8 6號、美國專利第3 247 1 27、 4042397、 4181225、 5213956、 5260179 號之各專利說明書。 也已揭示於日本公開專利特開昭 63 -220999 5、特開平 10-309871、特開 2002-249674 號公報。
有關本發明之該通式(1)與(3)所示之色素化合物, 可以單獨使用,或是也可以合倂二種以上使用。另外,也 可以將有關本發明之色素化合物與其他之色素化合物合倂 使用。合倂使用之色素,例如,可列舉··偶氮色素(包含 與金屬離子已配位化之色素)、亞甲基吡咯色素、花青 (cyanin)色素等。 用於本發明之色素的熱分解溫度較宜於1 0 0〜3 5 0 °c之範 圍內。再者,更佳爲150〜300 °C之範圍內。最好爲200〜300 °C範圍內。 用於本發明之色素的非晶形膜的光學特性上,雙折射率 之係數η (實部:折射率)、k (虛部:衰減係數)較宜爲 2·0€ 3.0、0.005 S kS 0.30。更佳爲 2 · 1 S n S 2.7、0.0 1 $k$0.15° 最好爲 2.15$nS2.50、0.03Sk‘0.10。 本發明之資訊記錄媒體之記錄層具有該通式(丨)與(3 ) -29- 1301973 所示之色素化合物,於該條件下,只要具有特定之最適記 錄功率的話,並無特別之限制,較宜爲於基板上至少依序 疊層而設置含有有機色素之記錄層、光反射層的光資訊記 錄媒體,於該條件下,具有特定之最適記錄功率。 將本發明之光資訊記錄媒體應用於CD-R之情形,於已 形成軌距1.4〜1.8 // m預溝槽的厚度1.2±0.2 mm的透明碟狀 基板上,較宜爲依序具有該通式(1)(較宜爲通式(3)) 所示之色素化合物的記錄層、光反射層與保護層。另外, 應用於DVD-R之情形下,較宜爲以下二個態樣。 [1] 於已形成軌距0.6〜0.9/zm預溝槽的厚度0.6±0.1mm之 透明碟狀基板上,設置含有該通式(1 )所示之色素化合物 的記錄層與光反射層而成的二片疊層物,分別使記錄層成 爲內側而相接合,成爲厚度1.2±〇. 2mm所構成的光資訊記 錄媒體。 [2] 於已形成軌距0.6〜0.9/zm預溝槽的厚度0.6±0.1mm之 透明碟狀基板上,設置含有由該通式(1)所示之色素化合 物的記錄層與光反射層而成的疊層物,與形狀相同於該疊 層物之碟狀基板的透明碟狀保護基板,使記錄層成爲內側 而相接合,成爲厚度1 .2±0.2 mm般之所構成的光資訊記錄 媒體。還有,於該DVD-R型光資訊記錄媒體中,也可以於 光反射層上,作成進一步設置保護層的構造。 本發明之光資訊記錄媒體,較宜作爲8倍速以上之高速 記錄再生媒體使用。再者,較宜作爲1 〇倍速以上之高速記 錄再生媒體使用。更佳作爲1 2倍速以上之高速記錄再生媒 體使用。最好作爲1 6倍速以上之高速記錄再生媒體使用。 -30- 1301973 資料之傳送速度’適宜爲80Mbps以上,較宜爲11() Mbps 以上,更佳爲130 MbPs以上,最好爲170 Mbps以上。 本發明之資訊記錄媒體,例如,可以利用如下所述之材 料與方法而進行製造。 基板(包含保護基板)能夠由各種材料進行任意選擇而 作爲習知之資訊記錄媒體的基板使用。基板材料,例如, 可列舉:玻璃;聚碳酸酯;聚甲基丙烯酸甲酯等之丙烯樹 脂;聚氯乙烯、氯乙烯共聚物等之氯化乙烯系樹脂;環氧 樹脂;非晶形聚烯烴與聚酯等;也可以依需求而將此等材 料合倂使用。還有,此等材料能夠作爲薄膜狀或具剛性基 板使用。基於耐濕性、尺寸安定性與價格等之觀點,該材 料之中較宜爲聚碳酸酯。 基於改善平面性與黏結劑與防止記錄層變質之目的,於 設置記錄層側之基板表面上,也可以設置底塗層。底塗層 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-羥甲基丙烯基醯胺、苯乙烯-乙烯基甲苯共聚物、氯颯化聚 乙烯、硝基纖維素、聚氯乙烯、氯化聚烯烴、聚酯、聚醯 亞胺、醋酸乙烯-氯化乙烯共聚物、乙烯-醋酸乙烯共聚物、 聚乙烯、聚丙烯、聚碳酸酯等之高分子物質;以及矽烷偶 合劑等之表面改質劑。底塗層能夠將該物質溶解或分散於 適當之溶劑中而調配塗布液之後,藉由旋轉塗布、浸漬塗 布、擠壓塗布等之塗布法,進行此塗布液於基板表面之塗 布而予以形成。 另外,於基板(或底塗層)上,形成表示循軌用溝或定 -31 - 1301973 址信號等資訊之凹凸(預溝槽)。此預溝槽較宜於進行聚 碳酸酯等樹脂材料之射出成型或擠壓成型之際,直接以該 軌距形成於基板上。另外,也可以藉由設定預溝槽層而進 行預溝槽之形成。預溝槽層之材料,可以使用丙烯酸之單 酯、二酯、三酯與四酯之中的至少一種單體(或是寡聚物) 與光聚合起始劑之混合物。預溝槽層之形成,例如,首先 於精密製得之母型(壓模)上,塗布由該丙烯酸酯與聚合起 始劑而成的混合液,進一步將基板放置於此塗布液層上之 後,藉由穿透基板或母型而進行紫外線之照射,使塗底層 硬化而使得基板與塗布層相黏著。接著,能夠將基板從母 型予以剝離。 基板上(或底塗層)已形成預溝槽的表面上,設置該有 機色素,較宜含有有關本發明該通式(1)所示之色素化合 物的記錄層。 於記錄層中,能夠進一步含有爲了使耐光性提高之各種 抗褪色劑。抗褪色劑之代表例,可列舉:揭示於日本公開 專利特開平3 -224793號公報之通式(III) 、(IV) 、(V) 所示之金屬配位化合物、二亞錢(diimonium)鹽、錢(aminium) 鹽或日本公開專利特開平2-3 002 8 7或平2- 3 0 0 2 8 8號公報 中所示之亞硝化合物、日本公開專利特開平1 〇 - 1 5 1 8 6 1號 公報所示之TCNQ衍生物等。 能夠藉由將有關本發明之色素、加上所需之消光劑、黏 結劑等溶於溶劑中而調配塗布液,接著,將此塗布液塗布 於基板表面而形成塗膜之後,經乾燥而進行記錄層之形 成。色素記錄層形成用塗布液之溶劑,可列舉:醋酸丁酯、 -32- 1301973 乳酸乙酯、纖維素醋酸酯等之酯類;甲基乙基酮、環己酮、 甲基異丁基酮等之酮類;二氯甲烷、1,2-二氯乙烷、氯仿 等之氯化碳氫化合物;二甲基甲醯胺等之醯胺類;環己烷 等之碳氫化合物;四氫呋喃、乙基醚、二噚烷等之醚類; 乙醇、π-丙醇、異丙醇、^丁醇、二丙酮醇等之醇類;2,2,3, 3-四氟丙醇等之氟系溶劑;乙二醇一甲基醚、乙二醇一乙基 醚、丙二醇一甲基醚等之二醇醚類等。該溶劑可以考量所 用之化合物的溶解性而單獨使用或組合二種以上而使用。 因應於目的,塗布液中也可以進一步添加抗氧化劑、UV吸 收劑、可塑劑、潤滑劑等各種添加劑。 黏結劑之例子,例如,可列舉:明膠、纖維素衍生物、 葡萄糖、松香、橡膠等之天然有機高分子物質;聚乙烯、 聚丙烯、聚苯乙烯、聚異丁烯等之烴系樹脂;聚氯乙烯、 聚氯偏乙烯、聚氯乙烯-聚醋酸乙烯共聚物等之乙烯基系樹 脂;聚丙烯酸甲酯、聚甲基丙烯酸甲酯等之丙烯基樹脂; 聚乙烯醇、氯化聚乙烯、環氧樹脂、丁縮醛樹脂、橡膠衍 生物、酚-甲醛樹脂等之熱硬化性樹脂的初期縮合物等之合 成的有機高分子。合倂黏結劑而作爲記錄層材料使用之情 形,相對於色素,黏結劑之使用量一般爲0 · 0 1〜5 0倍量(質 量比)之範圍,較宜爲〇 · 1〜5倍量(質量比)之範圍。進 行如此方式,所調配的塗布液之色素濃度一般爲 0 · 0 1〜1 0 質量%之範圍,較宜爲0.1〜5質量%之範圍。 塗布方法可列舉:噴霧法、旋轉塗布法、浸漬法、滾筒 塗布法、刀鋒塗布法、刮刀塗布法、網板印刷法等。記錄 層可以爲單層、也可以爲多層。記錄層之層厚一般於 -33- 1301973 20〜5 00nm之範圍,較宜爲50〜3 00nm之範圍。 基於改善資訊再生時之反射率的目的,於該記錄層上設 置反射層。反射層材料之光反射性物質係對雷射光之反射 率爲高的物質,其例子可列舉:Mg、Se、Y、Ti、Zr、Hf、 V、Nb、Ta、Cr、Mo、W、Μη、Re、Fe、Co、Ni、Ru、Rh、 Pd、Ir、Pt、Cu、Ag、An、Zn、Cd、Al、Ga、In、Si、Ge、
Te、Pb、P〇、Sn、Bi等之金屬、準金屬或是不銹鋼。此等 之中較宜爲Cr、Ni、Pt、Cu、Ag、Au、A1與不銹鋼,尤 以Ag特別理想。此等物質可以單獨使用,或是組合二種以 上而使用,或者也可以合倂使用。例如,反射層可以藉由 進行該反射性物質之蒸鍍、濺鍍或離子電鍍而形成於記錄 層上。 反射層之厚度一般於 10〜3 00nm之範圍內,更佳爲 50〜200nm之範圍內。 基於物性或化性保護記錄層等之目的,也可以於反射層 之上設置保護層。基於提高耐刮傷性、耐濕性之目的,此 保護膜也可以設置於未設置基板記錄層側。用於保護層之 材料,例如,可列舉:SiO、Si〇2、MgF2、Sn〇2、Si3N4 等 之無機物質;熱可塑性樹脂、熱硬化性樹脂、UV硬化性樹 脂等之有機物質。保護層能夠於反射層上與/或基板上’藉 由層壓例如塑膠之擠壓加工所得到的薄膜與黏著層而形 成。或是,也可以藉由真空蒸鍍、濺鍍、塗布等方法而予 以設置。另外,熱可塑性樹脂、熱硬化性樹脂之情形下, 可以溶於此等適當之溶劑而調配塗布液之後,藉由此塗布 液之塗布、乾燥而形成。UV硬化性樹脂之情形,也可以直 -34- 1301973 接或溶於適當之溶劑中而調配塗布液之後’塗布此塗布 液,藉由照射UV光而使其硬化而形成。也可以因應於目 的,於此等塗布液中進一步添加抗靜電劑、抗氧化劑、u V 吸收劑等之各種添加劑。保護層之厚度一般於〇 . 1〜1 〇 〇 // m 之範圍內。藉由以上之步驟,能夠於基板上製作設置記錄 層、反射層與所要之保護層的疊層物。進行該方式般之製 作二片疊層物,能夠藉由分別使此二片疊層物之記錄層成 爲內側而以黏結劑相貼合,製作具有二片記錄層之DVD-R 型資訊記錄媒體。另外,將所得到的疊層物與約略相同於 該疊層物基板大小之碟狀保護基板,使其記錄層成爲內側 而以黏結劑相貼合,製造僅於單面具有記錄層之DVD-R型 資訊記錄媒體。 本發明之資訊記錄方法係使用該資訊記錄媒體,例如, 如下之方式進行。首先,以一定線速度或一定角速度,使 資訊記錄媒體旋轉,從基板側照射半導體雷射光等之記錄 用雷射光。吾人認爲藉由此光之照射,於記錄層與反射層 之界面形成空洞(空洞之形成係伴隨記錄層或反射層之變 形,或二層之變形所形成的),或是基板變厚變形,或是 於記錄層中因變色、締合狀態變化等造成折射率改變而進 行資訊之記錄。CD-R型、DVD-R型之記錄光分別使用具 有 770〜790nm、600〜700nm(較宜爲 620〜680nm,更佳爲 6 3 0〜6 6 Onm)範圍之發射振動波長的半導體雷射光束。如 此方式’所記錄之資訊的再生能夠一面以相同於該一定線 速度使資訊記錄媒體旋轉,並從基板側照射具有相同於記 錄時之波長的半導體雷射光,檢測其反射光。 -35- 1301973 【實施方式】 【實施例1】 接著,顯示作爲光資訊記錄媒體的實施例。 [光資訊記錄媒體之製作] 射出成型方面,於具有螺旋狀之溝槽(深度130nm、寬 度310nm、軌距0.74// m)的厚度0.6mm、直徑120mm之 基板,進行聚碳酸酯樹脂之成型。 將本發明1.25g之化合物(3)溶於10ml之2,2,3,3-四 氟丙醇中而進行塗布液之調配,藉由旋轉塗布法,將此塗 布液塗布於形成該基板之溝槽表面上而形成色素層。 接著’於各個色素塗布面上’進行銀之濺鍍而形成膜厚 約150nm之反射層後,將紫外線硬化劑(Daicure ciear SD640、大日本油墨化學工業製)作爲黏結劑使用,與〇.6mm 厚之虛設基板相貼合而作成光碟。 (比較例1 ) 除了使用下列比較化合物(1 )以取代色素化合物(3 ) 之外,利用完全相同於實施例1之方法而作成光碟。 比較化合物(1 ) -36- 1301973
Ni :2+ ch3
[光資訊記錄媒體之評估] 使用DDU1000與多信號發生器(Plusetec公司製、雷射 波長=66 0nm、孔徑比=0.60 ),使線速度從D V D - R標準 線速度之3 . 5 m / s,變成3 5 m / s而記錄8 -1 6調變信號。
所用之記錄策略係使用表1所示者。 【表1】 記錄速度 IX 8X 8X 1 OX 記錄策略 A B C D 3 T t ο p 1.55 2.55 1.85 2.75 4 T t ο p 1.50 2.92 2.12 3.20 η T t ο p 1.55 1.70 1.30 1 .90 Tmp 0.65 — — — η T wt — 0.50 -0.30 0.55 η T1 p — 1.40 0.60 1.40 3 - η T 1 p — -0.03 -0.05 -0.03 3 Tdtop — -0.15 -0.05 -0.15 -37 - 1301973 4Tdtop — 0.20 0.35 0.20 nTdtop — 0.00 0.00 0.00 5Top2 — -0.15 -0.05 -0.20 5Τ1ρ2 — -0.1 -0.15 -0.20 5Tdlp2 — 0.00 0.00 0.00 P0/Pm — 1.48 1.58 1.36 糸己錄數據 _ _
一3T 1 fiT nTtop nTtop 記錄策略A 寫入脈動 — J / P〇 一 r Τ3-η1τδ mmm^\ ^— Tmp nTtop nTtop <—> P。
記錄策略B、C、D 寫入脈動 —1 「_ .......7 广...... -nTwt -; >_ tPm ζ"— Z=^i ^ΎΑ\ — 將此時之最適記錄功率與振動之測定結果顯示於【表 2] 〇 【表2】 實施例1 比較例1 線速度(m / s ) 3.5 28.0 3 5.0 3 . 5 28.0 3 5.0 記錄策略 A B D A B D 記錄功率(m W ) 12.0 34.7 39.0 8.5 26.0 3 3.0 -38- 1301973 反射率(% ) 49 49 49 52 52 52 振動(% ) 7.9 7.8 8.0 8.1 13.0 14.0 1 4 T調變度 0.52 0.72 0.77 0.63 0.66 0.67 相較於比較例1,實施例1之1倍速、8倍速、1 〇倍速 之振動均較低,反射率也較高。於比較例1,若AR (孔徑 比)成爲8Χ、1 0Χ般之高速記錄,振動將急遽惡化。另外’ 於實施例1,依Β記錄策略,針對最適記錄功率成爲34.7 ’ 推定於比較例1之Α記錄策略附近,振動變得最小’最適 記錄功率成爲8.6以下之値。 【實施例2】 除了合倂使用下列表3所記載之色素化合物4、5、7 ' 10、13、19、20、27、32、3與34倂用,並使用比較化合 物(1 )取代色素化合物(3 )之外,利用完全相同於實施 例1之方法而作成光碟試料202〜212。進行完全相同於實 施例1之記錄再生性能的評估。1 X至1 0X顯示優異的記錄 再生特性。將線速度35. Om/s進行記錄時之結果顯示於表 3。相較於比較化合物,得知本發明色素之反射率較高、振 動較低,可以得到足夠之調變度。 【表3】 試料編號 色素 編丨 號 反射率 振動 1 4T 備註 (% ) (°/〇 ) 調變度 20 1 化合 物 3 49 8.0 0.77 本發明 202 化合 物 4 45 8.2 0.78 本發明 203 化合 物 5 46 8 . 1 0.77 本發明 204 化合 物 7 47 7.9 0.77 本發明 -39- 1301973 205 化合物1 0 45 8 . 1 0.78 本發明 206 化合物1 3 46 7.8 0.77 本發明 207 化合物1 9 47 7.9 0.76 本發明 208 化合物2 0 47 8.4 0.75 本發明 209 化合物2 7 48 8.3 0.76 本發明 2 10 化合物3 2 45 8.2 0.78 本發明 2 11 化合物3 / 3 4 (質量比4 0 / 6 0 ) 46 7.5 0.78 本發明 2 12 比較化合物1 52 14.0 0.67 比較例 再者,以相當於12倍速與16倍速,記錄3T與14T之 單一頻率信號後,得到相同於1〜1 0倍速之C/N比、調變度 與振動。此顯示即使相當於至少1 〇〜1 6倍速,或以上之記 錄速度,均可以得到良好之特性。 【圖式簡單說明】 【主要元件符號說明】 姐。 -40-

Claims (1)

1301973 篱93136410號「光資訊記錄方法」專利案 I (2008年6月27日修正) ^'申請專利範圍: ‘ ~ _光資訊記錄方法,其特徵係以線速度v( m/ s )在3 . 5 (I»/s)的1〜16倍之範圍內、波長爲600〜700 nm之雷射, $鐵適記錄功率爲25mW以上,對透明基板上至少設置含 有_雜菁(〇xon〇l )之記錄.層與反射層的光資訊記錄媒體 行記錄,上述最適記錄功率在記錄8 - 1 6調變信號時成 馬辕動爲最小的記錄功率(Po),該Po係以下式表示, Po = PIx-v/(^/3.5)〜15尸1乂也/3.5) 記錄時之最適記錄功 (1)所示之構造, 但趣,Ρ1係以線速度3.5 ( m/s) % — ’其中該氧雜菁色素係下式通式 (1)
㊀ ^a1 Ma今=Ma3~\、 Qy 、、”_〆 ka \ 武中,Za1與Za2各白燏山生一 Mal 2 3 自獨凡表不形成酸性核的原子群, 技、Ma2、Ma3各自獨古丰一订、 ^ ^ 0 3 ^ ^ f^r 不取代或未取代的次甲基,ka 木0〜3之整數,k a M 埒以相Π ih ρΓ ιμ 上日寸,數個存在之Ma1、Ma2 M相同,也可以不同, 1301973 Q表示進行電荷中和的離子,y表示電荷中和所需要之 數目。 2 ·如申請專利範圍第1項之光資訊記錄方法,其中該氧雜 菁色素之以Q表示的離子係下式通式(2)所示之構造, 通式(2) 〇19 R20 R11 R12
表示氫原子或取代基,R1 3與R18各自獨立表示取代基。 3 ·如申請專利範圍第1項之光資訊記錄方法,其中前述氧
雜菁色素的以Q表示之離子係下述通式(3)所表示之 構造, 通式(3 )
取代之烷基、取代或無取代之芳基、取代或無取代之雜 -2- 1301973 R1與R2、R3與R4也可以相互鍵結而形成環構造, H21、r22、、r25、r26、r27、R28、r29 與 r3〇各自 獨立表不氫原子、羥基、氰基、鹵素原子、取代或無取 代之芳基、取代或無取代之烷基、或上述通式(2)的RI1、 R12、rm、Rl5、Rl6、Rn、&19與r2。中所述的取代基,或 者R23、R28爲羥基且R22、R27爲取代或無取代之苯基, 或者R23、以8爲羥基且R22、R27爲取代或無取代之苯基、 而且其他取代基爲氫原子。 4 ·如申請專利範圍第1至3項中任一項之光資訊記錄方 法,其中[1 ]於已形成軌距0 _ 6〜0 . 9 // m預溝槽之直徑 120±3mm或直徑80±3mm、厚度0.6±0.1mm透明碟狀基板 之已設置該預溝槽側之表面,將設置含色素之記錄層而 成的二片層壓物,使各自之記錄側向內接合而厚度成爲 1 . 2土0 · 2mm,或是[2]於由軌距0 . 6〜0 . 9// m預溝槽所形 成的直徑120±3mm或直徑80±3mm、厚度〇.6±0.1mm透明 碟狀基板之已設置該預溝槽側之表面,使記錄層成爲內 側,將設置含色素之記錄層而成的層壓物與碟狀保護板 予以接合的厚度成爲1.2±0.2mm。
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