CN1174398C - 光学记录介质和其中所采用的二吡咯甲烷金属螯合物 - Google Patents

光学记录介质和其中所采用的二吡咯甲烷金属螯合物 Download PDF

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CN1174398C
CN1174398C CNB981246559A CN98124655A CN1174398C CN 1174398 C CN1174398 C CN 1174398C CN B981246559 A CNB981246559 A CN B981246559A CN 98124655 A CN98124655 A CN 98124655A CN 1174398 C CN1174398 C CN 1174398C
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CN1218257A (zh
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三泽伝美
小木曾章
西本泰三
����һ
杉本贤一
塚原宇
沟上健二
诧摩启辅
加藤健一
政冈俊裕
熊谷洋二郎
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Yamamoto Chemicals Inc
Mitsui Chemical Industry Co Ltd
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Abstract

本文公开了在底物上具有至少一记录层和反射层的新的光学记录介质,其中在记录层中包含至少一种式(1)代表的二吡咯甲烷金属螯合物。其中R1和R9各自独立地为链烯基、芳基或杂芳基;R2至R8各自独立地为氢原子、卤原子、或具有20或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧基羰基、芳烷基、芳基或杂芳基;M为过渡金属。

Description

光学记录介质和其中所采用的二吡咯甲烷金属螯合物
本发明涉及一种其中采用二吡咯甲烷金属螯合物,并且与通常情况相比,在更高的密度下为可记录和可重现的光学记录介质。
目前,作为一种与CD相比,具有更大容量的光学记录介质,已开发并且商业化了具有4.7GB容量的数字录像盘。DVD为ROM介质,因此希望具有相应容量的可记录和可重现的光学记录介质。在DVDS中,一次性书写的类型被称为DVD-R。
在DVD中,为了实现高密度记录,激光束的振动波长在约630nm-680nm的范围内,它为比CD情况下更短的波长。作为用于可在该短波长中被采用的含有机染料的光学记录介质的染料,在日本申请公开号74690/1992,38878/1993,40161/1994,40162/1994,199045/1994,336086/1994,76169/1995,125441/1995,262604/1995,156218/1997,193544/1997,193545/1997,193547/1997,194748/1997,202052/1997,267562/1997和274732/1997中已建议了花青染料,偶氮染料,苯并吡喃类型染料,苯并二呋喃酮类型染料,靛类染料,二恶嗪类型染料和卟啉类型染料。然而,这些常规技术具有染料耐久性及尤其是使用短波长所特有的一些问题。例如,当用聚焦激光束打开一个小的纹孔时,其周边广泛被影响,这样不利地形成大大扩大的纹孔。这种不利导致振动的恶化和径向交调失真。相反地,在一些常规技术中,有时形成极其细小的纹孔,并且这种不利导致受调放大器失准。此外,当选择一种具有不适宜的光学常数(折射率和消光系数)的有机染料并在所希望的激光波长下用于记录层时,发生反射度,敏感性等的偏差。目前仍未根本上克服这些缺陷。
本发明的一个目的是提供一种光学记录介质,其用具有520-690nm波长的短波激光可记录和可重现。具有极好的耐久性,并适用于高密度记录。
本发明人已建议一种适用于高密度记录的可记录和可重现的光学记录介质,在这种记录介质中,采用二吡咯甲烷金属螯合物作为有机染料(日本专利申请公开号226172/1998)。本发明人已进一步广泛研究了其中采用二吡咯甲烷金属螯合物的光学记录介质。结果,已发现选择具有包含乙烯基或卤原子的取代基,取代基,如将特定的芳基或杂芳基引入吡咯环的α-位的二吡咯甲烷金属螯合物,或铜或钴作为上面二吡咯甲烷金属螯合物中的配位金属,并在记录层中使用两种或多种所选择的二吡咯甲烷金属螯合物可提供一种光学记录介质,其中由有机染料的缺陷导致的反射度和敏感性的偏差,即光学特性的波长依赖性被抑制,并且在不稳定性和耐久性方面是极好的。因此,已完成本发明。也就是说,本发明的各个方面如下。
1.本发明的第一个方面涉及一种在底物上具有至少一层记录层和一层反射层的光学记录介质,其中在该记录层中包含至少一种式(I)代表的二吡咯甲烷金属螯合物:
Figure C9812465500061
其中R1和R9各自独立地为链烯基、芳基或杂芳基;R2至R8各自独立地为氢原子、卤原子、或具有20或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧基羰基、芳烷基、芳基或杂芳基;及M为过渡金属。
2.本发明的第二个方面涉及根据上面段落1的光学记录介质,其中式(1)中的R1为-CH=CH-R10,其中R10为氢原子,卤原子,具有20个或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧羰基。
3.本发明的第三个方面是涉及根据上面段落1的光学记录介质,其中式(1)中的R1为具有20或更少碳原子的取代或未取代的芳基或杂芳基,及M为铜或钴。
4.本发明的第四个方面是涉及根据上面段落3的光学记录介质,其中式(1)中的R1和R3为具有20或更少碳原子的同时取代或未取代的芳基或杂芳基。
5.本发明的第五个方面是涉及根据上面段落4的光学记录介质,其中式(1)中的R1,R3和R9为具有20或更少碳原子的取代或未取代的芳基,并且至少一个芳基被卤素取代,或至少R2,R4至R8中的一个为卤原子。
6.本发明的第六个方面是涉及根据上面段落1-5任一段的光学记录介质,其中该记录层进一步包括至少一种另外的由式(2)代表的二吡咯金属螯合物
Figure C9812465500071
其中R11-R17各自独立地为氢原子、卤原子、硝基、氰基、羟基、氨基、羧基、磺酸基,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、烷硫基、芳氧基、芳硫基、链烯基、酰基、烷氧羰基、氨基甲酰基、酰基氨基、芳烷基、芳基或杂芳基,及R15和R16可相互结合形成可具有至少一个取代基的芳环;和M’为过渡元素。
7.本发明的第七个方面是涉及根据上面段落6的光学记录介质,其中另外的二吡咯甲烷金属螯合物选自式(3)代表的化合物:
其中R19-R25各自独立地为氢原子、卤原子、硝基、氰基、羟基、氨基、羧基、磺酸基,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、烷硫基、芳氧基、芳硫基、链烯基、酰基、烷氧羰基、氨基甲酰基、酰基氨基或芳烷基;R18和R26各自独立地为链烯基或芳基;和M”为铜或钴。
8.本发明的第八个方面是涉及根据上面段落1-7任一段的光学记录介质,其中在520-690nm的激光波长下,记录层的折射率和消光系数分别为1.8或更大及0.04-0.40。
9.本发明的第九个方面是涉及根据上面段落1-7任一段的光学记录介质,其可被在520-690nm的波长范围内选择的激光束记录和再现。
10.式(4)代表的二吡咯甲烷金属螯合物
Figure C9812465500081
其中R27-R35各自独立地为氢原子,卤原子,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧羰基、芳烷基、芳基或杂芳基;和M为过渡元素。
采用至少一种本发明的二吡咯甲烷金属螯合物作为记录层能提供非常引入注目的高密度记录介质,可被具有520-690nm波长的激光束记录和再现的,并且耐久性极佳的一次性书写类型的光学记录介质。
图1为截面结构图,说明通常情况和本发明的光学记录介质的层组成。
现在,详细说明本发明。
在由式(1)代表的二吡咯甲烷金属螯合物中,R1和R9各自独立地为链烯基、芳基或杂芳基,R2-R8各自独立地为氢原子、卤原子,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧羰基、芳烷基、芳基或杂芳基。
由R1和R9代表的芳基的例子包括具有20或更少碳原子的取代和未取代的芳基,如苯基、硝基苯基、氰基苯基、羟基苯基、甲基苯基、乙基苯基、正丁基苯基、叔丁基苯基、环己基苯基、2,4-二甲基苯基、2,4-二异丙基苯基、2,4,6-三甲基苯基、2,6-二甲基-4-叔丁基苯基、氟苯基、氯苯基、溴苯基、碘苯基、2,4-二氟苯基、2,4-二氯苯基、2,4-二溴苯基、2,4-二碘苯基、甲氧基苯基、乙氧基苯基、正丁氧基苯基、异戊氧基苯基、三氟甲基苯基、N,N-二甲基氨基苯基、N,N-二乙基氨基苯基、N,N-二丁基氨基苯基、2-N,N-二乙基氨基-4-异丙基苯基、萘基、硝基萘基、氰基萘基、羟基萘基、甲基萘基、甲氧基萘基、氯萘基、溴萘基和三氟甲基萘基;R1和R9代表的杂芳基的例子包括具有20或更少碳原子的取代和未取代的杂芳基,如吡咯基、噻吩基、呋喃基、噁唑基、异噁唑基、噁二唑基、噻二唑基、咪唑基、苯并噁唑基、苯并噻唑基、苯并咪唑基、苯并呋喃基和吲哚基。
由R1和R9代表的链烯基的例子包括可具有一个取代基的链烯基,其优选实例由-CH=CHR10表示,其中R10为氢原子、卤原子,具有20或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧基羰基、芳烷基,芳基或杂芳基。
R10的典型例子包括氢原子;卤原子,如氟、氯、溴和碘;具有20或更少碳原子的取代或未取代的烷基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、2-甲基丁基、1-甲基丁基、新戊基、1,2-二甲基丙基、1,1-二甲基丙基、环戊基、正己基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、3,3-二甲基丁基、2,3-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、1,2-二甲基丁基、1,1-二甲基丁基、3-乙基丁基、2-乙基丁基、1-乙基丁基、1,2,2-三甲基丁基、1,1,2-三甲基丁基、1-乙基-2-甲基丙基、环己基、正庚基、2-甲基己基、3-甲基己基、4-甲基己基、5-甲基己基、2,4-二甲基戊基、正辛基、2-乙基己基、2,5-二甲基己基、2,5,5-三甲基戊基、2,4-二甲基己基、2,2,4-三甲基戊基、3,5,5-三甲基己基、正壬基、正癸基、4-乙基辛基、4-乙基-4,5-二甲基己基、正十一烷基、正十二烷基、1,3,5,7-四乙基辛基、4-丁基辛基、6,6-二乙基辛基、正十三烷基、6-甲基-4-丁基辛基、正十四烷基、正十五烷基、3,5-二甲基庚基、2,6-二甲基庚基、2,4-二甲基庚基、2,2,5,5-四甲基己基、1-环戊基-2,2-二甲基丙基、1-环己基-2,2-二甲基丙基、氯甲基、二氯甲基、氟甲基、三氟甲基、环氟乙基和九氟丁基;
取代和未取代的具有20或更少碳原子的烷氧基,如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、正戊氧基、异戊氧基、新戊氧基、正己氧基、正十二烷氧基、甲氧基乙氧基、乙氧基乙氧基、3-甲氧基丙氧基和3-(异丙氧基)丙氧基;
取代和未取代的具有20或更少碳原子的链烯基,如乙烯基、丙烯基、1-丁烯基、异丁烯基、1-戊烯基、2-戊烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、2-甲基-2-丁烯基、2,2-二氰基乙烯基、2-氰基-2-甲基羰基乙烯基和2-氰基2-甲基-磺酰乙烯基;
取代和未取代的具有20或更少碳原子的酰基,如甲酰基、乙酰基、乙基羰基、正丙基羰基、异丙基羰基、正丁基羰基、正戊基羰基、异戊基羰基、新戊基羰基、2-甲基丁基羰基和硝基苄基羰基;
取代和未取代的具有20或更少碳原子的烷氧基羰基,如甲氧基羰基、乙氧基羰基、异丙基氧羰基和2,4-二甲基丁基氧羰基;和
取代和未取代的具有20或更少碳原子的芳烷基,如苄基、硝基苄基、氰基苄基、羟基苄基、甲基苄基、二甲基苄基、三甲基苄基、二氯苄基、甲氧基苄基、乙氧基苄基、三氟甲基苄基、萘基甲基、硝基萘基甲基、氰基萘基甲基、羟基萘基甲基、甲基萘基甲基和三氟甲基萘基甲基;
芳基;和上面提到的杂芳基。
R2-R8的典型例子包括氢原子;卤原子,如氟、氯、溴和碘;
和上面提到的烷基、烷氧基、链烯基、酰基、烷氧羰基、芳烷基、芳基和杂芳基。
在由式(2)代表的二吡咯甲烷金属螯合物中,R11-R17各自独立地为氢原子、卤原子、硝基、氰基、羟基、氨基、羰基、磺酸基、或具有20或更少碳原子的取代或未取代的烷基、烷氧基、烷硫基、芳氧基、芳硫基、链烯基、酰基、烷氧基羰基、氨基甲酰基、酰基氨基、芳烷基、芳基或杂芳基。这里R15和R16可互相结合形成可具有一个取代基或多个取代基的芳环。
卤原子、烷基、烷氧基、链烯基、酰基、烷氧基羰基、芳烷基、芳基和杂芳基的例子包括上面提到的那些。
而且,由R11-R17代表的烷硫基的典型例子包括烷硫基,如甲硫基、乙硫基、正丙基硫基、异丙基硫基、正丁基硫基、异丁基硫基、仲丁基硫基、叔丁基硫基、正戊基硫基、异戊基硫基、2-甲基丁基硫基、1-甲基丁基硫基、新戊基硫基、1,2-二甲基丙基硫基和1,1-二甲基丙基硫基;
由R11-R17代表的芳氧基的典型例子包括芳氧基,如苯氧基、2-甲基苯氧基、4-甲基苯氧基、4-叔丁基苯氧基、2-甲氧基苯氧基和4-异一丙基苯氧基;
由R11-R17代表的芳硫基的典型例子包括芳硫基,如苯硫基、4-甲基苯硫基、2-甲氧基苯硫基和4-叔丁基苯硫基;
由R11-R17代表的酰基氨基的典型例子包括酰基氨基,如乙酰基氨基、乙基羰基氨基、丁基羰基氨基、苯基羰基氨基、4-乙基苯基羰基氨基和3-丁基苯基羰基氨基;
和由R11-R17代表的氨基甲酰基的典型例子包括烷基氨基羰基,如甲基氨基羰基、乙基氨基羰基、正丙基氨基羰基、正丁基氨基羰基和正己基氨基羰基,和苯基氨基羰基,如苯基氨基羰基、4-甲基苯基氨基羰基、2-甲氧基苯基氨基羰基和4-正丙基苯基氨基羰基。
在式(3)代表的二吡咯甲烷金属螯合物中,R19-R25各自独立地为氢原子、卤原子、硝基、氰基、羟基、氨基、羰基、磺酸基,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、烷硫基、芳氧基、芳硫基、链烯基、酰基、烷氧基羰基、氨基甲酰基、酰基氨基或芳烷基。R18和R26各自独立地为链烯基或芳基。其典型的例子包括上面提到的基团。
在式(4)代表的二吡咯甲烷金属螯合物中,R27-R35各自独立地为氢原子、卤原子,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧基羰基、芳烷基、芳基或杂芳基。其典型的例子包括上面提到的基团。
对M,M’和M的典型例子没有特别的限定,只要它们是具有与二吡咯甲烷化合物形成螯合物能力的过渡金属,但其实例包括周期表组8、9和10(组VIII),组11(组Ib)、组12(组IIb),组3(组IIIa),组4(组IVa),组5(组Va),组6(组VIa)和组7(组VIIa)的金属。其优选例子包括镍、钴、铁、钌、铑、钯、铜、锇、铱、铂和锌,并且从耐光性角度来看,尤其优选的实例包括铜和钴。
对制备式(1)代表的二吡咯甲烷金属螯合物的方法没有限制,但例如,该化合物可根据描述在澳大利亚化学杂志vol.11,p.1835-45(1965),杂原子化学,vol.1,No.5,p.389(1990),美国专利号4,774,339和5,433,896中的任何方法来制备。通常,该上述二吡咯甲烷金属螯合物可通过下面两步骤反应来制备。
在第一个步骤中,在适宜溶剂中,在存在酸性催化剂,如氢溴酸或氢氯酸时,使式(5)代表的化合物和式(6)代表的化合物,或式(7)代表的化合物和式(8)代表的化合物发生反应,从而获得式(9)代表的二吡咯甲烷化合物,接着,在第二步中,将式(9)的二吡咯甲烷化合物与金属,如镍、钴、铁、钌、铑、钯、铜、锇、铱、铂或锌的乙酸盐或卤化物反应,获得式(1)代表的二吡咯甲烷金属螯合物。式(2)-(4)的每种化合物也可以类似方法通过适当改变取代基来获得:
其中R1和R9如上所定义。
由本发明式(1)-(3)代表的二吡咯甲烷金属螯合物优选的典型例子包括分别具有表1-3所示取代基的化合物。
表1
化合
       R1               R2       R3          R4 R5  R6   R7 R8   R9         M
物号
1-1  
Figure C9812465500141
            H               H    H    H     H    H
Figure C9812465500143
 Cu
1-2  
Figure C9812465500144
            Br              H    H    H     H    H  Cu
1-3  
Figure C9812465500147
            H               H    H    H     H    H  Zn
1-4  
Figure C98124655001410
        H         H             H    H    H     H    H
Figure C98124655001411
 Cu
1-5               H               H    H    H     H    H          Cu
1-6  
Figure C98124655001415
            Cl      
Figure C98124655001416
       H    H    H     H    H
Figure C98124655001417
  Cu
1-7  
Figure C98124655001418
    H         H            H    H    H     H    H
Figure C98124655001419
   Cu
1-8             H         -C(CH3)3  H    H    H     H    H
Figure C98124655001421
  Cu
1-9            H         H            H    H    Br    H    H
Figure C98124655001423
  Cu
1-10 
Figure C98124655001424
          H         H            H    H    H     H    H   Cu
1-11 
Figure C98124655001426
         H         Br           H    H    H     H    H   Cu
1-12 
Figure C98124655001428
          H         H            H    H    Br    H    H
Figure C98124655001429
  Cu
1-13 
Figure C98124655001430
          H         Br           H    H    H     H    H   Cu
1-14 
Figure C98124655001432
         H         -C(CH3)3  H    H    Br    H    H   Cu
1-15 
Figure C98124655001434
             -C2H5  -C(CH3)3  H    H    Br    H    H     Cu
1-16 
Figure C98124655001436
    H         Br           H    H    H     H    H   Cu
表1(续)
化合
          R1       R2          R3         R4   R5  R6 R7 R8     R9         M
物号
1-17
Figure C9812465500151
     H            H            H     H    Br   H    H   Cu
1-18
Figure C9812465500153
      H            H            H     H    Br   H    H   Cu
1-19
Figure C9812465500155
     H            H            H     H    H    Br   H   Cu
1-20      H            H           -CH3  H    Br   H    H  
Figure C9812465500158
Cu
1-21
Figure C9812465500159
        H       
Figure C98124655001510
          H     H    t-Bu H    H  
Figure C98124655001511
        Cu
1-22   H            H     H    H    H    H      Cu
1-23        -C2H5 
Figure C98124655001516
          H     H    H    H    H  
Figure C98124655001517
 Cu
1-24   H            H     H    H    H    H  
Figure C98124655001520
 Cu
1-25
Figure C98124655001521
       -C2H5 
Figure C98124655001522
          H     H    H    H    H      Cu
1-26
Figure C98124655001524
        H                  H     H    Cl   Cl   H   Cu
1-27         H       
Figure C98124655001528
          H     H    Br   H    H   Cu
1-28
Figure C98124655001530
        H                  H     H    -OBu H    H   Cu
1-29
Figure C98124655001533
  H            H     H    Cl   Cl   H  
Figure C98124655001535
Cu
1-30
Figure C98124655001536
        H          H     H    H    H    H           Cu
1-31
Figure C98124655001539
        H          H     H    H    H    H           Co
1-32
Figure C98124655001542
        H         -C(CH3)3     H     H    H    H    H  
Figure C98124655001543
        Cu
表1(续)
化合
         R1          R2                     R3           R4  R5 R6   R7  R8    R9          M
物号
1-33   H                   
Figure C9812465500162
   H    H    H     H    H            Cu
1-34          H                     -C(CH3)3       H    H    H     H    H     Cu
1-35       H                          H    H    H     H    H  
Figure C9812465500168
 Cu
1-36          -(CH2)2CH(CH3)2 
Figure C98124655001610
         H    H    H     H    H        Cu
1-37
Figure C98124655001612
         -(CH2)2CH(CH3)2 
Figure C98124655001613
         H    H    H     H    H     Cu
1-38          H                      -C(CH3)3      H    H    Br    H    H  
Figure C98124655001616
  Cu
1-39
Figure C98124655001617
         H                     
Figure C98124655001618
         H    H    Cl    H    H  
Figure C98124655001619
  Cu
1-40
Figure C98124655001620
         H                      H                H    H    Br    H    H  
Figure C98124655001621
  Cu
1-41          H                    
Figure C98124655001623
          H    H    H     H    H  
Figure C98124655001624
     Cu
1-42       H                    
Figure C98124655001626
          H    H    Br    H    H     Cu
1-43   H                       H    H    Br    H    H  
Figure C98124655001630
  Cu
1-44
Figure C98124655001631
      H                     -C(CH3)3       H    H    H     H    H  
Figure C98124655001632
  Cu
1-45       H                     -C(CH3)3       H    H    Cl    H    H     Cu
1-46
Figure C98124655001635
         H                     -C(CH3)3       H    H    Cl    H    H     Cu
1-47       H                     -C(CH3)3       H    H    Br    H    H     Cu
表1(续)
化合
        R1          R2     R3             R4  R5  R6 R7  R8    R9        M
物号
1-48
Figure C9812465500171
     H      
Figure C9812465500172
       H    H    H    H    H   Cu
1-49
Figure C9812465500174
     H              H    H    Br   H    H   Cu
1-50         H       -CH3             H    H    Br   H    H 
Figure C9812465500178
 Cu
1-51      H       H                 H    H    H    H    H   Cu
1-52         H      
Figure C98124655001712
           H    H    H    Br   H   Cu
1-53
Figure C98124655001714
        H       H                 H    H    Br   H    H 
Figure C98124655001715
Cu
1-54
Figure C98124655001716
  H       H                 H    H    Br   H    H   Cu
1-55      H       H                 H    H    Br   H    H   Cu
1-56
Figure C98124655001720
      H       -CH3             H    H    H    H    H 
Figure C98124655001721
         Co
1-57       H       -CH3             H    H    H    H    H     Co
1-58 H       H                 H    H    H    H    H 
Figure C98124655001725
 Cu
1-59
Figure C98124655001726
      H       -CH3             H    H    H    H    H           Zn
1-60       -C2H5 -CH3             H    H    H    H    H          Co
1-61       -C2H5 -CH3             H    H    H    H    H          Zn
1-62
Figure C98124655001732
 -C2H5 -C2H5           H    H    H    H    H       Fe
1-63      -C2H5 -C2H5           H    H    H    H    H 
Figure C98124655001735
 Cu
表1(续)
化合
           R1             R2        R3         R4 R5     R6    R7   R8        R9           M
物号
1-64 
Figure C9812465500181
      -n-C6H13 -CO2C2H5 H    H       H      H      H          zn
1-65           H           H            H    H       H      H      H         Co
1-66 
Figure C9812465500185
           -C2H5          H    H      -OCH3 -OCH3 H      
Figure C9812465500187
    Ni
1-67 
Figure C9812465500188
            -CH3      -CO2C2H5  H    -OCH3 -OCH3 -OCH3 -OCH3 
Figure C9812465500189
         Fe
1-68 
Figure C98124655001810
         -CH3      -C2H5      H    H       H      Cl     H      
Figure C98124655001811
          Fe
1-69           H           H            H    H       H      H      H      
Figure C98124655001813
          Cu
1-70 
Figure C98124655001814
         H           H            H    H       H      H      H      
Figure C98124655001815
Zn
1-71   -CH=CH2          -CH=CH2  H            H    H       H      H      H      
Figure C98124655001816
   zn
1-72            H          H            H    H       H      H      H                 Zn
1-73 
Figure C98124655001819
    H          H            H    H       H      H      H           Cu
1-74    H          H             H    H       H      H      H           Cu
1-75 
Figure C98124655001823
          -CH3      -CH3        H    H       H      H      H      
Figure C98124655001824
    Cu
1-76           -C2H5   -C2H5      H    H       H      H      H                Cu
表1(续)
化合
         R1        R2    R3       R4  R5 R6  R7  R8     R9       M
物号
1-77
Figure C9812465500191
       H  
Figure C9812465500192
      H    H    Br   H    H  
Figure C9812465500193
 Co
1-78  H  
Figure C9812465500195
H    H    Cl   Cl   H  
Figure C9812465500196
 Co
1-79        Br 
Figure C9812465500198
      H    H    H    H    H  
Figure C9812465500199
 Co
1-80
Figure C98124655001910
       Cl        H    H    H    H    H    Co
1-81
Figure C98124655001913
       H  
Figure C98124655001914
      H    H    Cl   H    H    Co
1-82
Figure C98124655001916
   H      H    H    H    H    H    Co
1-83  H  
Figure C98124655001920
 H    I    I    I    I   Cu
1-84
Figure C98124655001922
 H    H    Br   Br   Br   Br 
Figure C98124655001924
Cu
1-85
Figure C98124655001925
 H  
Figure C98124655001926
 H    Cl   Cl   Cl   Cl 
Figure C98124655001927
Cu
1-88
Figure C98124655001928
       H         H    F    F    F    F  
Figure C98124655001930
 Cu
1-87
Figure C98124655001931
       H  
Figure C98124655001932
      H    Cl   H    H    Cl 
Figure C98124655001933
 Cu
1-88        H         H    F    H    H    F   Cu
1-89  Cl 
Figure C98124655001938
 H    H    H    H    H  
Figure C98124655001939
      Cu
1-90
Figure C98124655001940
       Br 
Figure C98124655001941
      H    H    H    H    H  
Figure C98124655001942
Cu
表1(续)
化合
         R1        R2         R3              R4   R5     R6      R7    R8    R9            M
物号
1-91        H          
Figure C9812465500202
     H     H       Br        H      H             Cu
1-92        H                H     H       Br        H      H             Co
1-93 
Figure C9812465500207
      Cl         
Figure C9812465500208
          H     H     -OC5H11   H      H  
Figure C9812465500209
     Cu
1-94 
Figure C98124655002010
    -C2H5     
Figure C98124655002011
          H     Cl       H         H      Cl        Cu
1-95        Cl         
Figure C98124655002014
          H     H     -C(CH3)3  H      H             Cu
1-96      -COCH3     
Figure C98124655002017
           H     H       Br         H      H  
Figure C98124655002018
Co
1-97     -CO2C2H5 
Figure C98124655002020
           H     H       Cl         H      H  
Figure C98124655002021
    Cu
1-98 
Figure C98124655002022
      Cl        
Figure C98124655002023
           H     H     -OCH3     -OCH3  H  
Figure C98124655002024
      Cu
1-99     -CH=CH2   
Figure C98124655002026
          -CH3  H       Cl         Cl     H            Cu
1-100            H     H       Cl         H      H       Cu
1-101
Figure C98124655002030
  H         
Figure C98124655002031
           H     H       H          H      H        Cu
1-102
Figure C98124655002033
      H         -C(CH3)3         H     H       Br         H      H        Co
1-103
Figure C98124655002035
      H           -CH3            H     H       Br         H      H        Cu
1-104       H         -C(CH3)3         H     H       H          H      H      Cu
1-105 H         -C(CH3)3         H     H       H          H      H             Cu
表1(续)
化合
           R1   R2      R3         R4  R5 R6  R7  R8    R9       M
物号
1-106  H        -C(CH3)3  H    H    H    H    H 
Figure C9812465500212
 Co
1-107   H        -C(CH3)3  H    H    H    H    H 
Figure C9812465500214
  Cu
1-108
Figure C9812465500215
  H        -C(CH3)3  H    H    Br   H    H    Cu
1-109    -C2H5  -C(CH3)3  H    H    Br   Br   H    Cu
1-110
Figure C9812465500219
-C2H5  -C2H5     H    H    H    H    H    Cu
1-111
Figure C98124655002111
-C2H5  -C2H5     H    H    H    H    H 
Figure C98124655002112
  Cu
1-112 H         H           H    H    H    H    H    Cu
1-113     H         H           H    H    H    H    H 
Figure C98124655002116
   Cu
1-114    -OCH3    H           H    H    H    H    H    Cu
1-115
Figure C98124655002119
   Cl        H            H    H    H    H    H   Co
1-116
Figure C98124655002121
   -CH3     -CH3       H    H    H    H    H 
Figure C98124655002122
 Co
1-117
Figure C98124655002123
   H         H    H    H    H    H   Co
1-118
Figure C98124655002126
   -OC2H5 -OC2H5    H    H    H    H    H  Co
表1(续)
化合
         R1        R2        R3      R4 R5  R6     R7   R8    R9        M
物号
1-119    -CH3    H    H    H       H      H    Co
1-120
Figure C9812465500223
    -C4H9       H       H    Br   H       H      H 
Figure C9812465500224
 Cu
1-121
Figure C9812465500225
    H       H    H    H       H      H   Co
1-122       H       -C(CH3)3  H    H    H       H      H   Co
1-123
Figure C9812465500229
   H       
Figure C98124655002210
 H    H    H       H      H 
Figure C98124655002211
  Cu
1-124
Figure C98124655002212
   -C2H5   
Figure C98124655002213
      H    H    H       H      H   Cu
1-125       H       
Figure C98124655002216
     H    H    H       H      H 
Figure C98124655002217
 Co
1-126    H       
Figure C98124655002219
 H    H    H       H      H 
Figure C98124655002220
 Cu
1-127    H       
Figure C98124655002222
 H    H    H       H      H 
Figure C98124655002223
 Cu
1-128      H             H       H    H    H      H      H   Co
1-129    H         H    H  -OCH3 -OCH3  H      Cu
1-130
Figure C98124655002229
 H        H    H    H      H      H 
Figure C98124655002231
 Cu
1-131
Figure C98124655002232
-C2H5 
Figure C98124655002233
   H    H    H      H      H 
Figure C98124655002234
  Cu
表1(续)
化合
           R1      R2             R3      R4  R5   R6    R7    R8      R9         M
物号
1-132 H           
Figure C9812465500232
H    H      H      H      H      
Figure C9812465500233
     Cu
1-133
Figure C9812465500234
H            H    H      H      H      H       -CH3        Co
1-134   H              H    H      H      H      H      
Figure C9812465500238
  Co
1-135   H           
Figure C98124655002310
   H    H      H      H      H             Co
1-136
Figure C98124655002312
  -n-C6H13      H   -OCH3 -OCH3 -OCH3 -OCH3       Cu
1-137
Figure C98124655002315
 -CH=CH2   
Figure C98124655002316
   H    H      H      H      H       Cu
1-138
Figure C98124655002318
    -CO2C2H5 
Figure C98124655002319
    H    H      H      H      H        -C2H5      Co
1-139
Figure C98124655002320
     H            
Figure C98124655002321
     H    H      H      H      H      
Figure C98124655002322
 Cu
1-140  H               H    H      H      H      H      
Figure C98124655002325
 Co
1-141
Figure C98124655002326
    -COCH3            H    H      H      H      H         -C2H5      Cu
1-142
Figure C98124655002328
H            
Figure C98124655002329
  H    H      H      H      H      
Figure C98124655002330
 Cu
表2
化合
       R11             R12      R13          R14              R15         R16       R17         M
物号
2-1   
Figure C9812465500241
H         H             H             H          H            Zn
2-2   
Figure C9812465500243
     H         H                  H              H         H            Zn
2-3   -CH3             -C2H5  -CH3        H                 -CH3         -C2H5  -CH3         Zn
2-4   -CH3             -CH3    -C2H5      
Figure C9812465500245
  -C2H5       -CH3    -CH3         Zn
2-5   -CH3             -C2H5  -CH3        H                 -CH3         -C2H5  -CH3         Co
2-6         H         H                  H              H         H            Zn
2-7   -CH3             -C2H5  -CH3        
Figure C9812465500248
         -CH3         -C2H5  -CH3         Zn
2-8   -CH3             -C2H5  -CH3                  -CH3         -C2H5  -CH3         Co
2-9   -CH3             -C2H5  -CH3        
Figure C98124655002410
         -CH3         -C2H5  -CH3         Ni
2-10  -CH3             -C2H5        H               
Figure C98124655002412
       -C2H5  -CH3         Zn
2-11  -CH3             -C2H5        H               
Figure C98124655002414
       -C2H5  -CH3         Co
2-12  -CH3             -C2H5  
Figure C98124655002415
     H               
Figure C98124655002416
       -C2H5  -CH3         Ni
2-13  CH3              -C2H5        H               
Figure C98124655002418
       -C2H5  -CH3         Cu
2-14  -CH3             -C2H5  -CH3           -CH3         -C2H5  -CH3         Co
2-15  -CO2C2H5       -C2H5  -C2H5         -C2H5      -C2H5  -CO2C2H5  Co
2-16       H         H                  H         Cu
2-17  
Figure C98124655002425
          -C2H5        H                        -C2H5 
Figure C98124655002428
      Cu
表2(续)
化合
        R11     R12     R13     R14  R15     R16     R17                 M
物号
2-18    -CH3    H        -CH3    H    -CH=CH-CH=CH-                 Co
2-19    -CH3    H        -CH3    H    -CH=CH-CH=CH- 
Figure C9812465500252
         Co
2-20    -CH3    H        -CH3    H    -CH=CH-CH=CH-                 Zn
2-21    -CH3    H        -CH3    H    -CH=CH-CH=CH-    Co
2-22    -CH3    -C2H5 -CH3    H    -CH=CH-CH=CH- 
Figure C9812465500255
                Co
2-23    -CH3    -C2H5 -CH3    H    -CH=CH-CH=CH- 
Figure C9812465500256
                Zn
2-24    -CH3    -C2H5 -CH3    H    -CH=CH-CH=CH- 
Figure C9812465500257
          Zn
2-25    -CH3    H        -CH3    H    -CH=CH-CH=CH- 
Figure C9812465500258
  Zn
2-26    -CH3    -C2H5 -CH3    H    -CH=CH-CH=CH- 
Figure C9812465500259
          Ni
2-27    -CH3    -C2H5 -CH3    H    -CH=CH-CH=CH- 
Figure C98124655002510
          Co
2-28    -CH3    -C2H5 -CH3    H    -CH=CH-CH=CH-            Co
2-29    -CH3    -C2H6 -CH3    H    -CH=CH-CH=CH-            Zn
2-30    -CH3    -C2H5 -CH3    H    -CH=CH-CH=CH- 
Figure C98124655002513
Zn
2-31    -CH3    -C2H5 -CH3    H    -CH=CH-CH=CH-  Co
2-32    -CH3    -C2H5 -CH3    H    -CH=CH-CH=CH- 
Figure C98124655002515
       Zn
表2(续)
化合
        R11    R12       R13   R14    R15     R16     R17           M
物号
2-33    H       H          H       H      -CH=CH-CH=CH-   Co
2-34    -CH3   H         -CH3   H      -CH=CH-CH=CH- 
Figure C9812465500262
   Zn
2-35    -CH3   -C2H5   -CH3   H      -CH=CH-CH=CH-  Cl              Zn
2-36    -CH3   Br        -CH3   H      -CH=CH-CH=CH-    Zn
2-37    -CH3   H         -CH3   H      -CH=CH-CH=CH- 
Figure C9812465500264
  Zn
2-38    -CH3   -C2H5   -CH3   H      -CH=CH-CH=CH- 
Figure C9812465500265
  Zn
2-39    -CH3   -C2H5   -CH3   H      -CH=CH-CH=CH- 
Figure C9812465500266
  Co
2-40    -CH3   -C2H5   -CH3   H      -CH=CH-CH=CH-  Zn
2-41    -CH3   -C2H5   -CH3   H      -CH=CH-CH=CH- 
Figure C9812465500268
Co
2-42    -CH3   -C2H5   -CH3   H      -CH=CH-CH=CH-  -SC(CH3)3     Zn
2-43    -CH3   -C2H5   -CH3   H      -CH=CH-CH=CH- 
Figure C9812465500269
 Cu
2-44    -CH3   -C2H5   -C2H5 H      -CH=CH-CH=CH- 
Figure C98124655002610
 Cu
2-45    -CH3   -C2H5   -CH3   H      -CH=CH-CH=CH-   Zn
2-46    -CH3   -C2H5   -CH3   H      -CH=CH-CH=CH-   Co
2-47    -CH3   -C2H5   H      -CH=CH-CH=CH- 
Figure C98124655002614
 Zn
表2(续)
化合
        R11    R12              R13                 R14   R15    R16       R17          M
物号
2-48    -CH3  -C2H5                         H    -CH=CH-CH=CH-    Co
2-49    -CH3  -C2H5          -CH3                 H    -CH=CH-CH=CH- 
Figure C9812465500273
  Ni
2-50    -CH3  H                -CH3                 H    -CH=CH-CH=CH- 
Figure C9812465500274
   Co
2-51    -CH3  -CH3            -OCH3                H    -CH=CH-CH=CH-            Zn
2-52    -CH3  -CH3            -OCH3                H    -CH=CH-CH=CH-            Co
2-53    -CH3  -C2H5          -CH3                 H    -CH=CH-CH=CH- 
Figure C9812465500277
 Zn
2-54    -CH3  -CH3            -O(CH2)2CH(CH3)2 H    -CH=CH-CH=CH-             Co
2-55    -CH3  -C2H5          -C2H5              H    -CH=CH-CH=CH- 
Figure C9812465500279
    Co
2-56    -CH3  -C5H11         -CH3                 H    -CH=CH-CH=CH- 
Figure C98124655002710
 Zn
2-57    H      -OC2H5         -OC2H5              H    -CH=CH-CH=CH- 
Figure C98124655002711
   Co
2-58    -CH3  -C4H9          -OC2H5              H    -CH=CH-CH=CH-     Co
2-59    -CH3  -CH3            -OC2H5              H    -CH=CH-CH=CH- 
Figure C98124655002713
   Co
2-60    -CH3  -C5H11         -CH3                 H    -CH=CH-CH=CH- 
Figure C98124655002714
           Cu
2-61    -CH3  -CH2CH(CH3)2 -CH3                  H    -CH=CH-CH=CH- 
Figure C98124655002715
          Cu
2-62    -CH3  -C2H5         -CH3                  H    -CH=CH-CH=CH- 
Figure C98124655002716
    Co
2-63    -CH3  Br               -CH3                  H    -CH=CH-CH=CH-      Cu
表2(续)
化合
           R11           R11          R13            R14    R15       R16          R17          M
物号
2-64      -CH3           Br           -CH3            H      -CH=CH-CH=CH-          Co
2-65      -CH3       -C(CH3)3       -CH3           H      -CH=CH-CH=CH-       
Figure C9812465500282
         Cu
2-66      -CH3           Br           -CH3            H      -CH=CH-CH=CH-       
Figure C9812465500283
 Ni
2-67      -CH3         -C2H5        -CH3           H      -CH=CH-CH=CH-       
Figure C9812465500284
         Ni
2-68      -CH3    -CH((CH(CH3)2)2  -CH3           H      -CH=CH-CH=CH-       
Figure C9812465500285
        Cu
2-69      -CH3    -CH((CH(CH3)2)2  -CH3           H      -CH=CBr-CH=CH-      
Figure C9812465500286
 Cu
2-70      -CH3      -CH2CH(CH3)2   -CH3           H      -CH=CBr-CH=CH-        Cu
2-71      -CH3         -C2H5        -CH3           H      -CH=CH-CH=CH-          -SC(CH3)3   Cu
2-72      -CH3         -C2H6        -CH3          -CH3   -CH=CH-CH=CH-       
Figure C9812465500288
 Zn
2-73      -CH3         -C2H5        -CH3          -CH3   -CH=CH-CH=CH-         Cu
2-74      -CH3         -C2H5        -CH3           H    -CH=C(t-Bu)-CH=CH-    
Figure C98124655002810
         Co
2-75      -CH3         -C2H5        -CH3           H      -CH=CH-CH=CH-        Co
2-76   
Figure C98124655002812
     -C2H5       -C2H5          H      -CH=CH-CH=CH-               Br       Co
2-77   
Figure C98124655002813
            H      -CH=CH-CH=CH-              -CH3     Co
2-78   
Figure C98124655002814
     -CO2C2H5     -CH3           H      -CH=CH-CH=CH-               Cl       Zn
2-79   
Figure C98124655002815
 -C2H5        -CH3           H      -CH=CH-CH=CH-          -CO2C2H5  Mn
表3
化合
       R18     R19                 R20        R21  R22 R23   R24 R25     R26        M
物号
3-1  H                    H           H     H    NO2   H    H  
Figure C9812465500292
 Cu
3-2
Figure C9812465500293
    -C2H5                  H     H    -SPh    H    H    Cu
3-3
Figure C9812465500296
    -(CH2)2CH(CH3)2     H     H    -SPh    H    H  
Figure C9812465500298
 Cu
下文将描述本发明的具体结构。
如图1所示,本发明的光学记录介质具有层状结构。也就是说,在底物1上形成记录层2,且反射层3紧密排列在其上。在该反射层3上,另一底物与借助一粘附层4进一步粘着在其上。然而,在记录层2下面或其上可形成另一层,或在反射层3上形成另一层。
用作底物的材料应在记录光和再现光波长下基本上为透明的。例如,可使用聚合物材料,如聚碳酸酯树脂、氯乙烯树脂、丙烯酸树脂,聚甲基丙烯酸甲酯、聚苯乙烯树脂或环氧树脂,或无机材料,如玻璃。通过注压等方法将底物材料模压至盘状底物中。如果需要,可在底物表面形成导槽或纹孔。在模压底物时,按需要产生该导槽或纹孔,但它们可通过在底物上使用紫外线硬化树脂层来提供。当被用作DVD时,底物为具有约1.2mm厚度,约80-120mm直径,并且通过其中心形成直径为15mm的孔的盘。
在本发明中,在底物上形成记录层,且本发明的记录层包含至少一种由式(1)代表的二吡咯甲烷金属螯合物。较优选地,它进一步包含至少一种由式(2)代表的二吡咯甲烷金属螯合物,最优选地,它进一步包含至少一种式(3)代表的二吡咯甲烷金属螯合物。尤其是,需要该记录层在520nm-690nm中选择的记录和再现激光波长下,具有适宜的光学常数{光学常数用折射的复合指数来表示(n+ki),其中n和K分别为对应于实部n和虚部K的系数,并且这里,n和K分别被定义为折射率和消光系数}。
通常,有机染料特征在于折射率n和消光系数K很大程度上依赖于波长λ。当折射率n的值小于1.8时,不可能获得信号精确读数所必需的反射度和信号调制振幅,甚至如果消光系数K大于0.40时,反射度失准,这样不仅不能获得良好的可再现信号,而且信号容易再现光而变化。因此,通常的有机染料不是切实可行的。根据上面特性,应选择在所希望的激光波长下具有优选的光学常数的特定的有机染料。当该有机染料被选择并被用来形成记录层时,可获得具有高反射度和良好敏感性的介质。
可用于本发明的由式(I)代表的二吡咯甲烷金属螯合物具有上面优选的光学常数,采用两或多种二吡咯甲烷金属螯合物用于记录层使得容易选择所希望的光学常数。
从实用的观点来看,当采用两或多种二吡咯甲烷金属螯合物时,这些二吡咯甲烷金属螯合物的最大吸收波长之间差异优选为100nm或更少,较优选60nm或更少。对于这些二吡咯甲烷金属螯合物的混合比例没有特别限制。但由于上述原因,优选混合它们,这样光学常数n可为2.0或更大,消光系数K在.0.04-0.20范围内。
通常在520nm-690nm范围中选择的激光光线导致的本发明的光学记录介质的再现可通常在20%的反射度时实现,且30%或更大的反射度是优选的。
在形成记录层之前,如果需要,上面的染料可与骤冷剂,分解促进剂,紫外线吸收剂,粘合剂等混合,或具有这些效果的化合物可作为替代物被加入染料中。
骤冷剂典型的优选例子包括乙酰丙酮、双二硫酚,如双二硫-α-二酮和双苯基二硫酚、硫代儿茶酚、水杨醛肟和硫代双酚盐的金属复合物。此外,胺也是适宜的。
分解促进剂的例子包括金属化合物,如金属抗爆剂,金属茂化合物和乙酰丙酮的金属复合物。
而且,如果需要,粘合剂,均化剂和防沫剂可被一起使用。粘合剂的优选例子包括聚乙烯醇、聚乙烯吡咯烷酮、硝基纤维素、乙酸纤维素、酮树脂、丙烯树脂、聚苯乙烯树脂、聚氨酯树脂、聚乙烯醇缩丁醛、聚碳酸酯和聚烯烃。
在底物上形成记录层之前,为了提高底物的溶剂阻力、反射度和记录敏感性,可在底物上形成包含无机材料或聚合物的一层。
这里,在记录层中的由式(1)-(3)代表的二吡咯甲烷金属螯合物的含量为30%或更高,优选60%或更高。顺便说说,该含量实际上为100%也是优选的。
形成记录层方法的例子包括通过自旋涂布、喷雾、浇铸和浸渍的涂布方法,喷镀方法,化学蒸汽淀积法和真空蒸汽淀积法,但是通过自旋涂布的涂布方法简单,因而是优选的。
在采用如自旋涂布法的涂布方法的情况下,可使用通过将式(1)-(3)代表的二吡咯甲烷金属螯合物溶解或分散在溶剂中,以使在1-40%(重量计)的范围内,优选3-30%(重量计)制备的涂布溶液,但在这种情况下,优选选择不损害底物的溶剂。该溶剂的例子包括醇溶剂,如甲醇、乙醇、异丙醇、八氟戊醇、烯丙醇、甲基溶纤剂、乙基溶纤剂和四氟丙醇,脂族和脂环烃溶剂,如己烷、庚烷、辛烷、癸烷、环己烷、甲基环己烷、乙基环己烷和二甲基环己烷,芳香烃溶剂,如甲苯、二甲苯和苯,卤代烃溶剂,如四氯化碳、氯仿、四氯乙烷和二溴乙烷,醚溶剂,如二乙基醚、二丁基醚、二异丙基醚和二噁烷,酮溶剂,如丙酮和3-羟基-3-甲基-2-丁酮,酯溶剂,如乙酸乙酯和乳酸甲酯和水。可单独使用它们,或以其混合物状态使用。
如所需,用于记录层的染料可被分散在聚合物薄膜中。
当不能选择不损害底物的溶剂时,任何喷镀方法,化学蒸汽淀积法和真空蒸汽淀积法均是有效的。
对记录层的厚度没有特别的限制,但优选在50nm-300nm的范围内。如果记录层的厚度少于50nm,热扩散增加,这样记录不能完成,或在记录信号上发生失真,且信号振幅减小。而且,如果记录层的厚度大于300nm,反射度降低,这样可重现信号特征衰退。
接着,在记录层上形成具有优选50nm-300nm厚度的反射层。用于反射层的材料在重现光波长下具有足够高的反射度。反射层材料的例子包括金属,如Au,Al,Ag,Cu,Ti,Cr,Ni,Pt,Ta,Cr和Pd,它们可被单独使用或以其合金形式使用。尤其是,Au,Al和Ag具有高的反射度,因此它们适宜用作反射层材料。此外,反射层可包含任何金属和准金属,如
Mg,Se,Hf,V,Nb,Ru,W,Mn,Re,Fe,Co,Rh,Ir,Zn,Cd,Ga,In,Si,Ge,Te,Pb,Po,Sn和Bi。而且,包括Au作为主要成分的材料是适宜的,因为该材料使得有可能容易获得具有高反射度的反射层。这里,主要成分指该成分的含量大于50%。也可使用不为上面金属的材料,例如,也可使用通过相间地层压具有低折射率的薄膜和具有高折射率的薄膜而形成的多层膜作为反射层。
形成反射层方法的例子包括喷镀法,离子镀敷法,化学蒸汽淀积法和真空蒸汽淀积法。此外,在底物上或在反射层下,由于反射度,记录特性和粘附性质的改善的缘故,已知的无机或有机中间层或粘附层可被沉积下来。
而且,在反射层上形成一保护层,只要其可以保护反射层免于外力,对保护层材料没有特别的限制。用于保护层的有机材料的例子包括热塑性树脂,热固性树脂,电子束可固化树脂和紫外光可固化树脂。而且,用于保护层的无机材料的例子包括SiO2,Si3N4,MgF2和SnO2。将热塑性树脂或热固性树脂溶解在适宜溶剂中,施用产生的涂布溶液,接着让其干燥形成保护层。可直接运用紫外光可固化树脂,或可将它溶解在适宜溶剂中以制备涂布溶液,接着可施用该涂布溶液,然后用紫外光照射使其固化,从而形成保护层。紫外光可固化树脂的例子包括丙烯酸树脂,如聚氨酯丙烯酸,环氧丙烯酸和聚酯丙烯酸。这些材料可单独使用或以其混合物形成使用,或它们可以单层或多层膜的形式使用。
形成保护层方法的实例包括通过自旋涂布和浇铸的涂布方法,喷镀法,化学蒸汽淀积法,但在为记录层的情况下,尤其是自旋涂布法是优选。
保护层的厚度通常在0.1μm-100μm范围内,但在本发明中,它优选在3μm-30μm范围内,较优选5μm-20μm。
在保护层上,可进一步进行印刷,如标记。
另一方面,保护片或底物可被压制在反射层上,或可使用一种方法,其中将反射层放置成互相面对,然后两个光学记录介质可粘接在一起。
此外,在底物的镜面上,可形成紫外光可固化树脂,无机薄膜等以保护表面和防止灰尘沉积。
对本发明涉及的具有520nm-690nm波长的激光没有特别限制,但该激光的例子包括在宽的可见光范围内,允许波长选择的染料激光,具有633nm波长的氦氖激光,具有约680nm和最近开发的650和635nm波长的高输出半导体激光,和具有532nm波长的谐振转化YAG激光。在本发明中,在为选自这些激光的一种或多种波长时,可实现高密度记录和重现。
接下来将根据一些实施例描述本发明,但本发明的范围绝不应受这些实施例的限制。
实施例1
将0.2g二吡咯甲烷金属螯合物(1-4)溶解在10ml二甲基环己烷中以制备染料溶液。其中所用的底物由聚碳酸酯树脂制成,具有连续的导槽(径迹间距:0.8μm),120mm的直径,0.6mm的厚度,并为圆盘形。
以1500rpm的旋转速度将该底物用染料溶液自旋涂布,然后在70℃下干燥3小时以形成记录层。关于该记录层的光学常数,635nm下的n和K分别为2.3和0.11。
在该记录层上,通过使用由Bulzars Co.,Ltd.制备的喷镀设备(CDI-900)来喷镀Au,从而形成具有100nm厚度的反射层。作为喷镀气体,可使用氩气。关于喷镀条件,喷镀功率为2.5KW,喷镀气体压力为1.0×10-2托。
此外,紫外光可固化粘合剂SD-301(由Dainippon Ink&Chemicals,Inc生产)被自旋涂布在反射层上,在该粘合剂膜上,旋转了一个由聚碳酸酯树脂制成的,具有120mm直径和0.6mm厚度的盘状底物。此后,用紫外光照射以获得粘着的光学记录介质。
在因此获得的光学记录介质上,以3.8m/s的线速度和10mw的激光功率进行记录,这样通过使用由Pulstec Industrial Co.,Ltd.生产的带有半导体激光头的光学盘评价设备(DDU-1000),其中在635nm波长下,透镜的数字孔隙为0.6和由KENWOOD Co.,Ltd生产的EFM编码器,最短的纹孔长度可能为0.40μm。记录后,通过带有650nm和635nm红色半导体激光头(透镜的数字孔隙为0.6)的评价设备重现信号,接着测定反射度,振动和调制振幅。结果,这些值均优良,在650nm重现的情况下,反射度为56%,振动为8.5%,调制振幅为0.63。此外,甚至在用碳弧进行耐光性试验100小时和80℃,85%RH时进行的耐湿热性试验后,没有观察到任何变化。而且,甚至当在0.7mw重现光下,将重现过程重复上百万次时,振动的变化为1%或更小。
实施例2
通过如实施例1相同的方法制备的光学记录介质,除开使用一个由聚碳酸酯树脂制成的,具有连续导槽(径迹间距:0.74μm),120nm直径和0.6mm厚度的盘状底物。
在由此获得的光学记录介质上,用与实施例1相同的方法,通过使用由Pulstec Industrial Co.,Ltd.生产的光学盘评价设备(DDU-1000和KENWOODCo.,Ltd.生产的EFM编码器进行记录。记录后,用带有650nm红色半导体激光头的评价设备重现信号,接着测定反射度,振动和调制振幅。结果,这些值均为优良,在650nm下重现的情况时,反射度为56%,振幅为8.6%,调制振幅为0.62。此外,甚至在用碳弧进行耐光性试验100小时和80℃,85%RH时进行的耐湿热性试验后,没有观察到任何变化。而且,甚至当在0.7mw重现光下,将重现过程重复上百万次时,振动的变化为1%或更小。
实施例3-87
通过如实施例1相同的方法制备光学记录介质,除开使用如表1和2所示的各种二吡咯甲烷金属螯合物,接着进行记录。记录后,通过带有650nm红色半导体激光头的评价设备重现信号,接着测定反射度,振动和调制振幅。结果,这些值均为良好。此外,甚至在用碳弧进行耐光性试验100小时和80℃,85%RH时进行的耐湿热性试验后,没有观察到任何变化。而且甚至当在0.7mw重现光下,将重现过程重复上百万次时,振动的变化为1%或更小。
在上面描述的实施例1-87中,在635nm下记录各个光学记录介质并在650nm下重现的情况下,记录层的光学常数以及反射度,振动和调制振幅一起显示在表4中。
                                            表4
实施例    化合物序号   最大λ(nm)     光学常数(635nm)               在650nm下再现性能
     n      K    反射度(%)   振动(%)   调制振幅
    1     1-4    602     2.30     0.11       56      8.5     0.63
    2     1-4    602     2.30     0.11       56      8.6     0.62
    3     1-27    591     2.27     0.07       50      8.5     0.68
    4     1-77    581     2.28     0.06       53      10.0     0.68
    5     1-29    599     2.29     0.09       46      10.5     0.64
    6     1-78    588     2.26     0.06       55      11.0     0.68
    7     1-2    577     2.24     0.06       58      9.5     0.67
    8     1-79    565     2.26     0.07       56      10.0     0.66
    9     1-6    579     2.10     0.05       57      10.0     0.68
    10     1-80    568     2.29     0.05       56      10.2     0.64
    11     1-39    589     2.26     0.09       52      8.6     0.64
    12     1-81    579     2.27     0.06       56      10.3     0.67
    13     1-48    586     2.30     0.09       51      9.0     0.68
    14     1-82    575     2.27     0.07       58      10.2     0.62
    15     1-83    610     2.28     0.13       45      11.0     0.61
    16     1-84    604     2.29     0.09       48      9.0     0.65
    17     1-85    600     2.26     0.08       48      9.0     0.65
    18     1-86    592     2.26     0.08       50      9.2     0.64
    19     1-87    588     2.26     0.08       55      10.0     0.64
    20     1-88    584     2.10     0.08       50      10.0     0.65
    21     1-89    598     2.29     0.09       52      9.4     0.63
    22     1-90    592     2.26     0.08       47      9.0     0.67
    23     1-91    594     2.27     0.09       48      9.1     0.65
    24     1-92    583     2.30     0.06       52      9.9     0.65
    25     1-93    589     2.26     0.06       50      9.0     0.66
    26     1-94    602     2.29     0.09       51      9.1     0.65
    27     1-95    587     2.26     0.06       52      8.9     0.65
    28     1-96    570     2.26     0.05       55      10.2     0.64
                                   表4(续)
实施例    化合物序号    最大λ(nm)     光学常数(635nm)         在650nm下再现性能
     n      K 反射度(%) 振动(%)   调制振隔
    29     1-97     585     2.27     0.06     53     10.4     0.64
    30     1-98     595     2.26     0.07     48     9.0     0.65
    31     1-99     602     2.29     0.09     48     9.0     0.64
    32     1-100     598     2.28     0.09     50     9.2     0.64
    33     1-42     590     2.26     0.08     53     8.7     0.66
    34     1-49     591     2.27     0.08     53     8.6     0.66
    35     1-43     599     2.29     0.09     52     8.5     0.65
    36     1-41     602     2.27     0.09     47     9.3     0.62
    37     1-101     585     2.26     0.07     55     8.5     0.66
    38     1-38     592     2.27     0.08     49     8.8     0.67
    39     1-34     590     2.26     0.08     53     9.0     0.68
    40     1-32     597     2.30     0.09     48     9.4     0.62
    41     1-102     585     2.26     0.08     55     11.0     0.68
    42     1-40     581     2.10     0.06     58     9.2     0.66
    43     1-103     592     2.26     0.08     50     8.9     0.66
    44     1-104     593     2.26     0.08     57     10.0     0.68
    45     1-105     59     2.25     0.07     56     10.1     0.64
    46     1-8     598     2.24     0.08     52     8.8     0.64
    47     1-106     590     2.26     0.07     56     10.6     0.67
    48     1-14     595     2.29     0.08     51     9.0     0.68
    49     1-107     599     2.26     0.09     50     9.1     0.62
    50     1-108     603     2.24     0.09     48     8.9     0.61
    51     1-109     604     2.27     0.09     49     9.0     0.65
    52     1-110     583     2.22     0.06     48     9.8     0.64
    53     1-111     585     2.29     0.06     50     10.0     0.64
    54     1-112     590     2.23     0.07     55     10.0     0.64
    55     1-113     572     2.26     0.05     52     10.0     0.65
    56     1-114     594     2.27     0.08     50     8.9     0.63
    57     1-115     578     2.10     0.06     55     10.5     0.67
    58     1-116     580     2.15     0.06     52     10.2     0.65
                                  表4(续)
实施例     化合物序号   最大λ(nm)     光学常数(635nm)          在650nm下再现性能
     n      K 反射度(%) 振动(%)   调制振幅
    59     1-117    577     2.26     0.06     52     10.5     0.64
    60     1-118    580     2.22     0.06     54     10.5     0.66
    61     1-119    577     2.26     0.06     51     10.3     0.65
    62     1-120    592     2.30     0.88     52     8.8     0.65
    63     1-121    582     2.26     0.06     55     10.2     0.64
    64     1-122    585     2.29     0.06     53     10.4     0.64
    65     1-45    595     2.26     0.08     55     8.8     0.67
    66     1-46    591     2.28     0.08     56     9.2     0.66
    67     1-47    596     2.26     0.08     53     9.0     0.65
    68     1-123    581     2.30     0.07     56     9.5     0.62
    69     1-124    568     2.20     0.06     59     9.3     0.65
    70     1-125    575     2.40     0.09     60     9.7     0.65
    71     1-126    582     2.20     0.11     55     9.6     0.62
    72     1-127    570     2.20     0.08     58     9.8     0.67
    73     1-128    577     2.30     0.12     56     9.4     0.66
    74     1-129    583     2.30     0.10     57     9.3     0.63
    75     1-130    574     2.40     0.13     61     9.4     0.64
    76     1-131    586     2.30     0.08     55     9.2     0.64
    77     1-132    574     2.50     0.11     56     9.3     0.67
    78     1-133    578     2.20     0.07     56     9.4     0.68
    79     1-134    580     2.30     0.09     58     9.3     0.62
    80     1-135    575     2.30     0.06     59     9.5     0.66
    81     1-136    571     2.40     0.07     56     9.6     0.65
    82     1-137    582     2.40     0.06     57     9.3     0.65
    83     1-138    570     2.50     0.10     55     9.6     0.64
    84     1-139    569     2.30     0.07     58     9.7     0.64
    85     1-140    580     2.40     0.10     57     9.3     0.65
    86     1-141    573     2.40     0.07     59     9.5     0.63
    87     1-142    585     2.30     0.08     60     9.6     0.67
实施例88-106
通过如实施例2相同的方法制备光学记录介质,除开适当混合并使用表1-3所示的二吡咯甲烷螯合物,接着进行记录。记录后,通过带有650nm红色半导体激光头的评价设备重现信号,然后测定反射度,振动和调制振幅。结果,这些值均为优良。此外,甚至在用碳弧进行耐光性试验100小时和80℃,85%RH时进行湿热性试验后,没有观察到任何变化。而且,甚至当在0.7mw重现光下,将重现过程上百万次时,振动的变化为1%或更小。
比较实施例1
通过如实施例1相同的方法制备光学记录介质,除开将0.2g二吡咯甲烷金属螯合物(2-43)溶解在10ml二甲基环己烷中,接着进行自旋涂布。在由此获得的光学记录介质上,以如实施1相同的方法,以3.8m/s线速度和10mw激光功率,通过使用由Pulstec Industrial Co.,Ltd.生产的带有635nm半导体激光头的光学盘评价设备(DDU-1000)和由KENWOOD Co.,Ltd生产的EFM编码器进行记录。记录后,通过带有650nm红色半导体激光头的评价设备来重现信号,然后测定反射度,振动和调制振幅。结果,或650nm下的重现情况时,反射度为61%,振动为20%或更大,调制振幅为0.64。因此振动特性不佳。
比较实施例2
用如实施例1相同的方法制备光学记录介质。除开将0.2g二吡咯甲烷金属螯合物(2-23)溶解在10ml二甲基环己烷中,接着进行自旋涂布。在由此获得的光学记录介质上,用如实施例1相同方法,以3.8m/s线速度和10mw激光功率,通过使用由Pulstec Industrial Co.,Ltd生产的带有635nm半导体激光头的光学盘评价设备(DDU-1000)和由KENWOOD Co.,Ltd生产的EFM编码器进行记录。记录后,通过带有650nm和635nm红色半导体激光头的评价设备重现信号,然后测定反射度,振动和调制振幅。结果,在650nm下的重现情况时,反射度为60%,振动为20%或更大,调制振幅为0.65,在635nm下的重现情况时,反射度为61%,振动为20%或更大,调制振幅为0.66。因此,振动性质不佳。此外,在用碳弧将耐光性试验进行100小时后,信号衰变,这样重现是不可能的。
比较实施例3
用如实施例1相同的方法制备光学记录介质,除开将1g由Nippon KankouShikiso Laboratory Co.,Ltd生产的五甲炔花青染料“NK-2929”[1,3,3,1’,3’,3’-六甲基-2’,2’-(4,5,4’,5’-二苯并)靛二羰花青高氯酸盐溶解在10ml四氟丙醇中,接着进行自旋涂布。在由此获得的光学记录介质上,用如实施例1相同的方式,以3.8m/s线速度和10nw激光功率,通过使用由Pulstec Industrial Co.,Ltd.生产的带有635nm半导体激光头的光学盘评价设备(DDU-1000)和由KENWOOD Co.,Ltd.生产的EFM编码器进行记录。记录后,通过带有650nm红色半导体激光头的评价设备重现信号,然后测定反射度,振动和调制振幅。结果,在650nm下的重现情况时,反射度为9%,振动为20%或更大,调制振幅为0.13。因此,这些值不佳。此外,在用碳弧将耐光性试验进行100小时后,信号衰变,这样重现是不可能的。
在上面描述的实施例88-106和比较实施例1-3中,在635nm下记录各个光学记录介质在650nm下重现的情况时,记录层的光学常数以及反射度,振动和调制振幅均一起显示在表5(实施例)和表6(比较实施例)中。在表5中,各混合比率指二吡咯甲烷金属化合物的浓度相对于二甲基环己烷为20g/l的二吡咯甲烷金属化合物的重量比。
                                                        表5
实施例   化合物1(λmax(nm))   化合物2(λmax(nm))    Dif.ofλmax 混合比      光学常数           在650nm下的再现性能
    n     k   反射度(%)     振动(%) 调制振幅
88     1-1(580)     1-4(602) 22 7∶3 2.20 0.08 52 8.2 0.65
89     1-4(602)     1-27(591) 11 5∶5 2.30 0.10 49 7.8 0.64
90     1-9(614)     1-40(582) 32 3∶7 2.28 0.09 49 7.9 0.62
91     1-9(614)     1-38(581) 33 3∶7 2.29 0.09 50 8.0 0.61
92     1-9(614)     1-27(591) 23 3∶7 2.31 0.11 48 7.8 0.61
93     1-9(614)     1-27(591) 23 5∶5 2.40 0.15 47 7.5 0.61
94     1-11(607)     1-27(591) 16 5∶5 2.26 0.11 49 8.1 0.63
95     2-1(510)     1-56(553) 43 1∶9 2.10 0.06 55 8.7 0.69
96     1-19(6 16)     1-49(589) 27 4∶6 2.29 0.11 48 8.0 0.62
97     2-14(521)     1-8(598) 77 2∶8 2.26 0.09 51 2.8 0.64
98     1-34(590)     1-47(596) 6 5∶5 2.31 0.11 48 8.0 0.61
99     3-1(610)     2-72(561) 49 7∶3 2.08 0.07 55 8.6 0.67
100     1-14(595     2-74(565) 30 7∶3 2.26 0.09 49 7.9 0.62
101     2-43(565)     1-17(625) 60 2∶8 2.25 0.08 52 8.0 0.61
102     1-13(592)     1-55(585) 7 6∶4 2.29 0.12 48 8.1 0.63
103     1-15(604)     2-73(563) 41 8∶2 2.13 0.09 50 8.3 0.65
104     2-5(520)     1-7(607) 87 1∶9 2.15 0.08 51 8.4 0.64
105     1-4(602)     1-38(581) 21 3∶7 2.39 0.13 47 7.6 0.64
106     3-1(610)     1-40(614) 4 6∶4 2.35 0.12 48 7.7 0.63
                                          表6
对比实施例 化合物 λmax(nm)       光学常数             在650nm下的再现性能
  n   k     反射度(%)     振动(%)     调制振幅
    1   2-43   565   2.00   0.04     61     20<     0.64
    2   2-23   580   2.30   0.12     60     20<     0.65
    3   NK2929   -   1.80   1.30     9     20<     0.13
实施例107
二吡咯甲烷金属螯合物的合成(1-4)
将1.35g2-甲酰基-5-[(E)-苯基乙烯-1-基]吡咯和1.9g 1-甲酰基-3-(2,4-二异丙基苯基)异吲哚溶解在100ml乙醇中,接着滴加1.18g 47%氢溴酸,然后在室温下搅拌3小时,在减压浓缩后,用300ml氯仿进行萃取,用水洗涤和分离后,将溶剂蒸馏出以获得3.0g由下面结构式(9-a)代表的化合物
Figure C9812465500411
接着,将1.4g化合物(9-a)溶解在200ml乙醇中,加入0.56g乙酸铜,在回流温度下搅拌2小时。减压浓缩后,过滤收集产生的沉淀,然后用甲醇和水洗涤,获得1.2g由结构式(1-4)代表的化合物:
Figure C9812465500412
根据下面的分析结果证实由此获得的化合物为所需化合物。
元素分析(C66H62N4Cu)
                      C          H         N
计算值(%)             81.32        6.41        5.75
实测值(%)             81.82        6.61        5.69
MS(m/e):975(M+)
由此获得的化合物在589nm,在甲苯溶液中显示最大吸收,具有1.30×105ml/g.cm的Gram吸光系数。
实施例108
二吡咯甲烷金属螯合物的合成(1-58)
将1.74g 2-甲酰-5-[(E)-4-叔丁基苯基乙烯-1-基]吡咯和1.9g 1-甲酰基-3-(2,4-二异丙基苯基)-异吲哚溶解在100ml乙醇中,接着滴加1.18g 47%氢溴酸,随后在室温下搅拌3小时。减压浓缩后,用300ml氯仿进行萃取,用水洗涤和分离后,将溶剂蒸馏出来,获得3.1g由下面结构式(9-b)代表的化合物:
接着,将1.57g化合物(9-b)溶解在200ml乙醇中,加入0.56g乙酸铜,在回流温度下搅拌2小时。减压浓缩后,通过过滤收集产生的沉淀,然后用甲醇和水洗涤,获得1.5g由结构式(1-58)代表的化合物:
Figure C9812465500422
根据下面的分析结果证实由此获得的化合物为所需化合物。
元素分析(C74H78N4Cu)
                    C        H          N
计算值(%)           81.77      7.23         5.15
实测值(%)           81.48      7.46         5.22
MS(m/e):1087(M+)
由此获得的化合物在588nm,在甲苯溶液中显示最大吸收,具有1.15×105ml/g.cm的Gram吸光系数。
实施例109
二吡咯甲烷金属螯合物的合成(1-63)
将1.74g 2-甲酰基-3,4-二乙基5-[(E)-苯基乙烯-1-基]吡咯和1.9g 1-甲酰基-3-(2,4-二异丙基苯基)-异吲哚溶解在100ml乙醇中,然后滴加1.18g 47%氢溴酸,室温搅拌3小时。减压浓缩后,用300ml氯仿进行萃取,用水洗涤并分离后,将溶剂蒸馏出来,获得3.1克由下面结构式(9-C)代表的化合物:
接着,将1.57g化合物(9-C)溶解在200ml乙醇中,加入0.56g乙酸铜,回流温度下搅拌2小时。减压浓缩后,过滤收集产生的沉淀,接着用甲醇和水洗涤,获得1.6克由结构式(1-63)代表的化合物:
Figure C9812465500432
根据下面的分析结果证实由此获得的化合物为所需化合物。
元素分析(C74H78N4Cu)
                     C          H        N
计算值(%)            81.77        7.23       5.15
实测值(%)            81.52        7.52       5.33
MS(m/e):1087(M+)
由此获得的化合物在595nm下,在甲苯溶液中显示最大吸收,具有1.05×105ml/g.cm的Gram吸光系数。
实施例110
二吡咯甲烷金属螯合物的合成(1-65)
将1.4g式(9-a)代表的化合物溶解在100ml乙醇中,接着加入0.76g乙酸钴四水合物,回流温度下搅拌4小时。减压浓缩后,过滤收集产生的沉淀,用甲醇和水洗涤,获得1.3g由结构式(1-65)代表的化合物:
Figure C9812465500441
根据下面的分析结果证实由此获得的化合物为所需化合物。
元素分析(C66H62N4Co)
                    C            H            N
计算值(%)           81.71          6.44           5.77
实测值(%)           81.65          6.51           5.87
MS(m/e):970(M+)
由此获得的化合物在575nm下,在甲苯中显示最大吸收,具有1.50×105ml/g.cm的Gram吸光系数。
实施例111
二吡咯甲烷金属螯合物的合成(1-69)
将1.39g 2-甲酰基-5-(2-噻吩基乙烯-1-基)吡咯和1.32g 1-甲酰基-3-苯基异吲哚溶解在100ml乙醇中,接着滴加1.18g47%氢溴酸,室温下搅拌3小时。减压浓缩后,用300ml氯份进行萃取,用水洗涤和分离后,将溶剂蒸馏出来,获得2.6g由结构式(9-d)代表的化合物:
Figure C9812465500451
接着,将1.2g化合物(9-d)溶解在200ml乙醇中,加入0.56g乙酸酮,回流温度下搅拌2小时。减压浓缩后,过滤收集产生的沉淀,接着用甲醇和水洗涤,获得1.1g由结构式(1-69)代表的化合物:
Figure C9812465500452
根据下面的分析结果证实由此获得的化合物为所需化合物。
元素分析(C50H34N4S2Cu)
               C       H        N       S
计算值(%)      73.37     4.19       6.84      7.83
实测值(%)      73.56     4.33       6.75      8.00
MS(m/e):819(M+)
由此获得的化合物在602nm下,在甲苯中显示最大吸收,具有1.57×105ml/g.cm的Gram吸光系数。
实施例112
二吡咯甲烷金属螯合物的合成(1-72)
将1.2g式(9-d)代表的化合物溶解在200ml乙醇中,加入0.56g乙酸锌,回流温度下搅拌5小时。减压浓缩后,过滤收集产生的沉淀,接着用甲醇和水洗涤,获得1.2g结构式(1-72)代表的化合物:
根据下面的分析结果证实由此获得的化合物为所需化合物。
元素分析(C50H34N4S2Zn)
                 C           H           N         S
计算值(%)        73.21         4.18          6.83        7.82
实测值(%)        73.36         4.22          6.77        7.95
MS(m/e):820(M+)
由此获得的化合物在597nm下,在甲苯溶液中显示最大吸收,具有1.72×105ml/g.cm的Gram吸光系数。

Claims (14)

1.在底物上具有至少一记录层和一反射层的光学记录介质,其中在该记录层中包含至少一种式(I)代表的二吡咯甲烷金属螯合物:
其中R1和R9各自独立地为链烯基、芳基或杂芳基;R2-R8各自独立地为氢原子、卤原子,具有20或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧基羰基、芳烷基、芳基或杂芳基;和M为过渡金属。
2.根据权利要求1的光学记录介质,其中式(1)的R1为-CH=CH-R10,其中R10为氢原子,卤原子,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧基羰基、芳烷基、芳基或杂芳基。
3.根据权利要求1的光学记录介质,其中式(1)的R1为具有20或更少碳原子的取代或未取代的芳基或杂芳基,M为铜或钴。
4.根据权利要求3的光学记录介质,其中式(1)中的R1和R3为具有20或更少碳原子的同时取代或未取代的芳基或杂芳基。
5.根据权利要求4的光学记录介质,其中式(1)中的R1,R3和R9为具有20或更少碳原子的取代或未取代的芳基,并且至少一个芳基被卤素取代,或R2,R4-R8中至少一个为卤原子。
6.根据权利要求1-5任一项的光学记录介质,其中记录层进一步包含至少一种式(2)代表的另外的二吡咯甲烷金属螯合物:
Figure C981246550003C1
其中R11-R14和R17各自独立地为氢原子、卤原子、硝基、氰基、羟基、氨基、羧基、磺酸基,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、烷硫基、芳氧基、芳硫基、链烯基、酰基、烷氧基羰基、氨基甲酰基、酰基氨基、芳烷基、芳基或杂芳基,R15和R16各自独立地为氢原子、卤原子、硝基、氰基、羟基、氨基、羧基、磺酸基,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、烷硫基、芳氧基、芳硫基、链烯基、酰基、烷氧基羰基、氨基甲酰基、酰基氨基、芳烷基、芳基或杂芳基,或者R15和R16相互结合形成取代或未取代的芳环;和M′为过渡金属。
7.根据权利要求6的光学记录介质,其中另外的二吡咯甲烷金属螯合物选自由式(3)代表的化合物:
其中R19-R25各自独立地为氢原子、卤原子、硝基、氰基、羟基、氨基、羧基、磺酸基,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、烷硫基、芳氧基、芳硫基、链烯基、酰基、烷氧基羰基、氨基甲酰基、酰基氨基或芳烷基;R18和R26各自独立地为链烯基或芳基;和M″为铜或钴。
8.根据权利要求1-5任一项的光学记录介质,其中在520-690nm的激光波长下,记录层的折射率和消光系数分别为1.8-2.5以及0.04-0.40。
9.根据权利要求6的光学记录介质,其中在520-690nm的激光波长下,记录层的折射率和消光系数分别为1.8-2.5以及0.04-0.40。
10.根据权利要求7的光学记录介质,其中在520-690nm的激光波长下,记录层的折射率和消光系数分别为1.8-2.5以及0.04-0.40。
11.根据权利要求1-5任一项的光学记录介质,它可被在520-690nm波长范围内选择的激光束记录和重现。
12.根据权利要求6的光学记录介质,它可被在520-690nm波长范围内选择的激光束记录和重现。
13.根据权利要求7的光学记录介质,它可被在520-690nm波长范围内选择的激光束记录和重现。
14.式(4)代表的二吡咯甲烷金属螯合物:
Figure C981246550004C1
其中R27-R35各自独立地为氢原子,卤原子,或具有20或更少碳原子的取代或未取代的烷基、烷氧基、链烯基、酰基、烷氧基羰基、芳烷基、芳基或杂芳基;和M为过渡金属。
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