CN1147846C - 复合多次甲基染料及其用途 - Google Patents

复合多次甲基染料及其用途

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Publication number
CN1147846C
CN1147846C CNB971807159A CN97180715A CN1147846C CN 1147846 C CN1147846 C CN 1147846C CN B971807159 A CNB971807159 A CN B971807159A CN 97180715 A CN97180715 A CN 97180715A CN 1147846 C CN1147846 C CN 1147846C
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China
Prior art keywords
alkyl
unsubstituted
independently
halogen
alkoxy
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Expired - Fee Related
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CNB971807159A
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English (en)
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CN1240530A (zh
Inventor
H・沃勒布
H·沃勒布
椎露哈尔特
B·施米德尔哈尔特
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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Publication of CN1147846C publication Critical patent/CN1147846C/zh
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Abstract

本发明涉及一种光学记录介质，它包括基质、记录层和反射层，其中所述记录层包含至少一种具有以下结构式的染料：其中A1和A2分别独立地为C(CH3)2、O、S、Se、或未取代的或被C1-C5烷基或苄基取代的CH＝CH；M1和M2分别独立地为Cr2+或Co3+；L1和L1’分别独立地为具有以下结构式的配体：L2和L2’相互独立地为，独立于L1和L1’的结构式(II)、(III)或(VI)的配体：m为0.2-1.0的数；且根据m，n为0.0-0.8的数，使得m和n的总数等于1.0；p和q分别独立地为0或1；且Q为CR15、CR15-CR16＝CR17或CR15-CR16＝CR17-CR18＝CR19；本发明还要求式I染料本身、以及一种使用本发明记录介质来光学记录、储存和复制信息的方法，其中记录或复制优选在600-800纳米的相同波长范围内进行。

Description

复合多次甲基染料及其用途
本发明的技术领域是在一次性书写记录介质上进行信息的光学记录，其中信息凹坑通过着色剂在记录部位和未记录部位上的不同光学性能而加以区别。这种技术通常称作WORM，而且还包括，例如CD-R或DVD-R。
在“Optical Data Storage 1989(光学数据储存1989)”，Technical DigestSeries(技术文摘系列)，Vol.1(第一卷)，45(1989)中，可以得知能够在770-830纳米波长进行记录的压缩光盘(CD-R)。按照Orange BookStandard(橙皮书标准)，基质尤其应该在记录波长上具有65％或更高的基底反射率。记录介质可以是，例如花青染料或偶氮金属配合物。
由于最新使用了发射波长为630-690纳米的致密高功率二极管红色激光，因此原则上有可能将数据压缩密度提高5-8倍，因为轨道间距(2圈信息轨道之间的距离)和凹坑尺寸可降低到常规CD的大约一半。有关DVD-R体系的各种要求可在Violet Book Standard(紫皮书标准)中找到。
但是，这对所用记录层提出了基本上较高的要求，如高折射指数、高日光稳定性、和低激光辐射下的稳定性(在读取时)，同时还要求对高能激光辐射(记录时)的高敏感性以及在固态下吸收带的最优位置和形状。由于在固态下的吸收通常明显不同于溶液中的吸收而且又不能根据溶液中的吸收情况来预知，因此情况尤其复杂。为了在不同染料的不同性能之间进行折衷，已经尝试使用，尤其是几种染料组分的混合物。
EP-649884公开了在780-790纳米范围内具有特定光学性能的混合物在光学记录上的应用。这些混合物由特殊非离子偶氮吡啶酮染料和至少一种第二染料组成，其中用于一个实施例的第二染料为由花青染料阳离子和US-5426015的双偶氮吡啶酮镍阴离子组成的盐。两种染料都是深蓝色的，且该混合物具有宽带吸收。
US-5547728公开了光学记录层，它在780纳米上也具有特定光学性能、而且由阳离子花青染料(尤其是吲哚二碳花青染料)和非离子或阳离子镍金属化甲臜染料的混合物组成。在实施例中，混合物的比率为85∶15-50∶50。
EP-483387公开了具有光稳定记录层的光学记录介质，所述记录层由阳离子花青染料和中性或阳性杂环蓝色偶氮染料的混合物组成，所述偶氮染料，例如为二-[2-(5’-氯吡啶-2’-基)-偶氮-5-二乙基氨基-酚]-镍。这些染料混合物在600-800纳米范围内吸收。
EP-676751公开了在770-830纳米上反射率至少为65％且在630-690纳米上至少为15％的光学记录介质，它包括各组分的混合物，其中之一在630纳米以下吸收，另一种在630-690纳米吸收。所述组分为花青染料以及偶氮金属配合物。所公开的混合物包括，其中加入了少量离子花青染料的主要由非离子杂环偶氮金属配合物组成的混合物。
JP-3/51182描述了包含花青染料阳离子和亲电偶氮金属配合物阴离子的光学记录介质，其中所述阴离子被苯基中的硝基或卤素基团所取代、或被萘基环中的胺基或酰胺基团所取代。所公开的偶氮金属配合物阴离子为酚偶氮环烷铬配合物。但现已发现，这些配合物的缺点在于，在记录介质中，它们在600-800纳米范围内具有高第二吸收。还有，不能根据说明书确定出所述“花青”阳离子可包括的结构。
US-4626496描述了包括有机染料阳离子和金属配合物阴离子的“复盐”及其与另一种有机染料的混合物。在所描述的内容中，有机染料，例如为多次甲基；金属配合物阴离子，例如为双-(3，4，6-三氯苯基-1，2-二硫醇)镍(III)；其它染料，例如为多次甲基染料。按照其说明书，金属配合物阴离子应该相对染料阳离子优选具有红移吸收。此外，这些混合物的宽带吸收具有一个平坦的长波吸收边，因此如US-5426015所述不适于CD-R。
JP-03/224793公开了光学记录介质，其记录层由萘并吡咯花青染料与在短波处具有最大吸收的另一染料的混合物组成。从JP-03/150189中可以得知，这些萘并吡咯花青染料相对可比的苯并三唑花青染料具有较好的耐久性。至于其它染料，JP-03/224793只公开了花青，其最大吸收应该优选蓝移至少20纳米，但其波长应该长于650纳米。所公开的阴离子尤其是四硫醇镍配合物，它在US-5204220中是作为猝灭剂和萘并吡咯花青染料的光稳定剂而已知的。
JP-03/147356公开了光学记录介质，其吸收层由花青高氯酸盐和金属多硫醇铵配合物或金属多硫醇鏻配合物组成。据说它们的耐久性得到提高。
JP-08/310129公开了光学记录介质，其吸收层由假吲哚五次甲基花青染料和1-脱氢-2-(1’-吡唑基)-4-(4”-二烷基氨基苯基)-亚氨基-5-苯基咪唑过渡金属配合物组成。据说其复制性能的耐久性得到提高。
另外，JP-01/229694公开了特定花青混合物在光学记录上的应用，而JP-61/8384公开了包含花青染料和另外一种盐的光学记录介质，所述盐由花青染料阳离子和四硫代-配位过渡金属阴离子组成。
JP-04/308791公开了光学记录介质，其激光辐射吸收染料由具有相同发色团的至少3种组分的混合物组成，所述发色团包括特定花青或偶氮金属配合物的发色团。合适的是，该混合物中各组分的最大吸收应该相差不超过50纳米。
最后，其它混合物还可从EP-528512中得知，其中使用了具有不同最大吸收的两种花青阳离子，而且为了遮掩花青的非所需短波吸收，另外加入了一种优选在400-500纳米进行吸收的化合物，如4-硝基-4’-氨基偶氮苯。
但现已发现，由几种组分组成的已知记录层同样仍不具有能够完全令人满意的所需性能。尤其是，吸收带的半宽、长波吸收边的位置和陡度、其上的吸收、敏感性、折射指数在记录时的变化、或光稳定性、甚至几种这些参数的组合不能满足各种要求，或者仅达到不令人满意的程度。
非常令人惊奇的是，现已发现，如果用于记录层的染料为花青染料，且其阴离子由特定偶氮金属配合物或偶氮金属配合物的特定混合物组成时，可得到具有改进性能的光学记录介质。除了在高折射指数、敏感性和，尤其是光稳定性以及在固态下吸收带的位置和形状方面具有改进的折衷性能，本发明染料具有合适的无定形态和有利的分解温度。在使用激光进行记录时，折射指数变化非常大，而且可令人惊奇地在能量较低时进行记录。由于可有利地在记录时基本上保持高敏感性和合适形态而没有任何变化，因此可更好地控制凹坑的形成。这还可有利地增加数据压缩密度，而不使用多余的编码。
因此，本发明涉及包括基质、记录层和反射层的光学记录介质，其中所述记录层包含至少一种具有以下结构式的染料：
Figure C9718071500111
其中
A1和A2分别独立地为C(CH3)2、O、S、Se、或未取代的或被C1-C5烷基或苄基取代的CH＝CH；
M1和M2分别独立地为Cr2+或Co3+；
L1和L1’分别独立地为具有以下结构式的配体双阴离子：
Figure C9718071500112
或
L2和L2’相互独立地为，独立于L1和L1’的具有以下结构式的配体双阴离子：
Figure C9718071500115
或
Figure C9718071500116
m为0.2-1.0的数；且根据m，n为0.0-0.8的数，使得m和n的总数等于1.0；
p和q分别独立地为0或1；
Q为CR15、CR15-CR16＝CR17或CR15-CR16＝CR17-CR18＝CR19；
R1和R2分别独立地为未取代的或被卤素、羟基、C1-C12烷氧基或氰基单-或多取代的C1-C12烷基或C1-C12链烯基；或分别未取代的或被R20或被R20和R21所取代的C6-C12芳基或C7-C12烷芳基；
R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13和R14分别独立地为氢、卤素、硝基、氰基、羟基、氨基、NHR22、NHR22R23、CONH2、CONHR22、CONR22R23、SO2C1-C12烷基、SO2NH2、SO2NHR22、SO2NR22R23、COOH、COOR24、NHCOR25、NR24COR25、NHCOOR25、NR24COOR25、或分别未取代的或被卤素、羟基或氰基单-或多取代的C1-C12烷基、C1-C12烷基硫代或C1-C12烷氧基；或
R3和R4和/或R5和R6共同为未取代的或被R26或R26和R27所取代的1，4-丁-1，3-二烯基，这样所形成的萘基就具有共享苯基；
R15、R16、R17、R18和R19分别独立地为氢原子、卤素、C1-C12烷氧基；分别未取代的或被卤素、羟基或氰基单-或多取代的C1-C12烷基、C6-C12芳基、C7-C12烷芳基或NR22R23；
R15和R17、R16和R18、或R17和R19共同为1，2亚乙基亚乙基、1，2-亚丙基亚丙基、邻-亚苯基、分别未取代的或被R26或被R26和R27取代的α，2-亚苄基或1，8-亚萘基；
R20和R21分别独立地为氢、卤素、硝基、氰基、羟基、氨基、NHR22、NHR22R23、CONH2、CONHR22、CONR22R23、SO2C1-C12烷基、SO2NH2、SO2NHR22、SO2NR22R23、COOH、COOR24、NHCOR25、NR24COR25、NHCOOR25、NR24COOR25、或分别未取代的或被卤素、羟基或氰基单-或多取代的C1-C12烷基、C1-C12烷基硫代或C1-C12烷氧基；
R22和R23分别独立地为未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基、C2-C12链烯基；或分别未取代的或被R26或被R26和R27取代的C6-C12芳基或C7-C12烷芳基；或
R22和R23连同连接氮原子为未取代的或被1-4个C1-C4烷基取代的吡咯烷、哌啶、哌嗪或吗啉；或分别未取代的或被R26或被R26和R27取代的咔唑、吩噁嗪或吩噻嗪；
R24和R25分别独立地为未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基、C2-C12链烯基；或分别未取代的或被R26或被R26和R27取代的C6-C12芳基或C7-C12烷芳基；
R26和R27分别独立地为卤素、硝基、氰基、羟基、NR28R29、CONH2、CONHR28、CONR28R29、SO2C1-C12烷基、SO2NR28R29、COOH、COOR30、NHCOR31、NHCOOR31、NR30COR31、NR30COOR31、或分别未取代的或被卤素单-或多取代的C1-C12烷基、或C1-C12烷氧基；
R28和R29分别独立地为氢原子、C6-C12芳基、或C7-C12烷芳基；分别未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基、或C2-C12链烯基；
R28和R29连同连接氮原子为未取代的或被1-4个C1-C4烷基取代的吡咯烷、哌啶、哌嗪或吗啉；或咔唑、吩噁嗪或吩噻嗪；
R30和R31分别独立地为C6-C12芳基或C7-C12烷芳基；分别未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基或C2-C12链烯基。
烷基和链烯基可以是直链的、支链的、单环的或多环的。因此C1-C12烷基，例如为甲基、乙基、正丙基、正丁基、仲丁基、异丁基、叔丁基、环丁基、正戊基、2-戊基、3-戊基、2，2-二甲基丙基、环戊基、环己基、正己基、正辛基、1，1，3，3-四甲基丁基、2-乙基己基、壬基、三甲基环己基、癸基、基、苧基、冰片基、1-金刚烷基、2-金刚烷基或十二烷基。
C2-C12链烯基为单-或多取代的C2-C12烷基，其中两个或多个双键可选地为分离的或共轭的，例如乙烯基、烯丙基、2-丙烯-2-基、2-丁烯-1-基、3-丁烯-1-基、1，3-丁二烯-2-基、2-环丁烯-1基、2-戊烯-1-基、3-戊烯-2-基、2-甲基-1-丁烯-3-基、2-甲基-3-丁烯-2-基、3-甲基-2-丁烯-1-基、1，4-戊二烯-3-基、2-环戊烯-1-基、2-环己烯-1-基、3-环己烯-1-基、2，4-环己二烯-1-基、1-对-薄荷烯-8-基、4(10)-苧烯-10-基、2-冰片烯-1-基、2，5-冰片二烯-1-基、7，7-二甲基-2，4-降蒈二烯-3-基、或己烯基、辛烯基、壬烯基癸烯基或十二烯基的不同异构体。
C7-C12烷芳基通常为苄基、2-苄基-2-丙基、β-苯基-乙基、9-芴基、α，α-二甲基-苄基、ω-苯基丁基或ω，ω-二甲基-ω-苯基丁基。
C6-C12芳基通常为苯基、萘基、联苯基或2-芴基。
C1-C12烷氧基为O-C1-C12烷基。
卤素为氯、溴、氟或碘。氟或氯是优选的。
分别被卤素、羟基、C1-C12烷氧基或氰基单-或多取代的C1-C12烷基或C2-C12链烯基通常为：2-氯乙基、三氟甲基、2，2，2-三氟乙基、三氯乙烯基、全氟十二烷基、2-羟基乙基、2-甲氧基乙基、2-乙氧基乙基、2-丁氧基-乙基、2，3-二-羟基丙基、2，3-二甲氧基丙基、2，3-二甲氧基丙基或2-氰基乙基，优选三氟甲基、2-羟基乙基、2-甲氧基乙基、2-乙氧基乙基或2-氰基乙基。
记录层优选包含基于记录层重量的至少60％重量的至少一种式(1)化合物。
除了式(1)化合物，新记录介质可包含一种或多种盐，例如氯化铵、溴化胺、十五烷基氯化铵、氯化钠、溴化钾、硫酸钠、碘化钠、甲基磺酸钠或甲基硫酸钠，其离子可来自，例如所用组分。如果存在，这些附加盐优选为无色的，且其含量为基于记录层重量的20％重量以下，尤其优选最多10％重量，非常优选最多1％重量。
但新记录介质优选基本上不含任何其它的无机盐。
除了式(1)化合物，新记录介质的记录层还可包含其它的离子染料，如具有以下结构式的花青的氟化物、氯化物、溴化物、碘化物、高氯酸盐、高碘酸盐、碳酸盐、碳酸氢盐、硫酸盐、硫酸氢盐、磷酸盐、磷酸氢盐、磷酸二氢盐、六氟磷酸盐、四氟硼酸盐、六氟锑酸盐、乙酸盐、草酸盐、甲磺酸盐、三氟甲磺酸盐、甲苯磺酸盐、甲基硫酸盐、酚盐或苯甲酸盐：
Figure C9718071500141
或具有以下结构式的金属偶氮配合物的Li+、Na+、K+、[Mg2+]1/2[Ca2+]1/2甲基铵、乙基铵、十五烷基铵、异丙基铵、二环己基铵、四甲基铵、四乙基铵、四丁基铵、苄基三甲基铵、苄基三乙基铵、甲基三辛基铵、十三烷基甲基铵、四丁基鏻、四苯基鏻、丁基三苯基鏻或乙基三苯基鏻盐：
或
所有符号定义如上。如果存在，附加的离子染料的量优选为基于记录层总重的20％重量以下。
但新记录介质基本上不含任何其它的离子染料。
如果需要，也可加入附加的非离子染料，但其用量只能优选为基于记录层的最多20％重量，特别优选最多5％重量。但尤其优选不加入任何其它染料。如果加入，这些染料应当具有相对式(1)染料蓝移的最大吸收。
这种新记录介质还可包含可改进其性能的添加剂，如稳定剂、冲击剂或熔点抑制剂。用于可记录的记录介质的添加剂及其用量本身是已知的。通过加入添加剂，如EP-600427所描述的化合物，可更好地控制激光辐射所产生的凹坑形状，这样可复制出改进的无缺陷信号。优选的添加剂为过渡金属的有机金属化合物或金属配合物，如金属茂或金属乙酰丙酮化物、金属二硫代氨基甲酸盐或金属二硫代磷酸盐，其用量为基于记录层总重的最多100％重量，优选最多50％重量，最优选最多20％重量。
这种新记录介质优选包含单独一种式(1)染料。
以记录层的总重为基，本发明的记录层特别优选由占大多数的一种或多种式(1)染料、其用量为最多50％重量的任选的过渡金属的一种或多种可选有机金属化合物或金属配合物、以及其用量为20％重量以下的任选的一种或多种可选无色盐组成。该记录层尤其优选由式(1)染料、其用量最多为20％重量的过渡金属的可选有机金属化合物或金属配合物、以及其用量最多为1％重量的可选无色盐组成。
配体L2或L2’优选具有结构式(IV)或(V)。特别优选的是，至少两个配体L1、L1’、L2或L2’符合结构式(II)、(III)、(IV)或(V)。
M1和M2优选Co。
A1或A2分别独立地优选为C(CH3)2、O、S或CH＝CH。A1或A2特别优选为C(CH3)2或S，最优选S。
p和q优选等于0。
Q优选CR15-CR16＝CR17或CR15-CR16＝CR17-CR18＝CR19。
Q特别优选CR15-CR16＝CR17。
R1和R2分别独立地为未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基；或未取代的或被R20或被R20和R21所取代的C7-C12烷芳基；
R3、R4、R5和R6分别独立地为氢、卤素、硝基、氰基、氨基、NHR22、NHR22R23、CONH2、CONHR22、CONR22R23、COOH、COOR24、NHCOR25、NR24COR25，或分别未取代的或被卤素、羟基或氰基单-或多取代的C1-C12烷基或C1-C12烷氧基；或R3和R4和/或R5和R6共同为1，4-丁-1，3-二烯基，这样所形成的萘基就具有共享苯基。
R7、R8、R9、R10、R11、R12、R13和R14分别独立地优选为氢、卤素、硝基、氰基、氨基、NHR22、NHR22R23、CONH2、CONHR22、CONR22R23、SO2C1-C12烷基、SO2NH2、SO2NHR22、COOH、COOR24、NHCOR25、NR24COR25，或分别为未取代的或被卤素单-或多取代的C1-C12烷基或C1-C12烷氧基。
R15、R16、R17、R18和R19分别独立地为氢、卤素、C1-C4烷基或苯基。
R20和R21分别独立地优选为氢、卤素、硝基、氰基、氨基、NHR22、NHR22R23、NHCOR25、NR24COR25、C1-C12烷基或C1-C12烷氧基；
R22和R23分别独立地为未取代的或被C1-C8烷氧基单-或多取代的C1-C12烷基、C2-C12链烯基、C6-C12芳基或C7-C12烷芳基；或R22和R23连同连接氮原子为吡咯烷、哌啶、哌嗪或吗啉。
R24和R25分别独立地为C1-C12烷基、C2-C12链烯基、C6-C12芳基或C7-C12烷芳基。
特别优选的是，至少一个配体双阴离子L1、L1’、L2或L2’具有以下结构式：
Figure C9718071500171
或
尤其优选的是，所有配体双阴离子L1、L1’、L2和L2’具有选自这四种结构中的一种结构。
式(1)染料本身是新颖的，因此这也是本发明的一个目的。优选的染料与优选为光学记录层组分的染料相同。
类似于已知染料，式(1)染料可通过本身已知的方法由已知物质制备出来。合适的制备方法为，例如上述已有技术中所描述的各种方法，如从盐混合物中进行结晶，其中所需染料发生沉淀而相应的非所需抗衡离子则留在溶液中，或其中所需染料留在溶液中而非所需抗衡离子则发生沉淀；或在阳离子交换器或阴离子交换器中去除非所需的抗衡离子。在式(1)染料的情况下，如果m＝1，可使用均匀的偶氮金属配合物配体；同样在式(1)染料的情况下，如果m＜1，则代之以使用偶氮金属配合物配体的混合物。
这种新的式(1)染料通常具有对应于花青阳离子发色团的长波吸收、以及对应于偶氮金属配合物配体的发色团的弱短波吸收。
通过使用式(1)染料，可有利地得到均匀的、无定形的且低分散的记录层，令人惊奇的是，其在固态下的长波吸收也特别陡峭，而且还具有高吸收系数和高折射指数。其它优点为高日光稳定性和低激光辐射(读取时)下的稳定性、以及对高能激光辐射(记录时)的高敏感性、凹坑的均匀性、及良好的热稳定性和储存稳定性。
根据m和n，式(1)染料可只有一种阴离子[L1＝M1＝L1’]-、或两种阴离子[L1＝M1＝L1’]-和[L2＝M2＝L2’]-。尽管原则上不必使用第二种阴离子[L2＝M2＝L2’]-，但现已令人惊奇地发现，具有结构式(II)、(III)、(IV)、(V)或(VI)的偶氮金属配合物阴离子可对式(1)染料在固态下的的长波吸收产生不同的影响，这样，通过用具有结构式(IV)、(V)或(VI)的阴离子配体部分替代具有结构式(II)或(III)的阴离子配体，可选择性地将式(1)染料在固态下的最大吸收移动最多约10纳米。
由此可产生其它的主要优点，即，通过将均匀的偶氮金属配合物阴离子替代成其混合物，式(1)新染料可根据其光学性能进行优化调节。例如，通过使用其花青盐具有不同最大吸收的另一种偶氮金属配合物阴离子替代其花青盐具有特定最大吸收的偶氮金属配合物阴离子，可优化式(1)染料在固态下的长波吸收边的确切位置，而不改变花青发色团且长波吸收边不会出现拉平现象；或者通过使用其花青盐具有较好光稳定性的另一种偶氮金属配合物阴离子特定其花青盐具有较差光稳定性的偶氮金属配合物阴离子，可提高式(1)染料的光稳定性。
因此，金属配合物阴离子[L1＝M1＝L1’]-通常与金属配合物阴离子[L2＝M2＝L2’]-结合使用，两者结构上的差异使得其花青盐在固态下的最大吸收相差至少5纳米。这两者花青盐在固态下的最大吸收的差值优选至少10纳米。如果将金属配合物阴离子[L1＝M1＝L1’]-和[L2＝M2＝L2’]-结合使用，n优选0.1-0.7，特别优选0.2-0.5。
在这种情况下，结构不同的金属配合物阴离子[L1＝M1＝L1’]-和[L2＝M2＝L2’]-优选如下，其中
●M1和M2为不同金属；
●如果L1和L1’具有结构式(II)，L2和L2’具有结构式(V)和/或(VI)；
●如果L1和L1’具有结构式(III)，L2和L2’具有结构式(IV)和/或(VI)；
●L2具有结构式(V)或(VI)L1具有结构式(II)，L1’具有结构式(III)且L2’具有结构式(V)；
●L1和L2和/或L1’和L2’中的p和q分别不同；
或
●与L2或L2’中的R11和R12对连接到式(XI)偶氮基团的原子CB上的π-电子密度的作用相比，L1或L1’中的R7和R8可通过其特性和位置，对连接到式(X)偶氮基团的原子CA上的π-电子密度产生明显不同的影响。
Figure C9718071500191
合适的基质，例如为玻璃、矿物、陶瓷和热固性塑料或热塑性塑料。优选的基质为玻璃和均聚或共聚塑料。合适的塑料，例如为热塑性聚碳酸酯、聚酰胺、聚酯、聚丙烯酸酯和聚甲基丙烯酸酯、聚氨酯、聚烯烃、聚氯乙烯、聚偏二氟乙烯、聚酰亚胺、硬塑料聚酯和环氧树脂。基质可以是纯净态的或可包含各种常规添加剂，如紫外线吸收剂或染料，尤其是如JP 04/167239中提出用作记录层的光稳定剂的那些。在后一情况下，加入基质中的染料应当具有相对记录层染料蓝移至少10纳米，优选至少20纳米的最大吸收。
通常基质在600-700纳米的至少一部分范围内应该是透明的，这样它可透过具有记录或读出波长的入射光的至少90％。在涂层那面，该基质优选具有槽深50-500纳米、槽宽0.1-0.8μm且2圈间距0.4-1.6μm的螺旋导槽，特别优选的是，槽深为80-250纳米，更优选80-200μm，槽宽为0.2-0.5μm，特别优选0.2-0.4μm，且2圈间距为0.6-0.8μm，特别优选0.7-0.8μm。具有不同横截面轮廓的凹槽，例如为矩形、斜方形或V形凹槽。
特别适于反射层的反射材料包括，在记录和复制中用作激光辐射的良好反射物的各种金属，其例子为化学元素周期表的第三、第四和第五主族和副族的金属。特别合适的金属为Al、In、Sn、Pb、Sb、Bi、Cu、Ag、Au、Zn、Cd、Hg、Sc、Y、La、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt，和镧系金属Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu，及其合金。由于高反射率和易制备的原因，特别优选的是铝、银、铜、金或其合金的反射层。
根据层结构确定的最上层，如反射层或记录层应该具有厚度为0.1-1000μm，优选0.1-50μm，特别优选0.5-15μm的附加保护层。如果需要，该保护层还可用作粘合剂以将第二基质层粘附其上，该第二基质层的厚度优选为0.1-5毫米且由与载体基质的相同材质组成。如果按照该顺序涂以记录层和反射层的两种基质是通过粘附层连接的，那么所得记录介质可在两面进行记录。
适用于保护层的材料主要是塑料，其薄层是直接或通过粘附层施用到基质或最上层的。应该选择可另外进行修饰，例如记录的具有良好表面性能的机械和热稳定塑料。这些塑料可以是热固性或热塑性塑料。优选的是特别易于制备且经济的辐射固化(例如，使用紫外线辐射)保护层。已知许多辐射固化材料。可辐射固化单体和低聚物的例子为二醇、三醇和四醇的丙烯酸酯和甲基丙烯酸酯、由芳族四羧酸和在氨基的至少两个邻位具有C1-C4烷基的芳族二胺组成的聚酰亚胺，以及具有二烷基，如二甲基马来酰亚氨基的低聚物。
这种新记录介质的特征还在于附加层，如干涉层。还可形成具有几层(例如，两层)记录层的记录介质。这些材料的构造和应用是熟练技术人员所已知的。如果存在这些层，干涉层优选位于记录层和反射层之间和/或记录层和基质之间，且由介电材料，如TiO2、Si3N4、ZnS或EP353393中所描述的硅树脂组成。
这种新记录介质可由本身已知的方法来制备，而且可根据所用材料及其操作方式采用不同涂布方法。
涂布方法的合适例子为浸涂、流涂、铺开、刮刀涂布和旋涂、以及高真空蒸汽沉积法。例如，如果使用流涂法，通常使用在有机溶剂中的溶液。如果使用溶剂，应该小心选择以保证所用基质对这些溶剂不敏感。合适的涂布方法和溶剂，尤其在EP 401791中进行描述。
记录层优选通过将染料溶液进行旋涂而进行涂覆，现已发现，合适的溶剂尤其为醇类，如2-甲氧基乙醇、异丙醇或正丁醇；羟基酮类，如二丙酮醇或3-羟基-3-甲基-2-丁酮；羟基酯，如乳酸甲酯或异丁酸甲酯，或优选为氟化醇，典型的有2，2，2-三氟乙醇或2，2，3，3-四氟-1-丙醇、及其混合物。其它的合适溶剂尤其在EP-483387中公开。
金属反射层优选通过溅射、在真空下的蒸汽沉积或化学蒸汽沉积(CVD)进行涂覆。溅射技术由于可产生对技术反射层所用基质的高粘附性而特别优选。这些技术是已知的，且在文献(如，J.L.Vossen和W.Kern，“Thin Film processes(薄膜方法)”，Academic Press，1978)中有描述。
这种新记录介质的构造原则上取决于读出方法；已知的主要原理是对传输变化，优选反射变化的记录。
如果记录材料是按照反射变化进行构造的，那么以下结构就是可用结构的例子：透明载体/记录层(一层或多层)/反射层和，如果有用，保护层(不必是透明的)；或载体(不必是透明的)/反射层/记录层和，如果有用，透明的保护层。对于前者，光由载体面进行辐射；而对于后者，辐射是由记录层的那面或，如果合适，由保护层的那面进入的。在这两种情况下，光检测器位于光源的同侧。按照本发明进行使用的记录介质的前一结构通常是优选的。
如果记录材料按照光传输的变化进行构造，以下交替结构就是合适的例子：透明载体/记录层(一层或多层)和，如果有用，透明保护层。用于记录和用于读取的光可由载体面或由记录层的那面或，如果合适，由保护层的那面进行交替辐射，这时光检测器总是位于反面。
用于记录和/或读取凹坑的合适激光的例子为市售二极管激光，如波长为635、650、670、680、780或830纳米的GaAsAl、InGaAlP或GaAs激光二极管，其辐射聚焦在记录层上。记录可通过已知方法来进行，即，通过使用调制聚焦激光束来记录具有固定或变化长度的凹坑，所述激光束是在恒定或可变速率下在记录层的表面上进行导向。
信息的读取是通过本身已知的方法来进行的，即通过使用激光辐射来记录吸收变化或反射变化，这尤其在“CD-Player and R-DAT Recorder”(Claus Biaesch-Wiepke，Vogel Buchverlag.Wuerzburg 1992)中有描述。熟练技术人员熟悉这些要求。
这种新的包含信息的介质尤其是一种WORM型光学信息材料。它可用作，例如用于计算机的可演奏CD(压缩光盘)、CD-R(压缩光盘-可读的)或DVD-R(数字视频光盘-可读的)记录材料，或用作身份证和信用卡，或用于衍射光学元件，如全息图的生产。
因此，本发明还涉及这种新记录介质在光学记录、储存或复制信息中的应用。优选在300-800纳米，特别优选500-800纳米，尤其优选600-800纳米的波长范围内进行记录。复制优选在600-800纳米的波长范围内进行。记录和复制尤其优选在600-800纳米的相同波长范围内进行。
通过使用这种新方法，可以记录具有高可靠度和耐久性的信息，这种信息的特点之处在于其优异的机械和热稳定性、以及高光稳定性和凹坑的清晰边缘区。其特殊优点是令人惊奇的高信号/噪音比率和低跳动(可进行无缺陷读出)。高储存能力在视频部分是特别有价值的。
以下实施例用于更详细说明本发明(花青双键的立体化学是未知的，因此在Z形-拉伸双键中，必须考虑作为选择的其E式，而在反式-拉伸双键时，还存在顺式-它们还可以是不同异构体的混合物)：
实施例A1：将0.30克的结构式产品CY-1(Nippon Kankoh ShikisoKenKyusho)和0.39克的结构式产品AZ-1(Ciba Specialty ChemicalsInc.)溶解在20毫升二氯甲烷中。在50℃的旋转式蒸发器中，通过蒸发将该溶液完全浓缩。将残余物悬浮在300毫升水中，然后用搅拌器搅拌30分钟。过滤之后，将残余物再次悬浮在300毫升水中，然后用搅拌器搅拌30分钟。过滤之后，用水洗涤产物，然后在50℃/160毫巴下连夜干燥，得到0.60克(理论值的95％)的绿色粉末，按照元素分析，其中包含0.14％的钠。UV/VIS(乙醇)：λ最大＝679纳米，ε＝201’810L·mol-1·cm-1。
Figure C9718071500221
实施例A2-A24：重复实施例A1的一般步骤，但用花青CY-2至CY-24替代花青CY-1：
  实施例   花青   用量(克)   偶氮配合物   用量(克)   产量(克)     λ最大(乙醇)(纳米)     ε(乙醇)[1·mol-1·cm-1]
  A2   CY-2   0.17   AZ-1   0.26   0.28     548     104′280
  A3   CY-3   0.51   AZ-1   0.79   1.10     559     141′190
  A4   CY-4   0.50   AZ-1   0.67   0.84     564     153′170
  A5   CY-5   1.50   AZ-1   2.07   3.10     573     148′660
  A6   CY-6   0.50   AZ-1   0.69   1.00     578     126′640
  A7   CY-7   0.25   AZ-1   0.31   0.50     579     72′144
  A8   CY-8   0.50   AZ-1   0.60   0.90     580     98′280
  A9   CY-9   0.50   AZ-1   0.68   0.89     587     111′870
  A10   CY-10   0.50   AZ-1   0.64   0.94     596     123′010
  A11   CY-11   0.20   AZ-1   0.23   0.39     685     180′080
  A12   CY-12   0.50   AZ-1   0.68   0.95     565     119′390
  A13   CY-13   0.50   AZ-1   0.78   1.00     582     196′100
  A14   CY-14   0.50   AZ-1   0.65   0.99     573     138′120
  A15   CY-15   0.20   AZ-1   0.26   0.33     569     108′100
  A16   CY-16   0.20   AZ-1   0.24   0.40     579     90′550
  A17   CY-17   0.16   AZ-1   0.21   0.34     580     87′630
  A18   CY-18   0.20   AZ-1   0.22   0.18     563     99′640
  A19   CY-19   2.00   AZ-1   2.94   3.20     560     106′590
  A20   CY-20   2.00   AZ-1   2.86   3.94     565     122′860
  A21   CY-21   2.00   AZ-1   2.62   2.94     577     137′690
  A22   CY-22   2.00   AZ-1   2.20   3.60     679     222′770
  A23   CY-23   0.20   AZ-1   0.28   0.33     577     78′210
  A24   CY-24   2.50   AZ-1   3.23   5.00     577     154′910
Figure C9718071500261
CY-3(Aldrich)、CY-9、CY-10、CY-11、CY-13、CY-14、CY-16、CY-17(NK-3229、NK-467、NK-3219、NK-1533、NK-616、NK-1056、NK-716，都是Nippon Kankoh-Shikiso KenKyusho Co.，Ltd的产品)和CY-22(OM-65，Fuji Photo Film Co.，Ltd)是可买到的。CY-19、CY-20和CY-21可按照Makromol.Chem.182，3427(1981)中所描述的方法进行制备。其它花青可按照已知方法进行制备。
实施例A2-A54：重复实施例A1的一般步骤，但用以下化合物替代花青CY-1和/或偶氮配合物AZ-1：
  实施例   花青   用量(克)   偶氮配合物   用量(克)   产量(克)    λ最大(乙醇)(纳米)    ε(乙醇)[l·mol-1·cm-1]
  A25   CY-1   0.30   AZ-2   0.51   0.70     679    177′060
  A26   CY-4   0.50   AZ-2   0.87   1.06     564    142′460
  A27   CY-4   0.50   AZ-3   0.94   1.18     564    141′890
  A28   CY-4   0.50   AZ-4   0.78   1.03     564    123′760
  A29   CY-4   0.50   AZ-5   0.79   0.99     564    102′050
  A30   CY-4   0.50   AZ-7   0.82   1.10     564    126′420
  A31   CY-5   0.50   AZ-2   0.90   1.25     573    128′950
  A32   CY-5   0.50   AZ-3   0.96   1.17     572    118′860
  A33   CY-5   0.50   AZ-7   0.82   1.03     570    95′870
  A34   CY-6   0.50   AZ-2   0.93   1.20     569    105′570
  A35   CY-6   0.50   AZ-3   0.96   1.20     571    99′610
  A36   CY-6   0.50   AZ-7   0.84   1.00     573    97′780
  A37   CY-11   50   AZ-2   76.8   126.5     684    192′340
  A38   CY-11   50   AZ-3   79.8   127.5     684    181′450
  A39   CY-11   50   AZ-7   69.7   114.0     684    185′620
  A40   CY-12   2.50   AZ-2   4.56   6.50     576    136′620
  A41   CY-12   2.50   AZ-3   4.70   6.10     576    138′940
  A42   CY-12   3.00   AZ-7   5.00   6.60     576    132′060
  A43   CY-13   0.50   AZ-2   1.02   1.34     582     179′310
  A44   CY-13   0.50   AZ-3   1.10   1.40     582   127′800
  A45   CY-13   0.50   AZ-7   0.97   1.30     582   106′720
  A46   CY-15   0.20   AZ-2   0.35   0.50     568   108′180
  A47   CY-15   0.20   AZ-3   0.37   0.50     569   106′600
  A48   CY-15   0.20   AZ-7   0.26   0.34     569   75′200
  A49   CY-18   0.20   AZ-2   0.30   0.38     564   96′360
  A50   CY-18   0.20   AZ-3   0.31   0.28     563   116′070
  A51   CY-18   0.20   AZ-7   0.22   0.15     564   65′810
  A52   CY-24   2.00   AZ-2   3.50   5.20     577   141′230
  A53   CY-24   2.00   AZ-3   3.60   5.10     577   156′540
  A54   CY-24   2.50   AZ-7   3.90   5.60     577   132′280
Figure C9718071500301
Figure C9718071500311
实施例A55-A64：重复实施例A1-A24的一般步骤，但在每个实施例中使用两种不同偶氮金属配合物的混合物：
实施例  花青  用量(克) 偶氮配合物 用量(克)     产量(克)    λ最大(乙醇)(纳米)   ε(乙醇)[1·mol-1·cm-1]
A55  CY-4  0.50  AZ-5AZ-6 0.390.35     1.17     563   141′440
A56  CY-4  0.50  AZ-6AZ-1 0.350.34     1.08     564   156′190
A57  CY-4  0.50  AZ-2AZ-5 0.430.39     1.20     564   151′860
A58  CY-4  0.50  AZ-1AZ-3 0.340.47     1.10     564   138′450
A59  CY-4  0.50  AZ-6AZ-3 0.350.47     1.12     564   129′990
A60  CY-4  0.50  AZ-3AZ-2 0.470.43     1.18     564   127′530
A61  CY-4  0.50  AZ-4AZ-3 0.400.47     1.10     564   122′630
A62  CY-4  0.50  AZ-1AZ-2 0.340.43     1.20     565   150′530
A63  CY-1  0.20  AZ-5AZ-6 0.160.14     0.48     679   208′840
A64  CY-1  0.30  AZ-1AZ-2 0.200.25     0.65     679   195′760
实施例A65：将2克CY-11和2.28克AZ-1溶解在60毫升甲基·异丁基酮中，然后用3×60毫升水进行洗涤。将500毫升水加入有机相中，然后通过蒸汽蒸馏将溶剂蒸发出来。过滤，收集到深绿色固体，用3×50毫升水进行洗涤，然后在60℃/160毫巴下进行干燥。得到3.30克(理论值的84.4％)的蓝绿色粉末，其中包含0.34％的氯(钠的含量低于10ppm的检测极限)。
UV/VIS(乙醇)：λ最大＝684纳米，ε＝202′270L·mol-1·cm-1。
实施例A66：在回流下，将2.0克CY-5和3.01克AZ-1溶解在75毫升正丙醇中。在搅拌下，滴加600毫升水。将所得悬浮液冷却至室温，然后过滤，将残余物在50℃/160毫巴下连夜干燥，得到4.58克(理论值的99.5％)的红棕色粉末，其中包含286ppm的钠和0.69％的溴。
UV/VIS(N-甲基吡咯烷酮)：λ最大＝579纳米，ε＝135′180L·mol-1·cm-1。
实施例A67：在80℃下，将2.0克CY-5和3.01克AZ-1溶解在40毫升N-甲基吡咯烷酮中。在搅拌下，滴加150毫升水。将所得悬浮液冷却至室温并过滤，用3×100毫升的水洗涤残余物，然后在50℃/160毫巴下连夜干燥，得到3.97克(理论值的86.2％)的红棕色粉末，其中包含31ppm的钠(溴的量低于0.3％的检测极限)。
UV/VIS(N-甲基吡咯烷酮)：λ最大＝579纳米，ε＝137′050L·mol-1·cm-1。
实施例A68：在80℃下，将2.0克CY-5和3.01克AZ-1溶解在40毫升N，N-二甲基乙酰胺中。在搅拌下，滴加150毫升水。将所得悬浮液冷却至室温并过滤，用3×100毫升的水洗涤残余物，然后在50℃/160毫巴下连夜干燥，得到3.37克(理论值的81.9％)的红棕色粉末，其中包含19ppm的钠(溴的量低于0.3％的检测极限)。
UV/VIS(N-甲基吡咯烷酮)：λ最大＝579纳米，ε＝136′960L·mol-1·cm-1。
实施例A69：将2.0克CY-5和3.01克AZ-1、130毫升1-戊醇和100毫升水放入容器中，然后在搅拌下，将该混合物加热至80℃。分离出有机相，将另外2-100毫升水加入有机相中，混合搅拌，然后再次分离出有机相。向有机相中加入200毫升水，然后在常压下将溶剂共沸蒸馏出去。将所得悬浮液冷却至室温并过滤，用3×100毫升的水洗涤残余物，然后在50℃/160毫巴下连夜干燥，得到1.18克(理论值的39.3％)的红棕色粉末，其中不含任何可检测量的钠或溴。
UV/VIS(N-甲基吡咯烷酮)：λ最大＝579纳米，ε＝134′900L·mol-1·cm-1。
实施例A70·通过TGA(加热速率为10℃/分钟，35-400℃)来分析实施例A5的化合物。分解作用开始于250℃。
实施例A71：将0.25克的实施例A5的化合物和0.05克苯甲酰基二茂铁溶解在25毫升二氯甲烷中。通过在Rotavap(旋转式蒸发器)中进行蒸发，将该溶液完全浓缩，然后通过TGA(加热速率为10℃/分钟，35-400℃)来分析该混合物。分解作用开始于190℃。
实施例A72：将0.25克的实施例A5的化合物和0.05克乙酰丙酮铁(III)溶解在25毫升二氯甲烷中。通过在Rotavap(旋转式蒸发器)中进行蒸发，将该溶液完全浓缩，然后通过TGA(加热速率为10℃/分钟，35-400℃)来分析该混合物。分解作用开始于180℃。
实施例B1：将2.0％重量的实施例A5的产物溶解在2，2，3，3-四氟-1-丙醇中。将该溶液过滤通过孔宽0.2μm的Telflon过滤器，然后以200rpm的速度旋涂在直径120毫米的1.2毫米厚有槽聚碳酸酯光盘(槽深180纳米，槽宽0.45μm)的表面上，过量溶液离心抛出。蒸发去除溶剂之后，染料成为一种均匀的无定形固体层，其在597纳米的最大吸收下的光密度为1.3。然后在真空涂布装置中，将80纳米厚的铝层涂覆到记录层上。在该层中，通过旋涂法涂覆由紫外线可固化光敏聚合物(SD-17，Dainippon Ink)组成的13μm厚保护层。记录基质在650纳米下的基底反射率为60％。在4mW的功率和0.5米/秒的速度下，该活性层通过波长为633纳米的HeNe激光器进行记录。在记录部位上，该工艺步骤导致反射率由60％变成10％。
实施例B2：将实施例A4产物的固体层施用到玻璃基质上，然后通过光谱椭圆测量法进行测量(Sopra Instrument)。在635纳米的记录波长上，测得折射指数n＝2.3且吸收系数k＝0.03。
实施例B3：在光盘测试仪TMDDU-1000(Pulstec Industrial Co.)上，使用功率为9mW且线速率为3.84米/秒的635纳米红色激光二极管，在按照实施例B1生产的基质上记录具有不同脉冲宽度的凹坑。结果，最短凹坑(l3/l14)的调制比为0.17，而最长凹坑(l11/l14H)的调制比为0.78。跳动值达到了DVD-R Color Book 1.0中的规格(＜9％)，且记录材料的信号/噪音比率(CNR)为66dB。
实施例B4：将1.5％重量的实施例A6的产物溶解在2，2，3，3-四氟-1-丙醇中。按照实施例B1，将该溶液过滤，然后施用到0.6毫米厚的有槽聚碳酸酯光盘(直径120毫米，槽间距0.8μm，槽深110纳米，槽宽0.4μm)上，过量溶液通过在800rpm下进行旋涂而离心抛出。在溅射装置(TMTwister，Balzers AG)中，在3kW的功率下涂覆55纳米厚铝层(3.0×10-3毫巴氩气)。随后，涂覆5μm厚的紫外线可固化清漆保护层(SD-220，Dainippon Ink)。在光盘测试仪DDU-1000上，在11mW的功率(线速率为3.84米/秒)下，记录不同的凹坑。最短凹坑(l3/l14)的调制比为0.21，而最长凹坑(l11/l14H)的调制比为0.75。跳动值在规格(＜9％)范围内，且信号/噪音比率(CNR)为66dB。
实施例B5：将2.0％重量的实施例A1的产物溶解在2，2，3，3-四氟-1-丙醇中，然后过滤(Teflon过滤器，0.45μm孔宽)。以200rpm的速度，将该溶液旋涂到1.2毫米厚的有槽(槽深220纳米，槽宽06μm，槽间距1.6μm，)聚碳酸酯光盘(直径为120毫米)上。在70℃下涂布该固体层20分钟，然后溅射涂覆60纳米厚的金层。按照实施例1，将该光盘涂以清漆。使用CD-R燃烧炉(TMHP 6020 Surestone)，在2.4米/秒的速度下，将19.4MB的视频顺序记录在记录基质上。现象可在市售CD-ROM驱动器上读取。

Claims (20)

1.一种光学记录介质，它包括基质、记录层和反射层，其特征在于，所述记录层包含至少一种具有以下结构式的染料：
其中
A1和A2分别独立地为C(CH3)2、O、S、Se、或未取代的或被C1-C5烷基或苄基取代的CH＝CH；
M1和M2分别独立地为Cr2+或Co3+；
L1和L1’分别独立地为具有以下结构式的配体双阴离子：
L2和L2’相互独立地为，独立于L1和L1’的具有以下结构式的配体双阴离子：
Figure C9718071500023
m为0.2-1.0的数；且根据m，n为0.0-0.8的数，使得m和n的总数等于1.0；
p和q分别独立地为0或1；
Q为CR15、CR15-CR16＝CR17或CR15-CR16＝CR17-CR18＝CR19；
R1和R2分别独立地为未取代的或被卤素、羟基、C1-C12烷氧基或氰基单-或多取代的C1-C12烷基或C1-C12链烯基；或分别未取代的或被R20或被R20和R21所取代的C6-C12芳基或C7-C12烷芳基；
R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13和R14分别独立地为氢、卤素、硝基、氰基、羟基、氨基、NHR22、NHR22R23、CONH2、CONHR22、CONR22R23、SO2C1-C12烷基、SO2NH2、SO2NHR22、SO2NR22R23、COOH、COOR24、NHCOR25、NR24COR25、NHCOOR25、NR24COOR25、或分别未取代的或被卤素、羟基或氰基单-或多取代的C1-C12烷基、C1-C12烷基硫代或C1-C12烷氧基；或
R3和R4和/或R5和R6共同为未取代的或被R26或R26和R27所取代的1，4-丁-1，3-二烯基，这样所形成的萘基就具有共享苯基；
R15、R16、R17、R18和R19分别独立地为氢原子、卤素、C1-C12烷氧基；分别未取代的或被卤素、羟基或氰基单-或多取代的C1-C12烷基、C6-C12芳基、C7-C12烷芳基或NR22R23；
R15和R17、R16和R18、或R17和R19共同为1，2亚乙基亚乙基、1，2亚丙基亚丙基、邻-亚苯基、分别未取代的或被R26或被R26和R27取代的α，2-亚苄基或1，8-亚萘基；
R20和R21分别独立地为氢原子、卤素、硝基、氰基、羟基、氨基、NHR22、NHR22R23、CONH2、CONHR22、CONR22R23、SO2C1-C12烷基、SO2NH2、SO2NHR22、SO2NR22R23、COOH、COOR24、NHCOR25、NR24COR25、NHCOOR25、NR24COOR25、或分别未取代的或被卤素、羟基或氰基单-或多取代的C1-C12烷基、C1-C12烷基硫代或C1-C12烷氧基；
R22和R23分别独立地为未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基、C2-C12链烯基；或分别未取代的或被R26或被R26和R27取代的C6-C12芳基或C7-C12烷芳基；或
R22和R23连同连接氮原子为未取代的或被1-4个C1-C4烷基取代的吡咯烷、哌啶、哌嗪或吗啉；或分别未取代的或被R26或被R26和R27取代的咔唑、吩噁嗪或吩噻嗪；
R24和R25分别独立地为未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基、C2-C12链烯基；或分别未取代的或被R26或被R26和R27取代的C6-C12芳基或C7-C12烷芳基；
R26和R27分别独立地为卤素、硝基、氰基、羟基、NR28R29、CONH2、CONHR28、CONR28R29、SO2C1-C12烷基、SO2NR28R29、COOH、COOR30、NHCOR31、NHCOOR31、NR30COR31、NR30COOR31、或分别未取代的或被卤素单-或多取代的C1-C12烷基、或C1-C12烷氧基；
R28和R29分别独立地为氢原子、C6-C12芳基、或C7-C12烷芳基；分别未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基、或C2-C12链烯基；
R28和R29连同连接氮原子为未取代的或被1-4个C1-C4烷基取代的吡咯烷、哌啶、哌嗪或吗啉；或咔唑、吩噁嗪或吩噻嗪；
R30和R31分别独立地为C6-C12芳基或C7-C12烷芳基；分别未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基或C2-C12链烯基。
2.根据权利要求1的记录介质，其中所述记录层包含基于记录层重量的至少60％重量的至少一种式(I)化合物。
3.根据权利要求1的记录介质，其中，分别以记录层总重为基，所述记录层由以下物质组成：
●一种或多种式(I)染料，
●其用量可选为最多50％重量的过渡金属的一种或多种可选有机金属化合物或金属配合物，和
●其用量可选为20％重量以下的一种或多种可选无色盐。
4.根据权利要求3的记录介质，它包含用量最多为1％重量的一种或多种无色盐。
5.根据权利要求3的记录介质，其中所述记录层不含任何其它的无机盐。
6.根据权利要求1的记录介质，其中所述记录层还包含具有以下结构式的花青的氟化物、氯化物、溴化物、碘化物、高氯酸盐、高碘酸盐、碳酸盐、碳酸氢盐、硫酸盐、硫酸氢盐、磷酸盐、磷酸氢盐、磷酸二氢盐、六氟磷酸盐、四氟硼酸盐、六氟锑酸盐、乙酸盐、草酸盐、甲磺酸盐、三氟甲磺酸盐、甲苯磺酸盐、甲基硫酸盐、酚盐或苯甲酸盐：
或下式金属偶氮配合物的Li+、Na+、K+、[Mg2+]1/2、甲基铵、乙基铵、十五烷基铵、异丙基铵、二环己基铵、四甲基铵、四乙基铵、四丁基铵、苄基三甲基铵、苄基三乙基铵、甲基三辛基铵、十三烷基甲基铵、四丁基鏻、四苯基鏻、丁基三苯基鏻或乙基三苯基鏻的盐：
或
Figure C9718071500053
其用量为基于记录层总重的20％重量以下，A1、A2、L1、L2、L1’、L2’、M1、M2、Q、R1-R6、以及m和n具有如权利要求1所要求的相同含义。
7.根据权利要求1的记录介质，其中L2或L2’具有结构式IV或V。
8.根据权利要求1的记录介质，其中M1和M2为Co。
9.根据权利要求1的记录介质，其中p和q等于0。
10.根据权利要求1的记录介质，其中Q为CR15-CR16＝CR17。
11.根据权利要求1的记录介质，其中：R1和R2分别独立地为未取代的或被卤素、羟基或C1-C12烷氧基单-或多取代的C1-C12烷基；或未取代的或被R20或被R20和R21所取代的C7-C12烷芳基；R15、R16、R17、R18和R19分别独立地为氢、卤素、C1-C4烷基或苯基。且R3、R4、R5和R6分别独立地为氢原子、卤素、硝基、氰基、氨基、NHR22、NHR22R23、CONH2、CONHR22、CONR22R23、COOH、COOR24、NHCOR25、NR24COR25，或分别未取代的或被卤素、羟基或氰基单-或多取代的C1-C12烷基或C1-C12烷氧基；或R3和R4和/或R5和R6共同为1，4-丁-1，3-二烯基，这样所形成的萘基就具有共享苯基。
12.根据权利要求1的记录介质，其中：R7、R8、R9、R10、R11、R12、R13和R14分别独立地优选为氢、卤素、硝基、氰基、氨基、NHR22、NHR22R23、CONH2、CONHR22、CONR22R23、SO2C1-C12烷基、SO2NH2、SO2NHR22、COOH、COOR24、NHCOR25、NR24COR25，或分别为未取代的或被卤素单-或多取代的C1-C12烷基或C1-C12烷氧基；R20和R21分别独立地优选为氢、卤素、硝基、氰基、氨基、NHR22、NHR22R23、NHCOR25、NR24COR25、C1-C12烷基或C1-C12烷氧基；R24和R25分别独立地为C1-C12烷基、C2-C12链烯基、C6-C12芳基或C7-C12烷芳基；且R22和R23分别独立地为未取代的或被C1-C8烷氧基单-或多取代的C1-C12烷基、C2-C12链烯基、C6-C12芳基或C7-C12烷芳基，或R22和R23连同连接氮原子为吡咯烷、哌啶、哌嗪或吗啉。
13.根据权利要求1的记录介质，其中至少一个配体双阴离子L1、L1’、L2或L2’具有以下结构式：
或
14.根据权利要求1的记录介质，其中[L1＝M1＝L1’]-和[L2＝M2＝L2’]-在结构上是不同的，且n为0.2-0.5。
15.根据权利要求1的记录介质，它在涂层那面具有螺旋导槽，其中槽深为80-250纳米、槽宽为0.3-0.5μm且2圈间距为0.6-0.8μm。
16.一种具有权利要求1所要求的结构式I的化合物。
17.一种光学记录、储存或复制信息的方法，它包括使用权利要求1所要求的记录介质。
18.根据权利要求17的方法，其中记录是在300-800纳米的波长范围内进行的。
19.根据权利要求17的方法，其中复制是在600-800纳米的波长范围内进行的。
20.根据权利要求17的方法，其中记录和复制是在600-800纳米的相同波长范围内进行的。
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