TWI337193B

TWI337193B - Dye and its use for high density optical recording media

Info

Publication number: TWI337193B
Application number: TW95148751A
Authority: TW
Inventors: Shin Shin Wang; wen ping Chu; Chien Liang Huang; Wen Yih Liao; Hui Ping Tsai; Jong Lieh Yang; An Tse Lee
Original assignee: Ind Tech Res Inst
Priority date: 2006-12-25
Filing date: 2006-12-25
Publication date: 2011-02-11
Also published as: TW200827409A

Description

1337193 九、發明說明：【發明所屬之技術領域】本發明係關於一種染料，更特別關於此種染料於錄媒體之應用。 Ί 【先前技術】由於高畫質數位電視與其他數位媒體之儲存容量#托越來越高，目前的CD-R (650 MB)與DVD-R (4.7GB)等二錄媒體已無法滿足上述需求。下世代的藍光光碟其使用^ 射讀寫波長為405 nm，單層之儲存容量可達丨5GB以上田綜上所述，目前極需開發適用於藍光光碟的染料。曰本專利公開第200196918號已揭露香豆素（c〇umaHn) 衍生物可作為光記錄媒體染料。其適用之寫錄波長範_^ 320-500 nm ’但使用藍光雷射（405 ϊίιώ)進行寫錄動作時，其反射率高達50%以上。 ' 曰本專利公開第20022117號已揭露對二笨乙歸 (stilbene)可作為光記錄媒體染料。其適用之寫錄波長範圍為350-530 nm’當使用藍光雷射（405 nm)進行寫錄動作時，其吸收係數e為2.6*104至3.5*1〇4之間。美國專利第6815033號已揭露一種光記錄媒體染料。其適用之寫錄波長範圍為350-530 nm，當使用藍光雷射 (405 nm)進行寫錄動作時，其吸收係數e為1.7*丨〇4至 4.2*104 之間。 0954-A2l875TWF(N2)：P54950041TW：hsuhuche 5 1337193 美國專利第6576321號已揭露類〇卜琳azaporphyrin)可作為光記錄媒體染料。其適用之寫錄波長範圍為350-500 nm ’當使用藍光雷射(405 nm)進行寫錄動作時，其載波雜訊比（carrier to noise ratio，CNR)可達 50dB 以上。美國專利第6800347號已揭露一種光記錄媒體染料。其適用之寫錄波長範圍為350-500 nm，當使用藍光雷射 (405 nm)進行寫錄動作時，其CNR可達50dB以上。美國專利第6379768號已揭露共軛雙鍵胺化物可作為 φ 光記錄媒體染料。其適用之寫錄波長範圍小於550 nm，當使用藍光雷射（405 nm)進行寫錄動作時，其反射率高達 60%以上。雖然上述專利已揭露多種光記錄媒體染料，但熱穩定性、高載波雜訊比、高讀寫速度以及高靈敏度之光記錄媒體染料仍是目前極需開發的目標。【發明内容】 ▲ 本發明提供一種適用於光記錄媒體之染料，其包括：1337193 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a dye, and more particularly to the use of such a dye in a recording medium. Ί 【Prior Art】 Due to the increasing storage capacity of high-definition digital TVs and other digital media, the current CD-R (650 MB) and DVD-R (4.7 GB) and other secondary recording media cannot meet the above requirements. demand. The next generation of Blu-ray discs uses a wavelength of 405 nm for reading and reading, and a storage capacity of 单5GB or more for a single layer. It is extremely necessary to develop dyes suitable for Blu-ray discs. The coumarin (c〇umaHn) derivative has been disclosed as an optical recording medium dye. It is suitable for writing wavelengths of _^ 320-500 nm ’, but when using a blue laser (405 ϊίιώ) for writing, the reflectivity is as high as 50% or more. The disclosure of stilbene as an optical recording medium dye has been disclosed in the Japanese Patent Publication No. 20022117. It is suitable for writing wavelengths ranging from 350 to 530 nm. When using a blue laser (405 nm) for writing, the absorption coefficient e is between 2.6*104 and 3.5*1〇4. An optical recording medium dye has been disclosed in U.S. Patent No. 6,815,533. It is suitable for writing wavelengths ranging from 350 to 530 nm. When using a blue laser (405 nm) for writing, the absorption coefficient e is between 1.7*丨〇4 and 4.2*104. 0954-A2l875TWF(N2): P54950041TW: hsuhuche 5 1337193 U.S. Patent No. 6,576,321 discloses a class of 〇Brain azaporphyrin) which can be used as an optical recording medium dye. It is suitable for writing wavelengths ranging from 350 to 500 nm. When using a blue laser (405 nm) for writing, the carrier-to-noise ratio (CNR) can reach 50 dB or more. An optical recording medium dye has been disclosed in U.S. Patent No. 6,800,347. It is suitable for writing wavelengths ranging from 350 to 500 nm. When using a blue laser (405 nm) for writing, the CNR can be more than 50 dB. U.S. Patent No. 6,379,768 discloses that a conjugated double bond amide can be used as a φ optical recording medium dye. Its applicable wavelength range is less than 550 nm, and its reflectivity is over 60% when using a blue laser (405 nm) for writing. Although the above patents have disclosed a variety of optical recording medium dyes, thermal stability, high carrier noise ratio, high read/write speed, and high sensitivity of optical recording media dyes are still highly desirable targets. SUMMARY OF THE INVENTION The present invention provides a dye suitable for use in an optical recording medium, comprising:

其中m’n各自獨立，為〇到3之整數；X包括0、S、 N-K、或 C-R2R3 ; Y 包括〇或 S ;每一 Ri、R2、R3 各自 0954-A21875TWF(N2)；P54950041 TW：hsuhuche 6 1337193 獨立，包括氫、烷基、具有取代基之烷基、環烷基、具有取代基之環烷基、烷氧基、具有取代基之烷氧基、笨基、具有取代基之苯基、苯曱基、具有取代基之苯曱基、或鹵素；以及ζθ包括陽離子。本發明亦提供一種適用於光記錄媒體之染料，其包括:Wherein m'n is independent, and is an integer of 〇3; X includes 0, S, NK, or C-R2R3; Y includes 〇 or S; each of Ri, R2, and R3 is 0854-A21875TWF(N2); P54950041 TW :hsuhuche 6 1337193 independently, including hydrogen, alkyl, alkyl having a substituent, cycloalkyl, cycloalkyl having a substituent, alkoxy group, alkoxy group having a substituent, stupid group, having a substituent Phenyl, benzoinyl, phenylhydrazine having a substituent, or halogen; and ζθ includes a cation. The invention also provides a dye suitable for use in an optical recording medium, comprising:

其中m，η各自獨立，為0到3之整數；X包括0、S、 N-R4、或 C-R5R6，母一 R4、R5、尺6、R7、R8 各自獨立，包括氫、烷基、具有取代基之烷基、環烷基、具有取代基之環烷基、烷氧基、具有取代基之烷氧基、苯基、具有取代基之苯基、苯曱基、具有取代基之苯曱基、或鹵素；以及ζθ包括陽離子。本發明更提供一種適用於光記錄媒體之染料，其包括:Wherein m and η are each independently and are an integer from 0 to 3; X includes 0, S, N-R4, or C-R5R6, and the parent-R4, R5, 尺6, R7, and R8 are each independently, including hydrogen, alkyl, Alkyl group having a substituent, a cycloalkyl group, a cycloalkyl group having a substituent, an alkoxy group, an alkoxy group having a substituent, a phenyl group, a phenyl group having a substituent, a benzoinyl group, a benzene having a substituent Sulfhydryl, or halogen; and ζθ includes a cation. The invention further provides a dye suitable for use in an optical recording medium, comprising:

其中m，n各自獨立，為0到3之整數；每一 R7、Rs、 R9、R10各自獨立，包括氫、烷基、具有取代基之烷基、環 0954-A21875TWF(N2)：P54950041TW：hsuhuche 7 1337193 烷基、具有取代基之環烷基、烷氧基、具有取代基之烷氡基、苯基、具有取代基之笨基、苯甲基、具有取代基之苯曱基、函素、硝基、羧基酯基、酮基、磺醯基、或磺酸酯基；以及z®包括陽離子。本發明更提供一種藍光雷射記錄媒體，包括基板，以及位於該基板上方之記錄層，其雷射讀寫波長介於300 nm 至500 nm，且記錄層包括上述之染料。【實施方式】本發明提供一種染料，其結構式如下：Wherein m, n are each independently, an integer from 0 to 3; each R7, Rs, R9, and R10 are each independently, and include hydrogen, an alkyl group, an alkyl group having a substituent, and a ring 0954-A21875TWF(N2): P54950041TW: hsuhuche 7 1337193 alkyl group, substituted cycloalkyl group, alkoxy group, alkoxy group having a substituent, phenyl group, a stupid group having a substituent, a benzyl group, a phenyl fluorenyl group having a substituent, a element, a nitro group, a carboxyl ester group, a ketone group, a sulfonyl group, or a sulfonate group; and z® includes a cation. The present invention further provides a blue laser recording medium comprising a substrate, and a recording layer located above the substrate, the laser reading and writing wavelength is between 300 nm and 500 nm, and the recording layer comprises the dye described above. [Embodiment] The present invention provides a dye having the following structural formula:

其中m，η各自獨立，為0到3之整數；X包括0、S、 Ν-Κ、或C-R2R3 ;每一 Rq、R2、R3各自獨立，包括氫、烷基、具有取代基之烷基、環烷基、具有取代基之環烷基、烷氧基、具有取代基之烷氧基、苯基、具有取代基之苯基、苯甲基、具有取代基之苯曱基、或il素；以及Ζφ包括陽離子。烷基、具有取代基之烷基、環烷基、具有取代基之環烷基、烷氧基、具有取代基之烷氧基之碳數可為CM()，較佳為Cw，在更佳實施例中，烷基、具有取代基之烷基、烷氧基、具有取代基之烷氧基之碳數可為CN3。上述染料之合成方式如下式： 0954-A21875TWF(N2):P54950041TW;hsuhuche 8 1337193 (式 ιι) 在式II中，鹼可為常見之MOH或M2C03，而1^為對應鹼中的金屬離子，如對應碳酸鈉之鈉離子或對應氫氧化鉀之鉀離子。為了增加染料於有機溶劑之溶解度，可進一步以其他陽離子Ζθ置換M®形成式I之染料。其他陽離子Ζ®較佳為四級銨鹽，更佳為含有芳香基之四級敍鹽。Wherein m, η are each independently, an integer from 0 to 3; X includes 0, S, Ν-Κ, or C-R2R3; each Rq, R2, and R3 are each independently, including hydrogen, an alkyl group, a substituted alkane a group, a cycloalkyl group, a substituted cycloalkyl group, an alkoxy group, a substituted alkoxy group, a phenyl group, a substituted phenyl group, a benzyl group, a substituted phenyl fluorenyl group, or il And Ζφ include cations. The alkyl group, the alkyl group having a substituent, the cycloalkyl group, the cycloalkyl group having a substituent, the alkoxy group, the alkoxy group having a substituent may have a carbon number of CM(), preferably Cw, more preferably In the examples, the carbon number of the alkyl group, the alkyl group having a substituent, the alkoxy group, and the alkoxy group having a substituent may be CN3. The above dye is synthesized in the following formula: 0954-A21875TWF(N2): P54950041TW; hsuhuche 8 1337193 (Formula ιι) In Formula II, the base may be a common MOH or M2C03, and 1^ is a metal ion in the corresponding base, such as Corresponding to sodium ion of sodium carbonate or potassium ion corresponding to potassium hydroxide. In order to increase the solubility of the dye in the organic solvent, M® can be further substituted with other cationic Ζθ to form the dye of formula I. The other cations are preferably a quaternary ammonium salt, more preferably a quaternary salt containing an aryl group.

本發明亦提供一種適用於光記錄媒體之染料，其結構式如下： Z® Xk / 1 (式 III)The present invention also provides a dye suitable for use in an optical recording medium, which has the following structural formula: Z® Xk / 1 (Formula III)

其中m，n各自獨立，為0到3之整數；X包括0、S、 N-R4、或，母'~~ R4、R5、R6、R7、Rs 各自獨立’ 包括氫、烷基、具有取代基之烷基、環烷基、具有取代基之環烷基、烷氧基、具有取代基之烷氧基、苯基、具有取代基之笨基、笨甲基'具有取代基之笨曱基、或鹵素；以及Z®包括陽離子。烷基、具有取代基之烷基、環烷基、具有取代基之環烷基、烷氧基、具有取代基之烷氧基之碳數可為Cmo，較佳為Cm，在更佳實施例中，烷基、具有取代基之烷基、烷氧基、具有取代基之烷氧基之碳數可為Wherein m and n are each independently and are an integer from 0 to 3; X includes 0, S, N-R4, or, and the parent '~~ R4, R5, R6, R7, and Rs are each independently' including hydrogen, alkyl, and substituted. Alkyl group, cycloalkyl group, cycloalkyl group having a substituent, alkoxy group, alkoxy group having a substituent, phenyl group, a stupid group having a substituent, a stupid methyl group having a substituent , or halogen; and Z® includes cations. The carbon number of the alkyl group, the alkyl group having a substituent, the cycloalkyl group, the cycloalkyl group having a substituent, the alkoxy group, the alkoxy group having a substituent may be Cmo, preferably Cm, in a more preferred embodiment The carbon number of the alkyl group, the alkyl group having a substituent, the alkoxy group, and the alkoxy group having a substituent may be

0954-A2l875TWF(N2)；P54950041TW：hsuhuche 9 1337193 上述染料之合成方式如下式：0954-A2l875TWF(N2); P54950041TW: hsuhuche 9 1337193 The above dyes are synthesized as follows:

(式 IV) 與前一種染料之合成策略類似，在式IV中鹼可為常見 '之MOH或M2C03,而M®為對應鹼中的金屬離子，如對應碳酸鈉之鈉離子或對應氫氧化鉀之鉀離子。為了增加染料於有機溶劑之溶解度，可進一步以其他陽離子Z®置換Μθ 參形成式III之染料。其他陽離子乙@較佳為四級銨鹽，更佳為含有芳香基之四級銨鹽。本發明更提供一種適用於光記錄媒體之染料，其包括:(Formula IV) Similar to the synthesis strategy of the former dye, in the formula IV, the base may be the common 'MOH or M2C03, and M® is the metal ion in the corresponding base, such as the sodium ion corresponding to sodium carbonate or the corresponding potassium hydroxide. Potassium ion. In order to increase the solubility of the dye in the organic solvent, the cation of the formula III can be further replaced by another cation Z®. The other cation B is preferably a quaternary ammonium salt, more preferably a quaternary ammonium salt containing an aromatic group. The invention further provides a dye suitable for use in an optical recording medium, comprising:

(式V) 其中m，n各自獨立，為0到3之整數；每一 R9、Ri〇、 • Rn、R12各自獨立，包括氫、烷基、具有取代基之烷基、環烷基、具有取代基之環烷基、烷氧基、具有取代基之烷氧基、苯基、具有取代基之苯基、苯甲基、具有取代基之苯甲基、il素、硝基、羧基酯基、酮基、磺醯基、或磺酸酯基；以及Z®包括陽離子。烷基、具有取代基之烷基、環烷基、具有取代基之環烷基、烷氧基、具有取代基之烷氧基之碳數可為Cmo,較佳為Cm，在更佳實施例中，烷基、具有取代基之烷基、烷氧基、具有取代基之烷氧基之碳數 0954-A2l875TWF(N2):P54950041TW：hsuhuche 10 1337193 . 可為c! 上述染料之合成方式如下式：(Formula V) wherein m, n are each independently, an integer from 0 to 3; each R9, Ri, Rn, and R12 are each independently, and include hydrogen, an alkyl group, an alkyl group having a substituent, a cycloalkyl group, and Substituent cycloalkyl, alkoxy, substituted alkoxy, phenyl, substituted phenyl, benzyl, substituted benzyl, il, nitro, carboxy ester a keto group, a sulfonyl group, or a sulfonate group; and Z® includes a cation. The carbon number of the alkyl group, the alkyl group having a substituent, the cycloalkyl group, the cycloalkyl group having a substituent, the alkoxy group, the alkoxy group having a substituent may be Cmo, preferably Cm, in a more preferred embodiment In the alkyl group, the alkyl group having a substituent, the alkoxy group, the alkoxy group having a substituent, the carbon number is 0954-A2l875TWF(N2): P54950041TW: hsuhuche 10 1337193. It can be c! The above dye is synthesized as follows :

與則一種染料之合成策略類似’在式VI中鹼可為常見之MOH或M2C〇3’而M®為對應鹼中的金屬離子，如對應石反酸納之鈉離子或對應氫氧化鉀之鉀離子。為了增加染料 #於有機溶劑之溶解度’可進一步以其他陽離子ΖΘ置換M® 形成式V之染料。其他陽離子广較佳為四級銨鹽，更佳為含有芳香基之四級銨鹽。上述染料主要應用於高密度藍光可錄式光碟片的記錄層’形成光碟片的方法分為下列兩種。第一種是HD-DVD-R (high density digital versatile disc recordable)結構規格，如第1圖所示。hd-dvd-r之形成步驟包括提供透明基板 11 ;將本發明之光記錄媒體染料溶解於有機溶劑，並將此 _ 染料溶液塗佈於上述透明基板11上；進行烘乾製程，以形成一層光記錄媒體染料之記錄層12 ;將反射層材料濺鑛於上述5己錄層12上形成一反射層13，將上述塗有染料之透明基板11與另一透明基板14進行貼合，即完成記錄層j 2 與反射層13夾設於兩透明基板間之高密度藍光可錄式光碟片。第二種 BDR(blue-ray disc recordable)之結構規格如第 2圖所示。BDR之形成步驟包括提供透明基板21 ;將反射〇954-A21875TWF(N2)：P54950041TW：hsuhuche 1337193 材料濺鍍於透明基板21上以形成反射層22 ;將光記錄媒體染料溶解於有機溶劑中，形成染料溶液，並將此溶液塗佈於上述之反射層22上；烘乾染料溶液，以形成光記錄媒體染料之記錄層23 ;塗佈保護層24(cover layer)於記錄層 23上，即完成BDR結構之高密度藍光可錄式光碟片。上述之透明基板11及21具有溝槽，而透明基板14不具有溝槽。透明基板材質可為聚酯類、聚碳酸酯類 (Polycarbonate)、聚烯類等（PMMA)、環烯烴共聚物籲（Metallocene based Cyclic Olefin Copolymer，mCOC )。其中mCOC於波長範圍小於450nm時所具有高光穿透率，更適合作為本發明之高密度藍光可錄式光碟片之基板。反射層13及22可擇自金、銀、鋁、石夕、銅、鉻、鈦、或上述之金屬之合金。用以溶解本發明染料之有機溶劑可為Cu 之醇類（alcohol)、C〗-6 之酮類（ketone)、Cb6 之醚類（ether)、 dibutyl ether (DBE)、鹵素化合物、或醯胺（amide)。其中 C!-6之醇類可為曱醇（methanol)、乙醇（ethanol)、異丙醇 ❿（isopropanol)、二丙酮醇（diacetonalchol，DAA )、Cu 之 _ 醇類（ether alcohol) 、 2,2,3,3-四 It 丙醇 (2,2,3,3-tetrafluoropropanol)、三氣乙醇（trichloroethanol)、 2-氣乙醇（2-chloroethanol)、八氟戍醇（octafluoropentanol)、或六氟丁醇（hexafluorobutanol) ; C丨-6之酮類可為丙酮 (acetone)、甲基異丁 _(methyl isobutyl ketone，MIBK)、曱基乙基酮（methyl ethyl ketone，MEK)、丙二醇甲醚 (propylene glycol monoethyl ether，PGME)、丙二醇曱喊醋 0954-A21875TWF(N2)；P54950041TW：hsuhuche 12 Ί337193 i -·: 酸醋（propylene glycol monoethyl acetate，PGMEA)、或 3-經基-3-甲基-2-丁酮（3-hydroxy-3-methyl-2-butanone);鹵素化合物可為氣仿（chloroform)、二氣甲烧 (dichloromethane)、或 1-氣丁烧（Ι-chlorobutane);醯胺可為二曱基曱醯胺（dimethylformamide，DMF)、二曱基乙醢胺 ^ (dimethylacetamide ， DMA)、或甲基環己烧 (methylcyclohexane，MCH)。為提高染料溶液之塗佈性，本發明之染料可進一步與 φ 高分子一起溶解於有機溶劑中。合適之高分子可為甲殼素 (chitin);纖維素如纖維酯（cellulose ester)、硝化纖維 (nitrocellulose)、醋酸纖維（cellulose acetate)、或醋酸丁酸纖維（cellulose acetate butyrate);或聚乙烯樹脂類（如 polyvinyl butyral)等高分子。除了上述旋轉塗佈後烘乾的方式外，本發明形成記錄層的方法還包括滚壓塗佈、含浸、喷墨（inkjet printing)、及蒸鍍等方式，不過仍以旋轉塗佈的方式較佳。 φ 在HD-DVD-R之製程中，將基板貼合至塗有染料之基板的貼合方式可為網印、熱融膠法、雙面膠帶貼合法、或其他合適之貼合法。若採用BDR之結構，可考慮於記錄層23與保護層24 之間夾設介電層，較佳之介電層材料可為ZnS-Si02、ZnS、 AIN、SiN、SiC、或其他合適之介電材料。本發明之染料可進一步與其他染料如偶氮金屬螯合染料（azo metal chelate dye)、花菁染料（cyanine)、酿花菁 0954-A21875TWF(N2)：P54950041TW：hsuhuche 1337193 (phthalocyanine)染料、或其他合適之染料混合，以作為光記錄媒體記錄層之染料。本發明之染料與其他染料之混合比例為 1:99-99:1。本發明之染料於有機溶劑之溶解度佳，以四氟丙醇 (2,2,3,3-tetraflu〇r〇-pr〇pan-l-ol，TFP)為例，其溶解度大於 < 2.0%。此外’本發明之染料溶液於基板或反射層上的塗佈性質佳。本發明之染料於300-500 nm之間的吸收數值€大於 5*10 ’且訊雜比（Partial Response Signal-to-Noise φ Ratio，PRSNR)大於 12。為使本技藝人士更清楚本發明之特徵，特舉例於下述之較佳實施例。實施例1 (合成染料1_1) 取 4.21g (0,02mole)之 A-1 以及 L48g (O.Olmole)之三乙氧基甲烷溶於甲醇(40mL)後迴流隔夜。反應產物以碳酸鈉溶液萃取，萃取物經過濾烘乾可得2.13g橘黃色固體（M) ’ 產率47%。其反應式如下式：Similar to the synthesis strategy of a dye, 'in the formula VI, the base can be the common MOH or M2C〇3' and M® is the metal ion in the corresponding base, such as the sodium ion corresponding to the sodium sulphate or the corresponding potassium hydroxide. Potassium ion. In order to increase the solubility of the dye # in the organic solvent, the dye of the formula V can be further replaced by another cationic hydrazine. The other cation is preferably a quaternary ammonium salt, more preferably a quaternary ammonium salt containing an aromatic group. The above dyes are mainly used in the recording layer of high-density blue-recordable optical discs. The method of forming optical discs is divided into the following two types. The first is the HD-DVD-R (high density digital versatile disc recordable) structural specification, as shown in Figure 1. The forming step of hd-dvd-r includes providing a transparent substrate 11; dissolving the optical recording medium dye of the present invention in an organic solvent, and applying the dye solution to the transparent substrate 11; performing a drying process to form a layer The recording layer 12 of the optical recording medium dye; the reflective layer material is sputtered on the above-mentioned 5 recording layer 12 to form a reflective layer 13, and the dye-coated transparent substrate 11 is bonded to the other transparent substrate 14 to complete The recording layer j 2 and the reflective layer 13 are sandwiched between high-density blue-recordable optical discs between the transparent substrates. The structure specification of the second BDR (blue-ray disc recordable) is shown in Figure 2. The forming step of the BDR includes providing the transparent substrate 21; sputtering the reflective 〇954-A21875TWF(N2):P54950041TW:hsuhuche 1337193 material onto the transparent substrate 21 to form the reflective layer 22; and dissolving the optical recording medium dye in an organic solvent to form a dye solution, and the solution is applied onto the reflective layer 22; the dye solution is dried to form a recording layer 23 of the optical recording medium dye; and a cover layer is applied on the recording layer 23, that is, High-density blue-recordable optical discs of BDR structure. The above transparent substrates 11 and 21 have grooves, and the transparent substrate 14 does not have grooves. The material of the transparent substrate may be polyester, polycarbonate, polyolefin (PMMA) or metallocene based Cyclic Olefin Copolymer (mCOC). Among them, mCOC has a high light transmittance at a wavelength range of less than 450 nm, and is more suitable as a substrate for the high-density blue-recordable optical disk of the present invention. The reflective layers 13 and 22 may be selected from the group consisting of gold, silver, aluminum, stone, copper, chromium, titanium, or alloys of the foregoing. The organic solvent used to dissolve the dye of the present invention may be an alcohol of Cu, a ketone of C-6, an ether of Cb6, a dibutyl ether (DBE), a halogen compound, or a guanamine. (amide). The alcohol of C!-6 may be methanol, ethanol, isopropanol, diacetonalchol (DAA), Cu alcohol alcohol, 2, 2,3,3-tetraethylpropanol, trichloroethanol, 2-chloroethanol, octafluoropentanol, or hexafluoro Butyl alcohol (hexafluorobutanol); C丨-6 ketones can be acetone (acetone), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), propylene glycol methyl ether ( Propylene glycol monoethyl ether (PGME), propylene glycol vinegar 0954-A21875TWF (N2); P54950041TW: hsuhuche 12 Ί337193 i -·: propylene glycol monoethyl acetate (PGMEA), or 3-carbyl-3-methyl- 2-hydroxy-3-methyl-2-butanone; halogen compound can be chloroform, dichloromethane, or 1-chlorobutane; guanamine It can be dimethylformamide (DMF), dimethylacetamide (DMA), Methylcyclohexyl burning (methylcyclohexane, MCH). In order to improve the coatability of the dye solution, the dye of the present invention may be further dissolved in an organic solvent together with the φ polymer. Suitable polymers may be chitin; cellulose such as cellulose ester, nitrocellulose, cellulose acetate, or cellulose acetate butyrate; or polyethylene resin A polymer such as polyvinyl butyral. In addition to the above-described method of drying after spin coating, the method for forming a recording layer of the present invention further includes roll coating, impregnation, inkjet printing, and vapor deposition, but still in a spin coating manner. good. φ In the process of HD-DVD-R, the bonding method of bonding the substrate to the dye-coated substrate may be screen printing, hot melt bonding, double-sided tape bonding, or other suitable bonding method. If the structure of the BDR is adopted, a dielectric layer may be interposed between the recording layer 23 and the protective layer 24. Preferably, the dielectric layer material may be ZnS-SiO2, ZnS, AIN, SiN, SiC, or other suitable dielectric. material. The dye of the present invention may further be combined with other dyes such as azo metal chelate dye, cyanine, broccoli 0954-A21875TWF(N2): P54950041TW: hsuhuche 1337193 (phthalocyanine) dye, or Other suitable dyes are mixed to serve as a dye for the recording layer of the optical recording medium. The mixing ratio of the dye of the present invention to other dyes is 1:99-99:1. The dye of the present invention has good solubility in an organic solvent, and tetrafluoropropanol (2,2,3,3-tetraflu〇r〇-pr〇pan-l-ol, TFP) is taken as an example, and its solubility is greater than < 2.0% . Further, the coating solution of the present invention has a good coating property on a substrate or a reflective layer. The dye of the present invention has an absorption value of more than 5*10 ′ between 300 and 500 nm and a Partial Response Signal-to-Noise φ Ratio (PRSNR) of more than 12. To make the skilled person more aware of the features of the present invention, the preferred embodiments are exemplified below. Example 1 (Synthetic dye 1_1) 4.21 g (0,02 mole) of A-1 and L48g (O.Olmole) of triethoxymethane were dissolved in methanol (40 mL) and refluxed overnight. The reaction product was extracted with a sodium carbonate solution, and the extract was filtered and dried to yield 2.13 g of an orange solid (M) yield 47%. Its reaction formula is as follows:

(式 VII) 實施例2 (合成染料1-2) 取 4.32g (0,01mole)之 Μ，3.〇lg (〇.〇lmole)之 1，2,3,4-四曱基-3H-吲哚碘化物（l，H3-Tetramethyl-3H-ind〇lium iodide)溶於甲醇後（40mL)後於4〇°C下攪拌1小時。過濾 0954-A21875TWF(N2)；P54950041TW；hsuhuche 14 1337193 I-d P4H9 匕 4H9 c4H9- n n-c4h9 C4H9-N <n-c4h9 C^Hq C^Hq 460 1067 6.58 5.11 I-e P 0 0 F 471 7.58 I-f 。—。〇c^ 啦:>< 0 0 F \ 448 8.08 I-g x P ,o 0 、〇 F \ 463 12.99 I-h —7 〇 \ 462 18.5 I-i 谢i。0^ J cT L Y〇、^F 0 fT 464 12.2 H 谢 ¢0 oi1 J Λ 〇Vv_ 、 459 12.1 I-k ^V〇 J 0 λν 、 >。 460 11.8 1-1 0^- J 0 λν 、 461 12.5 0954-A21875TWF(N2)；P54950041TW；hsuhuche 1337193 【圖式簡單說明】第1圖係本發明之HD-DVD-R结構示意圖；第2圖係本發明之BDR結構示意圖。【主要元件符號說明】 1 1、14、21〜透明基板； 12、 23〜記錄層； 13、 22〜反射層； 24〜保護層。 0954-A21875TWF(N2)：P54950041TW：hsuhuche(Formula VII) Example 2 (Synthetic dye 1-2) Take 4.32 g (0,01 mole) of ruthenium, 3. 〇lg (〇.〇lmole) 1,2,3,4-tetradecyl-3H- After the hydrazine iodide (1,H3-Tetramethyl-3H-ind〇lium iodide) was dissolved in methanol (40 mL), it was stirred at 4 ° C for 1 hour. Filtration 0954-A21875TWF(N2); P54950041TW; hsuhuche 14 1337193 I-d P4H9 匕 4H9 c4H9- n n-c4h9 C4H9-N <n-c4h9 C^Hq C^Hq 460 1067 6.58 5.11 I-e P 0 0 F 471 7.58 I-f . —. 〇c^ 啦:>< 0 0 F \ 448 8.08 I-g x P ,o 0 , 〇 F \ 463 12.99 I-h —7 〇 \ 462 18.5 I-i Thank i. 0^ J cT L Y〇, ^F 0 fT 464 12.2 H Xie ¢0 oi1 J Λ 〇Vv_ , 459 12.1 I-k ^V〇 J 0 λν , >. 460 11.8 1-1 0^- J 0 λν , 461 12.5 0954-A21875TWF (N2); P54950041TW; hsuhuche 1337193 [Simplified Schematic] FIG. 1 is a schematic diagram of the HD-DVD-R structure of the present invention; Schematic diagram of the BDR structure of the present invention. [Main component symbol description] 1 1, 14, 21~ transparent substrate; 12, 23~ recording layer; 13, 22~ reflective layer; 24~ protective layer. 0954-A21875TWF(N2): P54950041TW: hsuhuche

Claims

I337L93 Revision date: 99.10.28 No. 95148751

Correct the original m, η is 0;

X includes Ο, S, N-Ri, or C-R2R3; Y includes 0 or S; each R], R2, and R3 are each independently, including nitrogen, a substituent, an alkyl group having a substituent, a cycloalkyl group, and a cycloalkyl group, an alkoxy group, or an alkoxy group having a substituent;

Derivative, or sigma

A quaternary ammonium salt of a ‘®) derivative. 2. A blue laser recording medium comprising: a substrate; and a recording layer above the substrate, the laser reading and writing wavelength of which is between 300 nm and 500 nm; wherein the recording layer comprises the first item of the patent application scope Said dye. 3. The blue laser recording medium according to claim 2, wherein the recording layer further comprises an azo metal chelate dye, a cyanine dye, or a hydrazine 20 13.37193 Amendment No. 95148751, date of revision: 99.: 1〇.28 Cyanine dye. 4. A dye, including,

R7 r8

X includes 0, S, N-R4, or C_R5R 6 ; each R4, R5, R6, R7, and Han 8 are each independently, including hydrogen, an alkyl group, a filament having a substitution S, a sulfhydryl group, and a substituent having a substituent. , alkoxy, or alkoxy having a substituent;

Z® is one. Alpha

Derivatives, or. A beta-ammonium salt of a beta-sodium derivative. 5. A blue laser recording medium comprising: a substrate; and - a recording layer above the substrate having a laser read/write wavelength of between 3 Å and 500 nm; The recorded layer includes the dye described in item 4 of the patent application. The blue laser recording medium according to item 5, wherein the recording layer further comprises an azo metal chelate dye, a flower, or a phthalocyanine dye. 21 1337193 No. 95148751 Revision date: 99.10.28 7. — Dyestuffs, including:

Correct the original m, η is 0;

Each of 119, 1^1〇, 尺]1, and 1112 are each independently and include hydrogen, an alkyl group, a substituted group, a cycloalkyl group, a substituted cycloalkyl group, an alkoxy group, or a substituent. Alkoxy group; and ζφ system

a quaternary ammonium salt of a derivative, or a thiazole derivative. 8. A type of blue laser recording media, including:

a substrate; and a recording layer above the substrate, the laser reading and writing wavelength is between 300 nm and 500 nm; wherein the recording layer comprises the dye according to claim 7 of the patent application. 9. The blue laser recording medium of claim 8, wherein the recording layer further comprises an oxime metal chelate dye, a cyanine dye, or a cyanine dye. twenty two