CN1513171A - 在信息层中包括菁染料作为吸光性化合物的光学数据载体 - Google Patents

在信息层中包括菁染料作为吸光性化合物的光学数据载体 Download PDF

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CN1513171A
CN1513171A CNA028108833A CN02810883A CN1513171A CN 1513171 A CN1513171 A CN 1513171A CN A028108833 A CNA028108833 A CN A028108833A CN 02810883 A CN02810883 A CN 02810883A CN 1513171 A CN1513171 A CN 1513171A
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expression
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cyanine dyes
data carrier
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Inventor
H
H·伯内斯
3
F·-K·布鲁德
W·黑泽
R·哈根
K·哈森吕克
S·科斯特罗米尼
���dz�
P·兰登伯格
R·奥泽尔
T·索默曼
ά
J·-W·施塔维茨
�ָ���
T·比林格尔
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Bayer AG
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Bayer AG
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Priority claimed from DE10115227A external-priority patent/DE10115227A1/de
Priority claimed from DE2001136064 external-priority patent/DE10136064A1/de
Priority claimed from DE2002102571 external-priority patent/DE10202571A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of CN1513171A publication Critical patent/CN1513171A/zh
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    • C07D221/02Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
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    • C07D217/00Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
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    • C07D311/04Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/12Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
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    • C07D455/03Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
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    • C09B23/04Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
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Abstract

本发明涉及含有优选透明的基材的光学数据载体,该基材任选已涂敷了一层或多层反射层,在其表面上施涂能够用光进行写的信息层,任选的一层或多层的反射层和任选的保护层或附加的基材或覆盖层。该光学数据载体能够利用蓝光,红光或红外光,优选激光来进行写和读,并且信息层包括吸光性化合物和任选的粘结剂。本发明的数据载体进一步的特征在于至少一种菁染料用作该吸光性化合物。

Description

在信息层中包括菁染料作为吸光性化合物的光学数据载体
本发明涉及在信息层中包括菁染料(cyaninfarbstoff)作为吸光性化合物的一次写入型光学数据载体,涉及它的生产方法和涉及由旋涂或汽相沉积将上述染料施涂于聚合物基材(尤其聚碳酸酯)上的方法。
采用特定的吸光物质或其混合物的一次写入型光学数据载体特别适合用于以蓝色激光二极管、尤其GaN或SHG激光二极管(360-460nm)操作的高密度可写光学数据储存介质(Datenspeicher)和/或用于以红色(635-660nm)或红外(780-830nm)激光二极管操作的DVD-R或CD-R盘片。
一次写入型光盘(CD-R,780nm)最近实现了巨大容量的生长并代表了技术上成熟的系统。
下一代的光学数据储存介质-DVD系列-目前已经引入到市场。由于短波激光照射(635-660nm)和较高的数值孔径NA的使用,该存储密度能够提高。在这种情况下可写格式是DVD-R。
今天,已经开发出了使用高激光功率的蓝色激光二极管(基于GaN,JP08 191171或二次谐波发生SHG,JP09 050 629)(360nm-460nm)的光数据存储格式。可写光学数据储存介质因此也用于这一代。能实现的存储密度取决于激光焦点在该信息面上的聚焦。焦点尺寸用激光波长λ/NA定标。NA所使用的物镜的数值孔径。为了获得最高可能的存储密度,最小可能的波长λ的使用是目标。目前,基于半导体激光二极管,390nm是可能的。
该专利文献描述了染料型可写光学数据储存介质,它们同样地适合于CD-R和DVD-R系统(JP-A 11 043 481和JP-A 10 181 206)。为了实现高反射率和读出信号的高调制高度和实现足够的写入敏感性,可利用以下事实:CD-R的780nm的IR波长位于染料的吸收峰的长波长侧翼(Flanke)的根部和DVD-R的635nm或650nm的红色波长位于染料的吸收峰的短波长侧翼的根部。在JP-A 02 557 335,JP-A 10058 828,JP-A 06336086,丁P-A 02 865 955,WO-A 09 917284和US-A 5 266699中,这一概念延伸到在吸收峰的短波长侧翼上的450nm工作波长区域和在长波长侧翼上的红色和IR区域。
除该上述的光学性质外,得自吸光性有机物质的可写信息层需要具有尽可能无定形的形态,以便在写或读过程中保持尽可能小的噪音信号。因此之故,特别优选的是,在随后的减压下的金属或电介质层覆盖中,在通过从溶液旋涂、通过汽相淀积(Aufdampfen)和/或升华来施涂吸光物质的操作防止该吸光物质的结晶。
得自吸光物质的无定形层优选具有高度耐热变形性,因为通过喷溅或汽相淀积被施涂于吸光性信息层中的有机或无机材料的其它附加层将由于散射而形成变模糊的边界,因此不利地影响反射率。此外,具有不够的耐热变形性的吸光物质能够在聚合物载体的界面,扩散到该载体中,和再次不利地影响该反射率。
蒸汽压力太高的吸光性物质能够在利用高真空下的上述喷溅或汽相淀积附加层的过程中发生升华和因此将层厚度降低到低于所需要的值。这进而不利地影响该反射率。
因此本发明的目的是提供满足可用于在一次写入型光学数据载体中的信息层中,尤其用于在340-830nm的激光波长范围内的高密度可写光学数据存储格式的高要求(例如光稳定性,有益的信号/噪声比,对基材的无损害式施涂,等)的合适的化合物。
令人吃惊地已经发现,选自菁染料类的吸光性化合物能够特别充分地满足上述要求范围(profil)。
因此本发明涉及包括优选透明的基材的光学数据载体,任选地该基材已涂敷了一个或多个反射涂层和在该基材的表面上已经涂敷了光可写型信息层、任选的一个或多个反射涂层和任选的保护层或附加基材或覆盖层,其能够利用蓝色、红色或红外光(优选激光)进行写和读,其中信息层包括吸光性化合物和任选的粘结剂,特征在于至少一种菁染料用作吸光性化合物。
吸光性化合物应该优选能够以加热途径来改变。热改变(thermische Vernderung)优选在<600℃的温度下,特别优选在<400℃的温度下,非常特别优选在<300℃的温度下,尤其<200℃下发生。该变化能够是,例如,吸光性化合物的发色中心的分解或化学变化。
优选的是通式(I)的菁染料
Figure A0281088300081
其中
X1和X3表示氮或
X1-R1和X3-R2彼此独立地表示S,
X2表示O,S,N-R6,CR8或CR8R9
X4表示O,S,CR10或N-R7
Y表示N或C-R5
R1,R2,R6和R7彼此独立地表示C1-C16-烷基,C3-C6-链烯基,C5-C7-环烷基或C7-C16-芳烷基,
R3,R4和R5彼此独立地表示氢,C1-C16-烷基或氰基或
当m=0和p>0时,R1和R3一起表示-(CH2)2-,-(CH2)3-或-(CH2)4-桥连基,或
当m=0和p=0时,R1和R5一起表示-(CH2)2-,-(CH2)3-或-(CH2)4-桥连基,或
当n=0时,R2和R5一起表示-(CH2)2-,-(CH2)3-或-(CH2)4-桥连基,
R8,R9和R10彼此独立地表示氢或C1-C16-烷基或
CR8R9表示下式的二价基团
Figure A0281088300082
Figure A0281088300083
其中两个键是从星号(*)标记的环中原子上引出,
m和n彼此独立地表示0或1,
p表示0,1或2,
包括X1、X2和连接X1和X2的基团的环A和包括X3、X4和连接X3和X4的基团的环B彼此独立地表示五元或六元芳族或准芳族(quasiaromatischen)或部分氢化的杂环,该杂环可含有1-4个杂原子和/或是苯并-或萘并-稠合的和/或被非离子基团取代,其中环A和B优选是不同的,和
An-表示阴离子。
可能的非离子基团是,例如,C1-C4-烷基,C1-C4-烷氧基,卤素,氰基,硝基,C1-C4-烷氧基羰基,C1-C4-烷硫基,C1-C4-链烷酰基胺基,苯甲酰基胺基,单或二-C1-C4-烷基胺基。
烷基,烷氧基,芳基和杂环基可以任选地携带其它基团,如烷基,卤素,硝基,氰基,CO-NH2,烷氧基,三烷基甲硅烷基,三烷基硅氧基或苯基,该烷基和烷氧基基团可以是直链或支化的,该烷基可以部分地卤化或全卤化,该烷基和烷氧基基团可以是乙氧基化或丙氧基化或甲硅烷基化的,在芳基或杂环基团上的相邻烷基和/或烷氧基基团可以一起形成三元或四元桥连基和该杂环基可以是苯并稠合的和/或季化的(quaterniert)。
通式II的基团
特别优选表示苯并噻唑-2-基,噻唑-2-基,噻唑啉-2-基,苯并噁唑-2-基,噁唑-2-基,噁唑啉-2-基,苯并咪唑-2-基,咪唑-2-基,咪唑啉-2-基,二氢吡咯-2-基,3-H-吲哚-2-基,苯并[c,d]吲哚-2-基,2-或4-吡啶基或2-或4-喹啉基,
其中X1表示N,
其中该上述的环可以各自被C1-C6-烷基,C1-C6-烷氧基,氟,氯,溴,碘,氰基,硝基,C1-C6-烷氧基羰基,C1-C6-烷硫基,C1-C6-酰胺基,C6-C10-芳基,C6-C10-芳氧基或C6-C10-芳基羰基胺基取代。
通式III的基团
Figure A0281088300092
特别优选表示苯并噻唑-2-叉基,噻唑-2-叉基,噻唑啉-2-叉基,异噻唑-3-叉基,1,3,4-噻二唑-2-叉基,1,2,4-噻二唑-5-叉基,苯并噁唑-2-叉基,噁唑-2-叉基,噁唑啉-2-叉基,1,3,4-噁二唑-2-叉基,苯并咪唑-2-叉基,咪唑-2-叉基,咪唑啉-2-叉基,二氢吡咯-2-叉基,1,3,4-三唑-2-叉基,3H-吲哚-2-叉基,苯并[c,d]吲哚-2-叉基,2-或4-吡啶基或2-或4-喹啉基,它们中的每一个在表示为N的X3上携带如以上所定义的基团R2
其中所提及的环可以各自被C1-C6-烷基,C1-C6-烷氧基,氟,氯,溴,碘,氰基,硝基,C1-C6-烷氧基羰基,C1-C6-烷硫基,C1-C6-酰胺基,C6-C10-芳基,C6-C10-芳氧基,C6-C10-芳基羰基胺基,单或二-C1-C6-烷基胺基,N-C1-C6-烷基-N-C6-C10-芳基胺基,吡咯烷基,吗啉基或哌嗪基取代。
在特别优选的实施方案中,所使用的菁染料是通式(I)的染料,
其中
环A和环B表示不同的杂环。
在同样特别优选的实施方案中,所使用的菁染料是通式(I)的染料,
其中
Y表示N。
在同样特别优选的实施方案中,所使用的菁染料是通式(I)的染料,
其中
Y表示C-CN。
在同样特别优选的实施方案中,所使用的菁染料是通式(I)的染料,
其中
p表示0或1。
可能的阴离子An-包括全部单价的阴离子或一当量的多价阴离子或一当量的低聚物或聚合物阴离子。优选的是无色阴离子。合适阴离子的例子是氯离子,溴离子,碘离子,四氟硼酸根,高氯酸根,六氟硅酸根,六氟磷酸根,甲硫酸根,乙硫酸根(Ethosulfat),C1-C10-链烷烃磺酸根,C1-C10-全氟链烷烃磺酸根,未被取代的或被氯-,羟基-或C1-C4-烷氧基-取代的C1-C10-链烷酸根,未被取代的或被硝基-,氰基-,羟基-,C1-C25-烷基-,全氟C1-C4-烷基-,C1-C4-烷氧基羰基-或氯-取代的苯磺酸根,或萘磺酸根或联苯磺酸根,未被取代的或被硝基-,氰基-,羟基-,C1-C4-烷基-,C1-C4-烷氧基-,C1-C4-烷氧基羰基-或氯-取代的苯二磺酸根,萘二磺酸根或联苯二磺酸根,未被取代的或被硝基-,氰基-,C1-C4-烷基-,C1-C4-烷氧基-,C1-C4-烷氧基羰基-,苯甲酰基-,氯苯甲酰基-或甲苯基-取代的苯甲酸根,萘二羧酸的阴离子,(二苯醚)二磺酸根,四苯基硼酸根,氰基三苯基硼酸根,四-C1-C20-烷氧基硼酸根,四苯氧基硼酸根,7,8-或7,9-dicarba-nido-undecaborat(1-)或(2-),其可以任选地在B和/或C原子上被一个或两个C1-C12-烷基或苯基取代,十二氢-dicarbadodecaborat(2-)或B-C1-C12-烷基-C-苯基-十二氢-dicarbadodecaborate(1-),聚苯乙烯磺酸根,聚(甲基)丙烯酸根,聚烯丙基磺酸根。
优选的是溴离子,碘离子,四氟硼酸根,高氯酸根,六氟磷酸根,甲烷磺酸根,三氟甲烷磺酸根,苯磺酸根,甲苯磺酸根,十二烷基苯磺酸根,十四烷磺酸根,聚苯乙烯磺酸根。
在非常特别优选的实施方案中,所使用的菁染料是通式(IV)到(XII)的染料
Figure A0281088300111
Figure A0281088300121
Figure A0281088300131
其中
X21表示O,S,N-R12或CR13R14
X41和X43独立地表示O,S,N-R22或CR23R14
X42表示N或C-R25
R11,R12,R21和R22彼此独立地表示甲基,乙基,丙基,丁基,戊基,己基,苄基,苯乙基,环己基,氯乙基,氰基甲基,氰基乙基,羟乙基,2-羟丙基,甲氧基乙基,乙氧基乙基或以下通式的基团
或,R11和R21表示-(CH2)2-或-(CH2)3-桥连基,
R23和R24表示氢,甲基或乙基或
CR23R24表示下式的二价基团
其中两个键是从星号(*)标记的环原子上引出,
R15表示氢,甲基,甲氧基,氯,氰基,硝基,甲氧基羰基,甲磺酰基或胺基磺酰基,
R16表示氢或
R15和R16一起表示-CH=CH-CH=CH-桥连基或
X21和R16一起表示*C=CH-CH=CH-,其中两个键从星号(*)标记的原子上引出,
R17和R18表示氢或一起表示-CH=CH-CH=CH-桥连基,
R25表示氢,甲基,苯基,氯,氰基,甲氧基羰基,乙氧基羰基或甲硫基,
R26表示氢,甲基,苯基,甲氧基,乙氧基,苯氧基,氰基,甲氧基羰基,乙氧基羰基,甲硫基,二甲基胺基,二乙基胺基,二丙基胺基,二丁基胺基,吡咯烷基,哌啶基,N-甲基哌嗪基或吗啉基或
R25和R26一起表示-(CH2)3-,-(CH2)4-,-S-(CH2)2-S-或-CH=CH-CH=CH-桥连基,它可以被甲基,甲氧基,氯,氰基,硝基,甲氧基羰基,甲磺酰基或氨基磺酰基取代,
R27和R28彼此独立地表示氢或甲基或一起形成-(CH2)3-或-(CH2)4-桥连基,
q表示0或1,
Y表示CH,C-CN或N和
An-表示四氟硼酸根,高氯酸根,六氟磷酸根,碘离子,硫氰酸根,氰酸根,羟基乙酸根,甲氧基乙酸根,乳酸根,柠檬酸根,甲烷磺酸根,乙烷磺酸根,三氟甲烷磺酸根,苯磺酸根,甲苯磺酸根,丁基苯磺酸根,氯苯磺酸根,十二烷基苯磺酸根,萘磺酸根或表示一当量的聚苯乙烯磺酸根,
其中对于通式(IV)的的菁染料而言,当X42表示C-R25和R25和R26一起表示-CH=CH-CH=CH-桥连基时,X21和X41不可以是相同的。
在该通式(IV)到(XII)中,尤其优选的是
X21表示O或S,
X41表示S或C(CH3)2
X42表示N或C-R25
R25表示氢或与R26一起表示-CH=CH-CH=CH-桥连基,
X43表示S或CH2
R27和R28表示氢,
q表示0和
Y表示N或CH,
其中其它的基团如以上所定义。
在同样地非常特别优选的实施方案中,所使用的菁染料是具有通式(XIII)到(XXV)的染料
Figure A0281088300151
Figure A0281088300161
Figure A0281088300171
其中
X21表示O,S,N-R12或CR13R14
X22,X41和X43独立地表示O,S,N-R22或CR23R24
X42表示N或C-R25
R11,R12,R21和R22彼此独立地表示甲基,乙基,丙基,丁基,戊基,己基,苄基,苯乙基,环己基,氯乙基,氰基甲基,氰基乙基,羟乙基,2-羟丙基,甲氧基乙基,乙氧基乙基或以下通式的基团
Figure A0281088300181
R23和R24表示氢,甲基或乙基或
CR23R24表示下式的二价基团
其中两个键是从星号(*)标记的环原子上引出,
R15表示氢,甲基,甲氧基,氯,氰基,硝基,甲氧基羰基,甲磺酰基或氨基磺酰基,
R16表示氢或
R15和R16一起表示-CH=CH-CH=CH-桥连基或
X21和R16-起表示*C=CH-CH=CH-,其中两个键从星号(*)标记的原子上引出,
R17和R18表示氢或一起表示-CH=CH-CH=CH-桥连基,
R25表示氢,甲基,苯基,氯,氰基,甲氧基羰基,乙氧基羰基或甲硫基,
R26表示氢,甲基,苯基,甲氧基,乙氧基,苯氧基,氰基,甲氧基羰基,乙氧基羰基,甲硫基,二甲基胺基,二乙基胺基,二丙基胺基,二丁基胺基,吡咯烷基,哌啶基,N-甲基哌嗪基或吗啉基或
R25和R26一起表示-(CH2)3-,-(CH2)4-,-S-(CH2)2-S-或-CH=CH-CH=CH-桥连基,其可以被甲基,甲氧基,氯,氰基,硝基,甲氧基羰基,甲磺酰基或氨基磺酰基取代,
R27到R30彼此独立地表示氢或甲基或
R27和R28或R29和R30一起表示-(CH2)3-,-(CH2)4-桥连基,
q和s彼此独立地表示0或1,
Y表示CH,C-CN或N和
An-表示四氟硼酸根,高氯酸根,六氟磷酸根,碘离子,硫氰酸根,氰酸根,羟基乙酸根,甲氧基乙酸根,乳酸根,柠檬酸根,甲烷磺酸根,乙烷磺酸根,三氟甲烷磺酸根,苯磺酸根,甲苯磺酸根,丁基苯磺酸根,氯苯磺酸根,十二烷基苯磺酸根,萘磺酸根或一当量的聚苯乙烯磺酸根,
其中对于通式(XIII)的菁染料,当X42表示C-R25,R25和R26一起表示-CH=CH-CH=CH-桥连基和Y表示CH时,X21和X41优选不是相同的,和对于通式(XXV)的菁染料,当q和s是相同的和Y表示CH时,X22和X43不可以是相同的。
在通式(XIII)到(XXV)中,尤其优选的是
X21表示O,S或C(CH3)2
X41表示S或C(CH3)2
X42表示N或C-R25
R25表示氢或与R26一起表示-CH=CH-CH=CH-桥连基,
X22和X43彼此独立地表示S或CH2
R27到R30表示氢,
q和s表示0和
Y表示N,CH或C-CN,
其中其它的基团如以上所定义,
其中对于通式(XIII)的菁染料,当X42表示C-R25,R25和R26一起表示-CH=CH-CH=CH-桥连基和Y表示CH时,X21和X41优选是不相同的,和对于通式(XXV)的菁染料,当Y表示CH时,X22和X43不可以是相同的。
在同样非常特别优选的实施方案中,所使用的菁染料是通式(XXVI)到(XXXVII)的染料
Figure A0281088300201
Figure A0281088300221
其中
X21表示O,S,N-R12或CR13R14
X41和X43独立地表示O,S,N-R22或CR23R24
X42表示N或C-R25
R11,R12,R21和R22彼此独立地表示甲基,乙基,丙基,丁基,戊基,己基,苄基,苯乙基,环己基,氯乙基,氰基甲基,氰基乙基,羟乙基,2-羟丙基,甲氧基乙基,乙氧基乙基或以下通式的基团
Figure A0281088300222
R23和R24表示氢,甲基或乙基或
CR23R24表示下式的二价基团
Figure A0281088300231
其中两个键是从星号(*)标记的环原子上引出,
R1表示氢,甲基,甲氧基,氯,氰基,硝基,甲氧基羰基,甲磺酰基或氨基磺酰基,
R16表示氢或
R15和R16一起表示-CH=CH-CH=CH-桥连基或
X21和R16一起表示*C=CH-CH=CH-,其中两个键从星号(*)标记的原子上引出,
R17和R18表示氢或一起表示-CH=CH-CH=CH-桥连基,
R25表示氢,甲基,苯基,氯,氰基,甲氧基羰基,乙氧基羰基或甲硫基,
R26表示氢,甲基,苯基,甲氧基,乙氧基,苯氧基,氰基,甲氧基羰基,乙氧基羰基,甲硫基,二甲基胺基,二乙基胺基,二丙基胺基,二丁基胺基,吡咯烷基,哌啶基,N-甲基哌嗪基或吗啉基或
R25和R26一起表示-(CH2)3-,-(CH2)4-,-S-(CH2)2-S-或-CH=CH-CH=CH-桥连基,其可以被甲基,甲氧基,氯,氰基,硝基,甲氧基羰基,甲磺酰基或氨基磺酰基取代,
R27和R28彼此独立地表示氢或甲基或一起表示-(CH2)3-或-(CH2)4-桥连基,
q表示0或1,
Y表示CH,C-CN或N和
An-表示四氟硼酸根,高氯酸根,六氟磷酸根,碘离子,硫氰酸根,氰酸根,羟基乙酸根,甲氧基乙酸根,乳酸根,柠檬酸根,甲烷磺酸根,乙烷磺酸根,三氟甲烷磺酸根,苯磺酸根,甲苯磺酸根,丁基苯磺酸根,氯苯磺酸根,十二烷基苯磺酸根,萘磺酸根或代表一当量的聚苯乙烯磺酸根,
其中对于通式(XXVI)的菁染料而言,当X42表示C-R25,R25和R26一起表示-CH=CH-CH=CH-桥连基和Y表示CH时,X21和X41优选是不相同的。
尤其优选的是通式(XXVI)到(XXVIII)和(XXXII)到(XXXIV)的菁染料
其中
X21表示O,S或C(CH3)2
X41表示S或C(CH3)2
X42表示N或C-R25
R25表示氢或与R26-起表示-CH=CH-CH=CH-桥连基,
X43表示S或CH2
R27和R28表示氢,
q表示0和
Y表示N,CH或C-CN,
其中其它的基团如以上所定义,
其中对于通式(XXVI)的菁染料而言,当X42表示C-R25,R25和R26一起表示-CH=CH-CH=CH-桥连基和Y表示CH时,X21和X41优选是不相同的。
对于可利用蓝光激光器的光来写和读的根据本发明的一次写入型光学数据载体而言,优选的是这样的菁染料,它的最大吸收λmax1是在340-410nm范围,其中在波长λmax1处的最大吸收的长波长侧翼中消光值是在λmax1处消光值的一半的那一波长λ1/2和在波长λmax1处的最大吸收的长波长侧翼中消光值是在λmax1处消光值的十分之一的那一波长λ1/10优选在各种情况下相隔不超过50nm。此类菁染料优选不具有最高达500nm,特别优选550nm,非常特别优选600nm的波长的更长波长最大值λmax2
优选的是具有345到400nm的最大吸收λmax1的菁染料。
特别优选的是具有350到380nm的最大吸收λmax1的菁染料。
非常特别优选的是具有360到370nm的最大吸收λmax1的菁染料。
对于这些染料而言,如以上所定义的λ1/2和λ1/10优选相隔不超过40nm,特别优选相隔不超过30nm,非常特别优选相隔不超过10nm。
在这方面合适的染料是具有其中Y是N的通式(IV)到(VI)和(X)到(XII)的染料,和具有其中Y是CH的通式(VII)到(IX)的染料。
对于利用蓝光激光器的光进行写和读的根据本发明的一次写入型光学数据载体,也优选的是这样的菁染料,它的最大吸收λmax2是在420-550nm范围,其中在波长λmax2处的最大吸收的短波长侧翼中的消光值是在λmax2处消光值的一半的那一波长λ1/2和在波长λmax2处的最大吸收的短波长侧翼中的消光值是在λmax2处的消光值的十分之一的那一波长λ1/10优选在各种情况下相隔不超过50nm。此类菁染料优选不具有最高达350nm,特别优选最高达320nm,非常特别优选最高达290nm的波长下的更短波长最大值λmax1
优选的是具有4 0到530nm的最大吸收λmax2的菁染料。
特别优选的是具有420到510nm的最大吸收λmax2的菁染料。
非常特别优选的是具有430到500nm的最大吸收λmax2的菁染料。
在这些菁染料中,如以上所定义的λ1/2和λ1/10优选相隔不超过40nm,特别优选相隔不超过30nm,非常特别优选相隔不超过20nm。
在这方面合适的染料是具有其中Y表示CH的通式(IV)到(VI)和(X)到(XII)的染料,和具有通式(XIII)到(XXIV)的染料。
对于利用红光激光器的光进行写和读的根据本发明的一次写入型光学数据载体而言,优选的是这样的菁染料,它的最大吸收λmax2是在500-650nm范围,其中在波长λmax2处的最大吸收的长波长侧翼中的消光值是在λmax2处消光值的一半的那一波长λ1/2和在波长λmax2处的最大吸收的长波长侧翼中的消光值是在λmax2处的消光值的十分之一的那一波长λ1/10优选在各种情况下相隔不超过50nm。此类菁染料优选不具有最高达750nm,特别优选最高达800nm,非常特别优选最高达850nm的更长波长最大值λmax3
优选的是具有530到630nm的最大吸收λmax2的菁染料。
特别优选的是具有550到620nm的最大吸收λmax2的菁染料。
非常特别优选的是具有580到610nm的最大吸收λmax2的菁染料。
在这些菁染料中,如以上所定义的λ1/2和λ1/10优选相隔不超过40nm,特别优选相隔不超过30nm,非常特别优选相隔不超过20nm。
在这方面合适的染料是具有通式(XIII)到(XV)和(XIX)到(XXI)的染料。
对于利用红外激光器的光进行写和读的根据本发明的一次写入型光学数据载体,优选的是这样的菁染料,它的最大吸收λmax3是在650-810nm范围,其中在波长λmax3处的最大吸收的长波长侧翼中的消光值是在λmax3处消光值的一半的那一波长λ1/2和在波长λmax3处的最大吸收的长波长侧翼中的消光值是在λmax3处的消光值的十分之一的那一波长λ1/10优选在各种情况下相隔不超过50nm。
优选的是具有660到790nm的最大吸收λmax3的菁染料。
特别优选的是具有670到760nm的最大吸收λmax3的菁染料。
非常特别优选的是具有680到740nm的最大吸收λmax3的菁染料。
在这些菁染料中,如以上所定义的λ1/2和λ1/10优选相隔不超过40nm,特别优选相隔不超过30nm,非常特别优选相隔不超过20nm。
在这方面合适的染料是具有通式(XXV)到(XXVII)和(XXXI)到(XXXIII)的染料。
该菁染料在最大吸收λmax2处具有>40000l/mol cm,优选>60000l/mol cm,特别优选>800001/mol cm,非常特别优选>100000l/molcm的摩尔消光系数ε。
该吸收光谱例如在溶液中测量。
具有所需的光谱性质的合适菁染料尤其是其中偶极矩变化Δμ=|μgag|,即在基态下的偶极矩与在第一激发态之间的正的差值尽可能小,优选<5D,特别优选<2D的那些染料。测定该偶极矩变化Δμ的方法例如描述在F.Würthner等,Angew.Chem.1997,109,2933,和其中所列举的文献中。低的溶剂-诱导波长偏移(Solvatochromie)(甲醇/二氯甲烷)同样地是合适的选择标准。优选的是这样的菁染料,它的溶剂-诱导波长偏移Δλ=|λ二氯甲烷甲醇|,即在溶剂二氯甲烷和甲醇中的吸收波长之间的正的差异,是<25nm,特别优选<15nm,非常特别优选<5nm。
通式(I)的一些菁染料例如可从DE-C 883 025,DE-OS 1 070316,DE-A 1170 569,J.Chem.Soc.1951,1087,Ann.Soc.Chim.Pol.1963,225中获知。
本发明进一步提供以下通式的菁染料
其中
R71表示C1-C16-烷基,C3-C6-链烯基,C5-C7-环烷基或C7-C16-芳烷基,
R72表示C1-C16-烷氧基,C1-C16-烷硫基,二-C1-C16-烷基胺基,N-C1-C16-烷基-N-C6-C10-芳基胺基,吡咯烷基,哌啶基,哌嗪基或吗啉基,
Y表示N和
其它的基团具有以上对于通式(I)所给出的意义。
优选的是具有通式(XL)的菁染料
其中
R1和R71彼此独立地表示甲基,乙基,丙基,丁基或苄基,
R72表示二甲基胺基,二乙基胺基,二丙基胺基,二丁基胺基,吡咯烷基,哌啶基或吗啉基,
Y表示N
p表示0或1,
R3和R4表示氢和
环A表示苯并噻唑-2-基,噻唑-2-基,噻唑啉-2-基,苯并噁唑-2-基,二氢吡咯-2-基或3,3-二甲基-3H-吲哚-2-基,其中苯并噻唑-2-基,噻唑-2-基,苯并噁唑-2-基和3,3-二甲基-3H-吲哚-2-基可以被甲基,甲氧基,氯,氰基,硝基或甲氧基羰基取代,和
An-表示阴离子。
特别优选的是,p是1和环A表示3,3-二甲基-3H-吲哚-2-基,5-甲基-3,3-二甲基-3H-吲哚-2-基,5-甲氧基-3,3-二甲基-3H-吲哚-2-基,5-硝基-3,3-二甲基-3H-吲哚-2-基,5-氯-3,3-二甲基-3H-吲哚-2-基或5-甲氧基羰基-3,3-二甲基-3H-吲哚-2-基,非常特别优选表示3,3-二甲基-3H-吲哚-2-基。
本发明进-步提供以下通式的菁染料
其中
R211表示C1-C16-烷基,C3-C6-链烯基,C5-C7-环烷基或C7-C16-芳烷基,
X44表示S,O或CH,
R271和R281彼此独立地表示氢或C1-C3-烷基或一起表示-(CH2)3-或-(CH2)4-桥连基,
u表示0或1,
Y表示CH和
其它的基团具有以上对于通式(I)所给出的意义。
优选的是具有通式(XLI)的菁染料
其中
R1和R211彼此独立地表示甲基,乙基,丙基,丁基或苄基,
X44表示S或CH,
R271和R281表示氢,
u表示0或1,
p表示0或1,
R3和R4表示氢和
环A表示苯并噻唑-2-基,噻唑-2-基,噻唑啉-2-基,苯并噁唑-2-基,二氢吡咯-2-基或3,3-二甲基-3H-吲哚-2-基,其中苯并噻唑-2-基,噻唑-2-基,苯并噁唑-2-基和3,3-二甲基-3H-吲哚-2-基可以被甲基,甲氧基,氯,氰基,硝基或甲氧基羰基取代,和
An-表示阴离子。
特别优选的是,p是1和环A表示3,3-二甲基-3H-吲哚-2-基,5-甲基-3,3-二甲基-3H-吲哚-2-基,5-甲氧基-3,3-二甲基-3H-吲哚-2-基,5-硝基-3,3-二甲基-3H-吲哚-2-基,5-氯-3,3-二甲基-3H-吲哚-2-基或5-甲氧基羰基-3,3-二甲基-3H-吲哚-2-基,非常特别优选3,3-二甲基-3H-吲哚-2-基。
同样优选的是,p是0和环A表示苯并噻唑-2-基,5-甲氧基-苯并噻唑-2-基,5-氯-苯并噻唑-2-基,5-氰基-苯并噻唑-2-基,3,3-二甲基-3H-吲哚-2-基,5-甲基-3,3-二甲基-3H-吲哚-2-基,5-甲氧基-3,3-二甲基-3H-吲哚-2-基,5-硝基-3,3-二甲基-3H-吲哚-2-基,5-氯-3,3-二甲基-3H-吲哚-2-基或5-甲氧基羰基-3,3-二甲基-3H-吲哚-2-基,非常特别优选苯并噻唑-2-基或3,3-二甲基-3H-吲哚-2-基。
该菁染料能够通过本身已知的方法来制备。
如果光的波长是在360-460nm和600-680nm的范围内所述的吸光性化合物确保了未写状态的光学数据载体的足够高的反射率(>10%)和在用聚焦光的点式照射时足够高的吸收以实现信息层的热降解。在数据载体上的写入和未写入点之间的对比度可通过根据入射光的波幅(Amplitude)和位相来说的反射率变化来获得,这是通过在热降解之后信息层的变化的光学性质。
该菁染料优选通过旋涂方法或真空汽相淀积方法被施涂于光学数据载体上。该菁染料能够彼此混合或与其它具有类似物光谱性质的染料混合。尤其,含有不同的阴离子的染料也可以混合。信息层能够不仅包括菁染料,而且包括诸如粘结剂,润湿剂,稳定剂,稀释剂和增感剂以及其它成分之类的添加剂。
同样有可能使用与其它染料(优选阳离子染料)的混合物。用于混合物的其它染料优选是其λmax与通式(I)的染料的λmax2或λmax3相差不超过30nm,优选不超过20nm,非常特别优选不超过10nm的那些染料。可提及的例子是选自菁类,Streptocyanine,Hemicyanine,Diazahemicyanine,Nullmethine,烯胺染料类,腙染料类,二-或三(杂)芳基甲烷染料类,呫吨染料类,吖嗪染料类(吩嗪类,噁嗪类,噻嗪)中或,例如,选自偶氮染料,蒽醌染料,Neutrocyanine,卟啉类或酞菁类中的染料。此类染料例如可从H.Berneth,“CationicDyes”,Ullmann′s Encyclopedia of Industrial Chemistry,VCH,第六版中获知。
除信息层外,其它的层如金属层,电介质层,阻隔层和保护层可以存在于该光学数据载体中。金属和电介质和/或阻隔层尤其用于调节反射率和热吸收/保留(Wrmehaushalts)。取决于激光波长,金属能够是金,银,铝等等。电介质层的例子是二氧化硅和氮化硅。阻隔层是电介质层或金属层。保护层是例如可光致固化的涂层,(压敏)粘合层和保扩膜。
压敏粘合剂层主要由丙烯酸粘合剂组成。在专利JP-A 11-2731471中公开的Nitto Denko DA-8320或DA-8310能够例如用于这一目的。
该光学数据载体具有,例如,下列层状结构(参见图1):透明基材(1),任选的保护层(2),信息层(3),任选的保护层(4),任选的粘合剂层(5),覆盖层(6)。
光学数据载体的结构优选:
-包括优选透明的基材(1),它的表面涂敷了能够利用光(优选激光)进行写的至少一层光可写的信息层(3),任选的保护层(4),任选的粘合剂层(5)和透明覆盖层(6)。
-包括优选透明的基材(1),它的表面涂敷了保护层(2),能够利用光(优选激光)进行写的至少一层光可写的信息层(3),任选的保护层(5)和透明覆盖层(6)。
-包括优选透明的基材(1),它的表面涂敷了任选的保护层(2),任选的可利用光(优选激光)进行写的至少一层光可写的信息层(3),任选的保护层(4),任选的粘合剂层(5)和透明覆盖层(6)。
-包括优选透明的基材(1),它的表面涂敷了能够利用光(优选激光)进行写的至少一层光可写的信息层(3),任选的粘合剂层(5)和透明覆盖层(6)。
另外地,光学数据载体具有例如下列层状结构(参见图2):优选透明的基材(11),信息层(12),任选的反射层(13),任选的粘合剂层(14),附加的优选透明的基材(15)。
本发明进一步涉及利用蓝光或红光,尤其激光写的根据本发明的光学数据载体。
下列实施例用于说明本发明的主题。
实施例
实施例1
8.1g的2-氨基-3-甲基-5-二异丙基胺基-1,3,4-噻二唑鎓甲硫酸盐(从2-氨基-5-二异丙基胺基-1,3,4-噻二唑和硫酸二甲酯制得)和5g的1,3,3-三甲基-2-亚甲基-3H-吲哚-ω-醛在25ml的甲苯和2.3g的甲磺酸的混合物中通过使用分水器来沸煮12小时。在冷却之后,添加50ml的己烷和分离所析出的油。将它置入在200ml的水中。该水相用每次200ml氯仿来萃取3次。该氯仿相在旋转蒸发器上蒸发。这得到2.3g(理论值的19%)的以下通式的红色粉
Figure A0281088300311
m.p.=115℃
λmax(甲醇)=544nm
ε=96235l/mol cm
λ1/21/10(短波长侧翼)=36nm
λ1/21/10(长波长侧翼)=13nm
溶解度:在TFP(2,2,3,3-四氟丙醇)中>2%
玻璃状膜
实施例2
3.1g的1-甲基-2-甲硫基-苯并噻唑鎓甲硫酸盐(从2-甲硫基苯并噻唑和硫酸二甲酯制得),和2.6g的1-乙基-2-甲基-噻唑啉鎓碘化物(从2-甲基噻唑啉和乙基碘制得)在50ml的吡啶中沸煮3小时。在冷却之后进行抽滤,用5ml的吡啶洗涤并干燥。这得到1.1g(理论值的27%)的以下通式的无色粉
Figure A0281088300312
m.p.=250-254℃
λmax(甲醇)=384nm
ε=54621l/mol cm
λ1/21/10(长波长侧翼)=10nm
溶解度:在TFP(2,2,3,3-四氟丙醇)中5%
0.4g的上述产物在15ml的甲醇中与0.1g的高氯酸锂一起在回流状态下搅拌1小时。在冷却之后进行抽滤,用3ml的甲醇洗涤并干燥。这得到0.3g(理论值的80%)的以下通式的无色粉
Figure A0281088300321
m.p.220-225℃
λmax(甲醇)=384nm
ε=56117l/mol cm
λ1/21/10(长波长侧翼)=10nm
溶解度:在TFP(2,2,3,3-四氟丙醇)中5%
玻璃状膜
同样合适的菁染料示于下列表中:
Figure A0281088300331
Figure A0281088300341
Figure A0281088300351
1)在甲醇中,除非另外说明。
2)Δλ=|λ二氯甲烷甲醇|
3)在短波长侧翼上
4)在长波长侧翼上
5)在甲醇/氯仿1∶1中
6)在丙酮中
7)在NMP中
实施例39
在室温下制备在2,2,3,3-四氟丙醇中由66.7wt%的实施例24的染料和33.3wt%的以下通式的染料组成的2wt%浓度溶液。
Figure A0281088300372
这一溶液利用旋涂法被施涂于预先刻槽的(pregrooved)聚碳酸酯基材上。预先刻槽的聚碳酸酯基材已经利用注射模塑法作为盘片形式制得。盘片和凹槽结构的尺寸对应于通常用于DVD-R的那些。作为信息载体的具有染料层的盘片涂敷了120nm的金和然后在金层上通过汽相淀积法涂敷了200nm的SiO。UV可固化的丙烯酸涂料随后通过旋涂法进行涂敷和利用UV灯来固化。该盘片通过建造在光测试仪工作台(Bank)上的动态写入试验装置来测试,该装置由用于产生线式偏振光的二极管激光器(λ=656nm),偏振-敏感的光束分裂器,λ/4板和具有数值孔径NA=0.6的可移动的悬挂式会聚透镜(激励器透镜)组成。从盘片的反射层上反射的光利用上述偏振-敏感的光束分裂器从射束路径中取出(ausgekoppelt)并利用像散透镜聚焦在四象限的(Vierquadranten)检测器上。在线性速度V=3.5m/s和写功率Pw=21mW下,测量信/噪比C/N=42dB。这里,该写功率是按照振荡脉冲序列来施加,该盘片交替地用上述写功率Pw辐射1μs和用读取功率Pr≈0.6mW辐射4μs。该盘片用这一振荡脉冲序列辐射,直至它绕自身旋转一次。以这种方式产生的标记然后使用读取功率Pr来读取和测量上述的信/噪比C/N。

Claims (14)

1.包括优选透明的基材的光学数据载体,该基材任选的已涂敷了一个或多个反射涂层,在该基材的表面上已经涂敷了光可写的信息层、任选的一个或多个反射层和任选的保护层或附加基材或覆盖层,其能够利用蓝色、红色或红外光,优选激光进行写和读,其中信息层包括吸光性化合物和任选的粘结剂,特征在于至少一种菁染料用作吸光性化合物。
2.根据权利要求1的光学数据载体,特征在于该菁染料具有通式(I)
Figure A0281088300021
其中
X1和X3表示氮或
X1-R1和X3-R2彼此独立地表示S,
X2表示O,S,N-R6,CR8或CR8R9
X4表示O,S,CR10或N-R7
Y表示N或C-R5
R1,R2,R6和R7彼此独立地表示C1-C16-烷基,C3-C6-链烯基,C5-C7-环烷基或C7-C16-芳烷基,
R3,R4和R5彼此独立地表示氢,C1-C16-烷基或氰基或
当m=0和p>0时,R1和R3一起表示-(CH2)2-,-(CH2)3-或-(CH2)4-桥连基,或
当m=0和p=0时,R1和R5一起表示-(CH2)2-,-(CH2)3-或-(CH2)4-桥连基,或
当n=0时,R2和R5一起表示-(CH2)2-,-(CH2)3-或-(CH2)4-桥连基,
R8,R9和R10彼此独立地表示氢或C1-C16-烷基或
CR8R9表示下式的二价基团
Figure A0281088300032
其中两个键是从星号(*)标记的环原子上引出,
m和n彼此独立地表示0或1,
p表示0,1或2,
包括X1、X2和连接X1和X2的基团的环A和包括X3、X4和连接X3和X4的基团的环B彼此独立地表示五元或六元芳族或准芳族或部分氢化的杂环,该杂环可含有1-4个杂原子和/或是苯并-或萘并-稠合的和/或被非离子基团取代,其中环A和B优选是不同的,和
An-表示阴离子。
3.根据权利要求1或2的光学数据载体,特征在于,在通式(I)中,以下通式的环A
Figure A0281088300033
表示苯并噻唑-2-基,噻唑-2-基,噻唑啉-2-基,苯并噁唑-2-基,噁唑-2-基,噁唑啉-2-基,苯并咪唑-2-基,咪唑-2-基,咪唑啉-2-基,二氢吡咯-2-基,3-H-吲哚-2-基,苯并[c,d]吲哚-2-基,2-或4-吡啶基或2-或4-喹啉基,
其中X1表示N,
其中该上述的环可以各自被C1-C6-烷基,C1-C6-烷氧基,氟,氯,溴,碘,氰基,硝基,C1-C6-烷氧基羰基,C1-C6-烷硫基,C1-C6-酰胺基,C6-C10-芳基,C6-C10-芳氧基或C6-C10-芳基羰基胺基取代,和
下式的环B
Figure A0281088300034
表示苯并噻唑-2-叉基,噻唑-2-叉基,噻唑啉-2-叉基,异噻唑-3-叉基,1,3,4-噻二唑-2-叉基,1,2,4-噻二唑-5-叉基,苯并噁唑-2-叉基,噁唑-2-叉基,噁唑啉-2-叉基,1,3,4-噁二唑-2-叉基,苯并咪唑-2-叉基,咪唑-2-叉基,咪唑啉-2-叉基,二氢吡咯-2-叉基,1,3,4-三唑-2-叉基,3H-吲哚-2-叉基,苯并[c,d]吲哚-2-叉基,2-或4-吡啶基或2-或4-喹啉基,它们中的每一个在表示为N的X3上携带如权利要求2中所定义的基团R2,其中所提及的环可以各自被C1-C6-烷基,C1-C6-烷氧基,氟,氯,溴,碘,氰基,硝基,C1-C6-烷氧基羰基,C1-C6-烷硫基,C1-C6-酰胺基,C6-C10-芳基,C6-C10-芳氧基,C6-C10-芳基羰基胺基,单或二-C1-C6-烷基胺基,N-C1-C6-烷基-N-C6-C10-芳基胺基,吡咯烷基,吗啉基或哌嗪基取代。
4.根据权利要求1到3中一项或多项的光学数据载体,特征在于该菁染料对应于通式(I)
其中
环A和环B表示不同的杂环。
5.根据权利要求1到4中一项或多项的光学数据载体,特征在于该菁染料对应于通式(I)
其中
Y表示N。
6.根据权利要求1到4中一项或多项的光学数据载体,特征在于该菁染料对应于通式(I)
其中
Y表示C-CN。
7.菁染料在一次写入型光学数据载体的信息层中的应用,其中该菁染料具有在340-410nm范围的最大吸收λmax1
8.菁染料在一次写入型光学数据载体的信息层中的应用,其中该菁染料具有在420-650nm范围的最大吸收λmax2
9.菁染料在一次写入型光学数据载体的信息层中的应用,其中该数据载体能够利用蓝光激光来写和读。
10.菁染料在一次写入型光学数据载体的信息层中的应用,其中该数据载体能够利用红光激光器光来写和读。
11.生产根据权利要求1的光学数据载体的方法,其特征在于,优选透明的、任选已涂敷了反射层的基材涂敷了菁染料,任选地与合适粘结剂和添加剂和任选地合适溶剂相结合,以及任选地还提供了反射层,附加的中间层和任选地保护层或附加基材或覆盖层。
12.根据权利要求1的光学数据载体,它是利用蓝光,红光或红外光,尤其是蓝光或红光,尤其是蓝光或红光激光光线来写的。
13.以下通式的菁染料
其中
R71表示C1-C16-烷基,C3-C6-链烯基,C5-C7-环烷基或C7-C16-芳烷基,
R72表示C1-C16-烷氧基,C1-C16-烷硫基,二-C1-C16-烷基胺基,N-C1-C16-烷基-N-C6-C10-芳基胺基,吡咯烷基,哌啶基,哌嗪基或吗啉基,
Y表示N和
其它的基团如权利要求2中所定义。
14.以下通式的菁染料
Figure A0281088300052
其中
R211表示C1-C16-烷基,C3-C6-链烯基,C5-C7-环烷基或C7-C16-芳烷基,
X44表示S,O或CH,
R271和R281彼此独立地表示氢或C1-C3-烷基或一起表示-(CH2)3-或-(CH2)4-桥连基,
u表示0或1,
Y表示CH和
其它的基团如权利要求2中所定义。
CNA028108833A 2001-03-28 2002-03-20 在信息层中包括菁染料作为吸光性化合物的光学数据载体 Pending CN1513171A (zh)

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CN103539792B (zh) * 2013-10-30 2016-06-01 大连理工大学 一种氰基取代的不对称菁类化合物,其制备方法及应用

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US6835725B2 (en) 2004-12-28
US7041354B2 (en) 2006-05-09
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