CN101166794A - 阳离子化合物、色素化合物及其使用方法、以及光信息记录介质 - Google Patents

阳离子化合物、色素化合物及其使用方法、以及光信息记录介质 Download PDF

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CN101166794A
CN101166794A CNA2006800111188A CN200680011118A CN101166794A CN 101166794 A CN101166794 A CN 101166794A CN A2006800111188 A CNA2006800111188 A CN A2006800111188A CN 200680011118 A CN200680011118 A CN 200680011118A CN 101166794 A CN101166794 A CN 101166794A
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general formula
expression
compound
information recording
optical information
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新居一巳
见上龙雄
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Fujifilm Corp
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Fujifilm Corp
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/02Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/04Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00Methine or polymethine dyes, e.g. cyanine dyes
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Abstract

本发明涉及右述通式(I)所示的阳离子化合物。通式(I)中,Ar1和Ar2各自独立地表示可以具有取代基的芳基或者芳香族杂环基,L1表示单键或者二价的连接基,Ar1、Ar2和L1中的至少一个具有一个以上的鎓阳离子;R3和R4各自独立地表示取代基,可以与其所取代的苯环形成环;m3和m4各自独立地表示0-4范围的整数,m3、m4为2-4范围的整数时,存在的多个R3、R4分别可以相同或不同。

Description

阳离子化合物、色素化合物及其使用方法、以及光信息记录介质
技术领域
本发明涉及新的阳离子化合物,利用该阳离子化合物可以提供适合用作光信息记录介质的记录层用色素的色素化合物。进而,本发明涉及含有上述阳离子化合物的色素化合物及其使用方法、以及作为记录层用色素含有上述色素化合物的光信息记录介质。上述色素化合物适合作为用可见激光记录信息的追记型数字通用光盘(DVD-R)等加热模式型信息记录介质的记录层用色素。
背景技术
作为使用激光只能记录一次信息的信息记录介质(光盘),已知有追记型CD(所谓CD-R)。与以往的CD的制作相比,其具有的优点是能够以适当的价格迅速地提供少量的CD,随着个人计算机的普及,对其需求也有所增大。CD-R型的信息记录介质的典型结构是,在透明的圆盘状基板上依次层叠由有机色素构成的记录层、由金等金属构成的反射层以及树脂制的保护层而形成的。在光盘上记录信息,是通过照射近红外区域的激光(通常是780nm左右波长的激光),使记录层局部发热变形来进行的。另一方面,信息的读出(再现)通常是,照射与记录时用的激光相同波长的激光,通过检测记录层中发生发热变形的部位(记录部分)和未变形的部位(未记录部分)的反射率差异来进行的。
近年来,随着个人计算机的高性能化和网络的高速化,如图像信息(特别是动画等)等也可以处理,因此需要更加大容量的信息记录介质。作为记录密度更高的信息记录介质,市售的是为了提高记录密度而用波长短的激光进一步缩小、聚集化的被称为追记型数字通用光盘(所谓的DVD-R)的光盘。该光盘是按照以下所述的步骤制造的,即,在形成有磁道间距比CD-R的1.6μm窄即为0.8μm的预置槽(プレグル-ブ)的、直径120mm或直径80mm的透明圆盘状基板上,设置含有色素的记录层,通常在该记录层上还设置反射层和保护层,将这样形成的两片盘或者一片盘和与该盘尺寸大致相同的圆盘状保护基板,按照该记录层朝内侧的方式用粘结剂粘合在一起,由此完成制造。就DVD-R而言,通过照射可见激光(通常是600~700nm范围波长的激光)就可以进行信息的记录和再现,可以实现比CD-R型的光盘更高密度的记录。另外,市售的还有被称为DVD+R的与DVD-R相似规格的光盘。
与以往的CD-R型相比,追记型DVD-R型信息记录介质可以记录相当于前者数倍的信息量,因而希望其具有高的记录灵敏度,而且由于必须快速地处理大量的信息,因而还希望高速记录中的错误的发生率也比较少。此外,含有色素的记录层对于热或光的经时稳定性通常较低,因而还希望开发出在热或光的作用下也能长时期稳定保持性能的记录层。
另外,与CD-R相同,对于追记型DV 也要求记录时间短,即记录速度高,希望追记型DVD记录介质的感光度更高、改善随着写入激光的高功率化而下降的写入精度(图像跳动性的劣化)。
在特开昭63-209995公报[专利文献1]中,公开了一种在基板上设置有由氧杂菁(オキソノ-ル)色素构成的记录层的CD-R型信息记录介质。通过使用这种色素化合物,可以长期保持稳定的记录和再现性能,该文献中还记载了在分子内以盐的形式导入了铵的氧杂菁色素化合物。另外,在特开平10-109475号公报[专利文献2]中,记载了作为以盐的形式导入铵的联吡啶鎓对提高耐光性是有效的。其中记载了色素并不限于氧杂菁,各种色素都是有效的。另外,在特开平10-297103号公报[专利文献3]中,记载了具有氧化还原平衡盐的氧杂菁色素是有效的。此外,在特开2000-52658公报[专利文献4]、特开2002-249674号公报[专利文献5]中,记载了可以提供显示高的耐光性和耐久性、良好记录性能的光信息记录介质的氧杂菁色素化合物。另外,在特开2002-59652号[专利文献6]中,公开了将两种感光度不同的色素混合的技术,其中有关于氧杂菁色素的记载。在特开2004-188968号[专利文献7]中,公开了一种特定结构的双型氧杂菁色素。
近年来,有人公开了一种可以利用1层介质(4.7GB)的约1.8倍的单面8.5GB容量的具有2层记录面的DVD-R DL(双层)介质,与单层型DVD-R相同,对此也进行了缩短记录时间方面的研究。DVD-R DL介质由于层叠有2层色素层,从感光度、反射率、图像跳动性等观点考虑,对构成各层的色素所要求的物性比在1层型介质中使用的色素还要严格,因此希望开发出更高性能的色素。
另外,作为光信息记录介质的记录层用色素,除了要求上述物性以外,还要求调制色素涂布液时的溶解性、涂布液的溶解时效稳定性、使用高浓度涂布液时的涂布性(涂布膜平滑性)等制造适宜性优异。
发明内容
本发明是在这种情况下提出的,目的是提供新的色素,用该色素可以提供能表现出优良的感光度、图像跳动性和反射率的光信息记录介质,而且该色素具有优良的制造适宜性,特别是作为DVD-R介质用色素可表现出优良特性。
本发明者等为了实现上述目的进行了反复的研究,结果发现利用由在一分子中具有三个以上阳离子部分的新的阳离子化合物和阴离子形成的色素化合物,可获得具有优良的感光度、图像跳动性、反射率的光信息记录介质,还发现上述色素化合物具有出色的调制色素涂布液时的溶解性、涂布液的溶解时效稳定性,同时涂布高浓度涂布溶液时涂布面形状良好,至此完成了本发明。
即,作为实现上述目的的手段的本发明,涉及下述通式(I)表示的阳离子化合物。
Figure S2006800111188D00031
[通式(I)中,Ar1和Ar2各自独立地表示可以具有取代基的芳基或者芳香族杂环基,L1表示单键或者二价的连接基,Ar1、Ar2和L1中的至少一个具有一个以上的鎓阳离子;R3和R4各自独立地表示取代基,可以与其所取代的苯环形成环;m3和m4各自独立地表示0-4范围的整数,m3、m4为2-4范围的整数时,存在的多个R3、R4分别可以相同或不同。]
上述通式(I)中,
Ar1可以用下述结构表示,
Figure S2006800111188D00041
Ar2可以用下述结构表示。
[上述中,R1和R2各自独立地表示取代基,可以与其所取代的苯环形成环;m1和m2的一方表示0-5范围的整数,另一方表示1-5范围的整数,m1、m2为2-5范围的整数时,存在多的个R1、R2分别可以相同或不同。]
另外,上述通式(I)中,R1和R2的至少一方可以表示具有氮阳离子的取代基,L1可以表示单键。上述氮阳离子可以是四取代氮原子阳离子或者含有氮原子的芳香族杂环阳离子,上述含有氮原子的芳香族杂环阳离子可以是吡啶鎓阳离子、咪唑鎓阳离子、噻唑鎓阳离子、_唑鎓阳离子或者亚胺鎓阳离子。
另外,通式(I)中,L1可以用下述结构表示。
Figure S2006800111188D00051
[上述中,R5和R6各自独立地表示取代基;m5和m6各自独立地表示0-4范围的整数,m5、m6为2-4范围的整数时,多个存在的R5、R6分别可以相同或不同;La表示二价的连接基。]
另外,上述通式(I)表示的化合物可以是下述通式(IV)表示的化合物。
Figure S2006800111188D00052
[通式(IV)中,R51和R52各自独立地表示氢原子或者烷基;R53、R54、R55、R56、R57和R58各自独立地表示氢原子、烷基、芳基、或者芳香族杂环基,R55和R56、R57和R58可以通过连接形成五或六元环,R51、R52、R53、R54、R55、R56、R57和R58各自还可以具有取代基。]
本发明的另一种方式涉及含有上述本发明的阳离子化合物和可以中和上述阳离子化合物的电荷的量的阴离子的色素化合物。该色素化合物中,上述阴离子可以是阴离子性色素,上述阴离子性色素可以是氧杂菁色素,上述氧杂菁色素可以用下述通式(V)表示。
Figure S2006800111188D00053
[通式(V)中,Za25和Za26各自独立地表示形成酸性核的原子群;Ma27、Ma28和Ma29各自独立地表示取代或未取代的次甲基;Ka23表示0-3范围的整数,Ka23为2或3时,多个存在的Ma27、Ma28分别可以相同或不同。]
上述氧杂菁色素还可以用下述通式(VI)表示。
Figure S2006800111188D00061
[通式(VI)中,Za21、Za22、Za23和Za24各自独立地表示形成酸性核的原子群;Ma21、Ma22、Ma23、Ma24、Ma25和Ma26各自独立地表示取代或未取代的次甲基;L表示不与两个键形成π共轭体系的二价连接基;Ka21和Ka22各自独立地表示0-3范围的整数,Ka21、Ka22为2或3时,多个存在的Ma21、Ma22、Ma25、Ma26分别可以相同或不同。]
另外,本发明涉及一种光信息记录介质,其中在基板上具有记录层,上述记录层含有上述本发明的色素化合物。该光信息记录介质可以是追记型光信息记录介质或者DVD-R型光信息记录介质。
此外,本发明涉及把上述本发明的色素化合物用作光信息记录介质的记录层用色素的方法。该方法中,上述光信息记录介质可以是追记型光信息记录介质或者DVD-R型光信息记录介质。
根据本发明,可以提供显示出优良的感光度、图像跳动性、反射率的光信息记录介质。此外,本发明的色素化合物在调制色素涂布液时的溶解性和涂布液的溶解时效稳定性优良,即使在涂布高浓度涂布溶液来形成记录层时,也可以形成具有良好的涂布面形状的记录层。
附图说明
图1是具有单层记录层的追记型DVD的截面示意图。
图2是具有双层记录层的追记型DVD的截面示意图。
具体实施方式
[阳离子化合物]
本发明的阳离子化合物是下述通式(I)表示的阳离子化合物。
Figure S2006800111188D00071
本发明的阳离子化合物在一分子中具有三个以上的阳离子部分,可以与阴离子部位一起形成适宜用作光信息记录介质的记录层用色素的色素化合物。下面,对本发明的阳离子化合物进行详细说明。
通式(I)
通式(I)中,Ar1和Ar2各自独立地表示可以具有取代基的芳基或者芳香族杂环基,Ar1和Ar2的至少一个具有一个以上的鎓阳离子。Ar1、Ar2表示的芳基的优选碳原子数为6-30,更优选碳原子数为6-20,特别优选碳原子数为6-12,可列举例如苯基、对甲基苯基、萘基、蒽基等。
Ar1、Ar2表示的芳香族杂环基优选碳原子数为1-30,更优选碳原子数为1-20,特别优选碳原子数为1-12,作为上述芳香族杂环基中含有的杂原子,可列举例如氮原子、氧原子、硫原子。作为上述芳香族杂环基的具体例子,可列举吡咯基、吡唑基、咪唑基、吡啶基、呋喃基、噻吩基、_唑基、噻唑基和它们的苯并稠环体和杂环稠环体等。Ar1、Ar2特别优选为苯基。
当Ar1和Ar2的至少一个具有鎓阳离子时,该鎓阳离子可以含在Ar1、Ar2的取代基中。或者,上述鎓阳离子可以是Ar1、Ar2表示的芳香族杂环基的杂原子进一步被取代而产生的鎓阳离子。作为鎓阳离子,没有特别限制,优选表示铵阳离子、氧鎓阳离子、鏻例子、锍阳离子、硒鎓离子、碘鎓阳离子,特别优选表示铵阳离子。在这里铵阳离子表示在氮原子上具有正电荷的阳离子基,优选表示四取代氮原子阳离子(作为取代基表示以下说明的烷基、芳基、芳香族杂环基)、吡啶鎓阳离子、咪唑鎓阳离子、噻唑鎓阳离子、_唑鎓阳离子、亚胺鎓阳离子。
Ar1、Ar2还可以具有取代基。作为上述取代基,可列举例如烷基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-10,可列举例如甲基、乙基、异丙基、叔丁基、正辛基、正癸基、正十六烷基、环丙基、环戊基、环己基等)、烯基(优选碳原子数2-30,更优选碳原子数2-20,特别优选碳原子数2-10,可列举例如乙烯基、烯丙基、2-丁烯基、3-戊烯基等)、炔基(优选碳原子数2-30,更优选碳原子数2-20,特别优选碳原子数2-10,可列举例如丙炔基、3-戊炔基等)、芳基(优选碳原子数6-30,更优选碳原子数6-20,特别优选碳原子数6-12,可列举例如苯基、对甲基苯基、萘基、蒽基等)、氨基(优选碳原子数0-30,更优选碳原子数0-20,特别优选碳原子数0-10,可列举例如氨基、甲基氨基、二甲基氨基、二乙基氨基、二苄基氨基、二苯基氨基、二甲苯基氨基等)、烷氧基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-10,可列举例如甲氧基、乙氧基、丁氧基、2-乙基己氧基等)、芳氧基(优选碳原子数6-30,更优选碳原子数6-20,特别优选碳原子数6-12,可列举例如苯氧基、1-萘氧基、2-萘氧基等)、芳香族杂环氧基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如吡啶氧基、吡嗪氧基、嘧啶氧基、喹啉氧基等)、酰基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如乙酰基、苯甲酰基、甲酰基、特戊酰基(pivaloyl)等)、烷氧基羰基(优选碳原子数2-30,更优选碳原子数2-20,特别优选碳原子数2-12,可列举例如甲氧基羰基、乙氧基羰基等)、芳氧基羰基(优选碳原子数7-30,更优选碳原子数7-20,特别优选碳原子数7-12,可列举例如苯氧基羰基等)、酰氧基(优选碳原子数2-30,更优选碳原子数2-20,特别优选碳原子数2-10,可列举例如乙酰氧基、苯甲酰氧基等)、酰基氨基(优选碳原子数2-30,更优选碳原子数2-20,特别优选碳原子数2-10,可列举例如乙酰基氨基、苯甲酰基氨基等)、烷氧基羰基氨基(优选碳原子数2-30,更优选碳原子数2-20,特别优选碳原子数2-12,可列举例如甲氧基羰基氨基等)、芳氧基羰基氨基(优选碳原子数7-30,更优选碳原子数7-20,特别优选碳原子数7-12,可列举例如苯氧基羰基氨基等)、磺酰基氨基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如甲磺酰基氨基、苯磺酰基氨基等)、氨磺酰基(优选碳原子数0-30,更优选碳原子数0-20,特别优选碳原子数0-12,可列举例如氨磺酰基、甲基氨磺酰基、二甲基氨磺酰基、苯基氨磺酰基等)、氨基甲酰基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如氨基甲酰基、甲基氨基甲酰基、二乙基氨基甲酰基、苯基氨基甲酰基等)、烷硫基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如甲硫基、乙硫基等)、芳硫基(优选碳原子数6-30,更优选碳原子数6-20,特别优选碳原子数6-12,可列举例如苯硫基等)、芳香族杂环硫基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如吡啶硫基、2-苯并咪唑硫基、2-苯并_唑硫基、2-苯并噻唑硫基等)、磺酰基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如甲磺酰基、甲苯磺酰基等)、亚磺酰基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如甲烷亚磺酰基、苯亚磺酰基等)、脲基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如脲基、甲基脲基、苯基脲基)、磷酰胺基(优选碳原子数1-30,更优选碳原子数1-20,特别优选碳原子数1-12,可列举例如二乙基磷酰胺基、苯基磷酰胺基等)、羟基、巯基、卤原子(可列举例如氟原子、氯原子、溴原子、碘原子)、氰基、磺基、羧基、硝基、羟肟酸基、亚磺基、肼基、亚氨基、芳香族杂环基(优选碳原子数1-30,更优选碳原子数1-12,作为杂原子,可列举例如氮原子、氧原子、硫原子,具体地讲,可列举例如咪唑基、吡啶基、喹啉基、呋喃基、噻吩基、哌啶基、吗啉代基、苯并_唑基、苯并咪唑基、苯并噻唑基、咔唑基、吖庚因基等)、甲硅烷基(优选碳原子数3-40,更优选碳原子数3-30,特别优选碳原子数3-24,可列举例如三甲基甲硅烷基、三苯基甲硅烷基等)等。这些取代基还可以再被取代。
R3、R4各自独立地表示取代基,作为R3、R4表示的取代基的例子,优选列举上述的Ar1、Ar2的取代基,更优选为烷基、芳基、杂环基、氨基、烷氧基、酰基、酰氧基、酰基氨基,特别优选烷基、芳基、烷氧基、酰基。另外,R3、R4表示的取代基彼此也可以结合。即,左右的吡啶环也可以通过R3和R4结合形成的连接基进行结合。另外,R3、R4可以分别与所取代的苯环形成环。
m3、m4各自独立地表示0-4范围的整数。m3、m4分别优选为0-2,更优选为0-1。m3、m4为2-4范围的整数时,多个存在的R3、R4分别可以相同或不同。
L1表示单键或者二价的连接基。作为二价的连接基,优选在两末端具有吡啶鎓基的基团。L1表示的二价的连接基,如同后述的对通式(III)中的连接基的描述。
通式(I)中的阳离子部分的数量优选为3以上1000以下,更优选为3以上10以下,特别优选为4以上6以下。
作为本发明的阳离子化合物的优选方式,可列举通式(I)中,Ar1如下述结构式所示、
且Ar2如下述结构式所示的阳离子化合物,
即下述通式(II)表示的阳离子化合物。
作为更优选的方式,可列举通式(II)中,L1是单键,R1和R2的至少一方表示具有氮阳离子的取代基的阳离子化合物。
另外,作为本发明的阳离子化合物的更优选的方式,可列举通式(II)中的各基团如下所述的结构,即,L1为下述结构,
Figure S2006800111188D00112
R1和R2分别独立地表示取代基,该取代基可分别与所取代的苯环形成环,即可列举下述通式(III)表示的阳离子化合物。
Figure S2006800111188D00113
作为本发明的阳离子化合物的更优选的另一种方式,还可列举下述通式(IV)表示的阳离子化合物。
Figure S2006800111188D00114
下面,对通式(II)、(III)、(IV)按顺序进行说明。
通式(II)
通式(II)中,R1和R2各自独立地表示取代基。作为所述取代基的例子,除了上述R3、R4的取代基说明中记载的取代基以外,还可以列举具有氮阳离子的取代基。在这里,所述的“氮阳离子”指含有一个以上氮原子、而且所含的氮原子中的至少一个具有正电荷的阳离子。
在上述氮阳离子,可以优选列举四取代氮原子阳离子(取代基表示作为Ar1、Ar2的取代基的例子说明的烷基、芳基、芳香族杂环基)、含有氮原子的芳香族杂环阳离子。
作为四取代氮原子阳离子的更优选的方式,可列举下述阳离子。
上述中,Ra、Rb、Rc、Rd和Re各自独立地表示作为Ar1、Ar2的取代基的例子说明的烷基、芳基或者芳香族杂环基。
作为含有氮原子的芳香族杂环阳离子,可列举吡啶鎓阳离子、咪唑鎓阳离子、噻唑鎓阳离子、_唑鎓阳离子或者亚胺鎓阳离子,具体地,可列举下述阳离子。
Figure S2006800111188D00122
上述中,X1表示O、N、S或CR(R表示氢原子或者取代基),优选为N。Rf、Rg和Rh各自独立地表示氢原子或者取代基,Rg和Rh分别可以与含在杂环中的N一起形成环,X1表示CR时,X1和Rf或者Rh可以连接形成环。X2、X3和X4各自独立地表示N或CR’(R’表示氢原子或者取代基),Ri和Rj各自独立地表示氢原子或者取代基,Ri和Rj分别可以与含在杂环中的N一起形成环,X2表示CR’时,X2和Ri可以连接形成环,X4表示CR’时,X4和Rj可以连接形成环。上述取代基是前面作为Ar1、Ar2的取代基的例子说明的烷基、芳基或者芳香族杂环基。
作为上述含有氮原子的芳香族杂环阳离子的具体例子,可列举下述的含有氮原子的芳香族杂环中至少一个氮被取代形成的阳离子,
作为上述具体例中优选的阳离子,可列举在吡啶、1,3-_唑、1,3-噻唑、咪唑或苯并咪唑中至少一个氮被取代形成的阳离子。
当L1是单键时,优选R1、R2中的至少一个表示上述具有氮阳离子的取代基,更优选两个都表示具有氮阳离子的取代基。R1、R2可以分别与所取代的苯环形成环。
m1和m2的一方表示0-5、优选0-2范围的整数,另一方表示1-5、优选1-2范围的整数。m1、m2为2-5范围的整数时,多个存在的R1、R2分别可以相同或不同。
通式(II)中,R3、R4、L1、m3、m4分别与通式(I)中的定义同义,其详细内容如上所述。通式(II)中的阳离子部分的数量与通式(I)相同,优选为3以上1000以下,更优选为3以上10以下,特别优选为4以上6以下。
通式(III)
通式(III)中,R1、R2、R3、R4与通式(I)和(II)中的定义同义,R5和R6各自独立地表示取代基。R5、R6表示的取代基的优选例子等的详细内容如同上述R3、R4的取代基的说明中所记载的内容。通式(III)中,作为R1、R2、R3、R4、R5、R6表示的取代基的特别优选的例子,可列举烷基、芳基、烷氧基、芳氧基、酰基、烷氧基羰基、酰胺基、氨磺酰基、脲基等。
通式(III)中,m5和m6各自独立地表示0-4范围的整数,优选0-2范围的整数,特别优选0。m5、m6为2-4范围的整数时,多个存在的R5、R6分别可以相同或不同。
通式(III)中,m1、m2、m3、m4与通式(I)和(II)中的定义同义。通式(III)中,m1和m2更优选表示0-2范围的整数,m3、m4优选表示0-4范围的整数,更优选表示0-2范围的整数,特别优选0。
通式(III)中,La表示连接基,优选表示由单键、氧原子、硫原子、氮原子、亚甲基、亚苯基、羰基、スルフアニル基、酰胺基及其组合组成的基,特别优选下述连接基。
Figure S2006800111188D00151
通式(III)中的阳离子部分的数量与通式(I)、通式(II)相同,优选为3以上1000以下,更优选为3以上10以下,特别优选为4以上6以下。
通式(IV)
通式(IV)中,  R51和R52各自独立地表示氢原子或者烷基,R53、R54、R55、R56、R57和R58各自独立地表示氢原子、烷基、芳基、或者芳香族杂环基,R55和R56、R57和R58可以通过连接形成五或六元环。作为形成的环,可列举脂肪族环、苯环、芳香族杂环等。R51、R52、R53、R54、R55、R56、R57和R58表示的烷基、芳基、芳香族杂环基可列举上述取代基的例子中示出的基团,还可以再具有取代基。
R51、R52优选为取代或未取代的烷基(例如,甲基、苄基),更优选两者为相同的烷基。优选R53、R54、R55、R56、R57、R58都是氢原子的情况,或者R53、R54是氢原子而且R55和R56、R57和R58通过连接形成苯环的情况。
下面,列举了本发明阳离子化合物的优选的具体例,但是本发明并不限于下述具体例。
(V-1)
Figure S2006800111188D00171
(V-2)
Figure S2006800111188D00172
(V-3)
Figure S2006800111188D00173
(V-4)
Figure S2006800111188D00174
(V-5)
Figure S2006800111188D00175
(V-6)
Figure S2006800111188D00181
(V-8)
Figure S2006800111188D00182
(V-9)
Figure S2006800111188D00183
(V-10)
(V-11)
Figure S2006800111188D00185
Figure S2006800111188D00186
Figure S2006800111188D00191
(V-14)
Figure S2006800111188D00192
(V-15)
Figure S2006800111188D00193
Figure S2006800111188D00194
Figure S2006800111188D00196
Figure S2006800111188D00201
(V-22)
Figure S2006800111188D00203
(V-23)
(V-24)
Figure S2006800111188D00205
(V-25)
Figure S2006800111188D00211
(V-26)
Figure S2006800111188D00212
(V-27)
Figure S2006800111188D00213
(V-28)
(V-29)
Figure S2006800111188D00215
(V-30)
Figure S2006800111188D00216
(V-31)
Figure S2006800111188D00221
(V-33)
(V-34)
Figure S2006800111188D00224
(V-35)
Figure S2006800111188D00225
(V-36)
Figure S2006800111188D00226
(V-37)
Figure S2006800111188D00227
(V-38)
Figure S2006800111188D00231
(V-39)
(V-40)
(V-41)
Figure S2006800111188D00234
(V-42)
Figure S2006800111188D00235
(V-43)
Figure S2006800111188D00236
(V-44)
Figure S2006800111188D00237
(V-45)
Figure S2006800111188D00241
(V-46)
Figure S2006800111188D00242
(V-47)
Figure S2006800111188D00243
(V-48)
Figure S2006800111188D00244
(V-49)
Figure S2006800111188D00245
(V-50)
Figure S2006800111188D00246
(V-51)
Figure S2006800111188D00247
Figure S2006800111188D00251
(V-53)
Figure S2006800111188D00252
(V-54)
Figure S2006800111188D00253
(V-55)
Figure S2006800111188D00254
(V-56)
Figure S2006800111188D00255
(V-57)
Figure S2006800111188D00256
(V-58)
Figure S2006800111188D00257
(V-59)
Figure S2006800111188D00262
(V-61)
(V-62)
Figure S2006800111188D00264
(V-63)
Figure S2006800111188D00265
(V-64)
(V-65)
(V-66)
(V-67)
Figure S2006800111188D00272
(V-68)
(V-69)
Figure S2006800111188D00274
(V-70)
(V-71)
Figure S2006800111188D00276
(V-72)
Figure S2006800111188D00277
本发明的阳离子化合物,如特开2003-128654号公报中所记载,可以通过将在吡啶鎓化合物的氮上取代有二硝基苯或杂芳基形成的化合物用苯胺或杂芳基胺取代来合成。另外,具有三个以上阳离子基的本发明的阳离子化合物可以使用已经具有阳离子基的化合物作为该苯胺或杂芳基胺来合成,或者通过将联吡啶鎓化合物的氮上的芳基或者杂芳基的取代基进行鎓盐化来合成。
另外,得到的化合物也可以用公知的方法进行精制。此外,得到的本发明的阳离子化合物可以用NMR等公知的分析方法确认。
[色素化合物]
本发明的色素化合物含有本发明的阳离子化合物和可以中和上述阳离子化合物的电荷的量的阴离子。上述色素化合物优选为上述阳离子化合物与上述阴离子形成盐而成的化合物。本发明的色素化合物优选色素膜中吸收极大波长为500nm以上、低于720nm,更优选为550nm以上、低于600nm,最优选为565nm以上、低于590nm。
上述阴离子,只要是可以中和本发明的阳离子化合物的电荷而形成盐的阴离子即可,可以是无机阴离子或者有机阴离子中的任何一种,可列举例如卤素离子(Cl-、Br-、I-等)、磺酸根离子(CH3SO3 -、CF3SO3 -、CF3(CF2)7SO3 -、对甲苯磺酸根离子、萘-1,5-二磺酸根离子等)、硫酸离子(CH3SO4 -等)、ClO4 -、BF4 -、SbF6 -、和磷酸离子(PF6 -
Figure S2006800111188D00281
等)、金属配位化合物离子(例如,
Figure S2006800111188D00291
等)、阴离子色素(例如氧杂菁色素、阴离子性离解性基(OH基、NH基、COOH基、SO3H基等)离解形成的阴离子性色素部位(优选偶氮基、甲亚胺色素、茋色素))。上述阴离子优选为阴离子性色素,更优选为氧杂菁色素。所述的氧杂菁色素是下述通式(A)表示的化合物,只要是吸收极大波长为350nm以上、低于720nm的即可,结构没有特别限制。优选的是次甲基数为5-7并且具有链状酸性核或者环状酸性核的色素。
通式(A)
Figure S2006800111188D00292
R:氢或取代基,n:0以上的整数。
通式(A)中,n优选为1-4范围的整数。作为R表示的取代基的例子,可列举作为Ar1、Ar2的取代基的例子说明的基团,更优选碳原子数1-20的烷基(例如,甲基、乙基、异丙基)、卤原子(例如,氯、溴、碘、氟)、碳原子数1-20的烷氧基(例如,甲氧基、乙氧基、异丙氧基)、碳原子数6-26的芳基(例如,苯基、2-萘基)、碳原子数0-20的杂环基(例如,2-吡啶基、3-吡啶基)、碳原子数6-20的芳氧基(例如,苯氧基、1-萘氧基、2-萘氧基)、碳原子数1-20的酰基氨基(例如乙酰基氨基、苯甲酰基氨基)、碳原子数1-20的氨基甲酰基(例如N,N-二甲基氨基甲酰基)、磺基、羟基、羧基、碳原子数1-20的烷硫基(例如甲硫基)、氰基等,多个R彼此可以连接形成环。上述阴离子更优选是下述通式(V)表示的具有环状酸性核的氧杂菁色素,
Figure S2006800111188D00301
特别优选是下述通式(VI)表示的氧杂菁色素。
下面,对通式(V)、(VI)的详细内容按顺序进行说明。
通式(V)
通式(V)中,Za25和Za26分别独立地表示形成酸性核的原子群,其例子记载在James编:The Theory of the Photographic Process,第4版,マクミラン社,1977年,第198页中。具体地说,分别可列举可以被取代的吡唑-5-酮、吡唑烷-3,5-二酮、咪唑啉-5-酮、海因、2或4-海硫因、2-亚氨基噁唑烷-4-酮、2-噁唑啉-5-酮、2-硫噁唑啉-2,4-二酮、异绕丹酸、绕丹酸、噻吩-3-酮、噻吩-3-酮-1,1-二氧化物、3,3-二氧[1,3]氧杂四氢噻吩(オキサチオラン)-5-酮、吲哚满-2-酮、吲哚满-3-酮、2-氧代吲唑鎓、5,7-二氧代-6,7-二氢噻唑并[3,2-a]嘧啶、3,4-二氢异喹啉-4-酮、1,3-二噁烷-4,6-二酮(例如メルドラム酸等)、巴比土酸、2-硫巴比土酸、香豆素-2,4-二酮、吲唑啉-2-酮、吡啶并[1,2-a]嘧啶-1,3-二酮、吡唑并[1,5-b]喹唑啉酮、吡唑并吡啶酮、5或6员的碳环(例如,己烷-1,3-二酮、戊烷-1,3-二酮、茚满-1,3-二酮)等的核,优选的是吡唑-5-酮、吡唑烷-3,5-二酮、巴比土酸、2-硫巴比土酸、1,3-二噁烷-4,6-二酮、或者3,3-二氧[1,3]氧杂四氢噻吩-5-酮、茚满二酮、吡唑啉酮、吡唑啉二酮、苯并噻吩酮二氧化物。Za25、Za26分别最优选为可以取代的1,3-二噁烷-4,6-二酮。
作为取代酸性核的取代基的例子,可列举卤原子、烷基(包括环戊基、二环烷基)、烯基(包括环烯基、二环烯基)、炔基、芳基、杂环基、氰基、羟基、硝基、羧基、烷氧基、芳氧基、甲硅烷氧基、杂环氧基、酰氧基、氨基甲酰氧基、烷氧基羰氧基、芳氧基羰氧基、氨基(包含烷基氨基、芳基氨基)、酰氨基、氨基羰基氨基、烷氧基羰基氨基、芳氧基羰基氨基、氨磺酰基氨基、烷基及芳基磺酰基氨基、巯基、烷硫基、芳硫基、杂环硫基、氨磺酰基、磺基、烷基及芳基亚磺酰基、烷基及芳基磺酰基、酰基、芳氧基羰基、烷氧基羰基、氨基甲酰基、芳基及杂环偶氮基、酰亚胺基、膦基、氧膦基、氧膦基氧基、氧膦基氨基、或者甲硅烷基。其中,还优选碳原子数1-20的取代或未取代的烷基、或者碳原子数6-20的取代或未取代的芳基。
酸性核优选为未取代、或者被碳原子数1-20的取代或未取代的烷基取代的核、或者被碳原子数6-20的取代或未取代的芳基取代的核。
Ma27、Ma28和Ma29各自独立地表示取代或未取代的次甲基。作为取代基,优选列举碳原子数1~20的烷基(例如,甲基、乙基、异丙基)、卤原子(例如,氯、溴、碘、氟)、碳原子数1-20的烷氧基(例如,甲氧基、乙氧基、异丙氧基)、碳原子数6-26的芳基(例如,苯基、2-萘基)、碳原子数0-20的杂环基(例如,2-吡啶基、3-吡啶基)、碳原子数6-20的芳氧基(例如,苯氧基、1-萘氧基、2-萘氧基)、碳原子数1-20的酰基氨基(例如乙酰基氨基、苯甲酰基氨基)、碳原子数1-20的氨基甲酰基(例如N,N-二甲基氨基甲酰基)、磺基、羟基、羧基、碳原子数1-20的烷硫基(例如甲硫基)、氰基等。另外,可以与其它的次甲基结合形成环结构,也可以与Za27-Za29表示的原子群结合形成环结构。
Ma27、Ma28和Ma29各自独立地优选为未取代的次甲基、或者被乙基、甲基、或苯基取代的次甲基中的任何一种。最优选为未取代的次甲基。
通式(V)中,Ka23表示0-3范围的整数。Ka23为2或3时,多个存在的Ma27、Ma28分别可以相同或不同。优选Ka23为2。
本发明的阳离子化合物和通式(V)表示的阴离子性色素部位成盐形成的色素为中性,色素化合物的阳离子数和阴离子数为相同数量,阳离子数和阴离子数分别优选为3-10,特别优选为4-6。
通式(V)中,优选的是Za25和Za26分别独立地为未取代、或者被碳原子数1-20的取代或未取代的烷基取代的、或者碳原子数6-20的取代或未取代的芳基取代的吡唑-5-酮、吡唑烷-3,5-二酮、巴比土酸、2-硫巴比土酸、1,3-二噁烷-4,6-二酮、3,3-二氧[1,3]氧杂四氢噻吩-5-酮,Ma27、Ma28和Ma29各自独立地为未取代的次甲基、或者被乙基、甲基、或苯基取代的次甲基中的任何一种,Ka23为2。特别优选的是Za25和Za26分别独立地为未取代、或者被碳原子数1-20的取代或未取代的烷基取代的、或者被碳原子数6-20的取代或未取代的芳基取代的1,3-二噁烷-4,6-二酮,Ma27、Ma28和Ma29为未取代的次甲基,Ka23为2。
通式(VI)
通式(VI)中,Za21、Za22、Za23和Za24各自独立地表示形成酸性核的原子群。酸性核与通式(V)的Za25、Za26形成的酸性核同义,其具体例子也相同。形成Za21、Za22、Za23和Za24的酸性核优选为吡唑-5-酮、吡唑烷-3,5-二酮、巴比土酸、2-硫巴比土酸、1,3-二噁烷-4,6-二酮、或者3,3-二氧[1,3]氧杂四氢噻吩-5-酮、茚满二酮、吡唑啉酮、吡唑啉二酮、苯并噻吩酮二氧化物。其中,最优选1,3-二噁烷-4,6-二酮。
Ma21、Ma22、Ma23、Ma24、Ma25和Ma26各自独立地表示取代或未取代的次甲基,与通式(V)的Ma27、Ma28和Ma29同义,具体例子、优选的例子也都相同。Ma21、Ma22、Ma23、Ma24、Ma25和Ma26优选为未取代的次甲基。
Ka21和Ka22各自独立地表示0-3范围的整数,与通式(V)的Ka23同义。Ka23为2或3时,多个存在的Ma21、Ma22、Ma25、Ma26分别可以相同或不同。
L是不与两个键形成π共轭体系的二价连接基。关于二价连接基,除了与和它们结合形成的生色团(クロモフォア)间不形成π共轭体系以外,没有特别限制,优选表示由下述基团的一个或者一个以上组合构成的碳原子数0-100、优选1-20的连接基:亚烷基(碳原子数1-20,例如亚甲基、亚乙基、亚丙基、亚丁基、亚戊基)、亚芳基(碳原子数6-26,例如亚苯基、亚萘基)、亚烯基(碳原子数2-20,例如亚乙烯基、亚丙烯基)、亚炔基(碳原子数2-20,例如亚乙炔基、亚丙炔基)、-CO-N(R101)-、-CO-O-、-SO2-N(R102)-、-SO2-O-、-N(R103)-CO-N(R104)-、-SO2-、-SO-、-S-、-O-、-CO-、-N(R105)-、亚杂环基(ヘテリレン)  (碳原子数1-26,例如6-氯-1,3,5-三嗪-2,4-二基、嘧啶-2,4-二基)。上述R101、R102、R103、R104、R105各自独立地表示氢原子、取代或未取代的烷基、和取代或未取代的芳基中的任何一种。另外,L表示的连接基可以在它们结合的生色团间存在一个以上,也可以多个(优选两个)结合形成环。
作为L,分别优选的是两个亚烷基(优选亚乙基)结合形成环的连接基。其中,更优选的是形成五或六元环(优选环己基)的情况。
下面,列举了上述氧杂菁色素的优选的具体例,但是本发明并不限于这些。
Figure S2006800111188D00341
Figure 0000391
Figure S2006800111188D00343
  No.     Ra     Rb     X
  B-23     H     H     H
  B-24     CH3     H     H
  B-25     CH3     H     苯基
  B-26     苯基     H     H
  B-27     苯基     H     苯基
  B-28     苯基     苯基     H
  B-29     C2H5     C2H5     H
  B-30     C2H5     C2H5     CH3
  B-31     C2H5     苯基     H
Figure S2006800111188D00351
  No.     Ra     Rb     X     Y
  B-32     H     H     H     O
  B-33     H     H     CH3     O
  B-34     苯基     H     H     O
  B-35     苯基     H     CH3     O
  B-36     CH3     CH3     CH3     O
  B-37     CH3     CH3     H     O
  B-38     H     H     H     S
  B-38     苯基     H     H     S
  B-40     C2H5     C2H5     H     S
  B-41     C2H5     C2H5     CH5     S
Figure S2006800111188D00352
Figure 0000401
Figure S2006800111188D00361
  No.     Ra     Rb     X
  B-63     COOC2H5     苯基     H
  B-64     CN     苯基     H
  B-65     CONHC4H0(n)     苯基     H
  B-66     CN     苯基     Cl
  B-67     NHCOCH3     苯基     H
  B-68     CH3     苯基     H
  B-69     CH3     CH3     CH3
  B-70     NH2     苯基     H
Figure S2006800111188D00362
 No.     Ra     Rb     Rc     X
 B-71     H     H     H     H
 B-72     H     CH3     H     H
 B-73     H     t-C4H0     H     H
 B-74     NO2     H     H     H
 B-75     NH2     H     H     H
 B-76     H     苯基     H     H
 B-77     H     Cl     Cl     H
 B-78     H     H     H     苯基
 B-79     H     H     H     CH3
 B-80     H     H     H     CONH2
B-90
Figure S2006800111188D00371
B-91
Figure S2006800111188D00372
B-92
Figure S2006800111188D00373
B-93
Figure S2006800111188D00374
B-94
Figure S2006800111188D00375
B-95
B-96
Figure S2006800111188D00377
Figure S2006800111188D00381
    No.     Ra     Rb     n
    B-97     CH3     C2H5     3
    B-98     CH3     苯基     3
    B-99     CH3     苯基     2
    B-100     CH3     CH(CH3)2     2
    B-101     CH3     CH(CH3)2     3
    B-102     CH3     CF3     3
Figure 0000431
Figure S2006800111188D00384
  No.     Ra     n
  B-110     苯基     2
  B-111     苯基     1
  B-112     CH3     2
  B-113     CH3     1
Figure S2006800111188D00391
Figure 0000441
Figure S2006800111188D00393
Figure 0000442
Figure S2006800111188D00401
Figure 0000451
Figure S2006800111188D00403
Figure S2006800111188D00404
B-155
Figure S2006800111188D00411
B-156
Figure S2006800111188D00412
B-157
Figure S2006800111188D00413
B-158
B-159
Figure S2006800111188D00415
B-160
B-161
Figure 0000463
B-162
Figure 0000462
(Ph:表示苯基,以下同。)
Figure 0000464
Figure S2006800111188D00441
Figure S2006800111188D00461
化合物序号     Ra     Rb     Rc
 C-1     CH3     C2H5     H
 C-2     CH3     C4H9-t     H
 C-3     C2H5     C3H7-i     H
 C-4     C2H5     C2H6     H
 C-5     CH3     C3H7-n     H
 C-6     CH3     C3H7-n     CH3
 C-7     CH3     CH2OCH3     H
 C-8     CH3     C3H4CO3CH3     H
 C-9     CH3     C2H4CO2C2H5     H
 C-10     CH3     CH3     H
Figure S2006800111188D00462
Figure S2006800111188D00471
一般的氧杂菁色素可以通过相应的活性亚甲基化合物和次甲基源(用于在次甲基染料中引入次甲基的化合物)的缩合反应合成。关于该种化合物的详细内容可以参考特公昭39-22069号、特公昭43-3504号、特公昭52-38056号、特公昭54-38129号、特公昭55-10059号、特公昭58-35544号、特开昭49-99620号、特开昭52-92716号、特开昭59-16834号、特开昭63-316853号、特开昭64-40827号各公报、和英国专利第1133986号、美国专利第3247127号、美国专利第4042397号、美国专利第4181225号、美国专利第5213956号、美国专利第5260179号各说明书。
双型氧杂菁色素的合成方法公开在欧洲专利EP1424691A2中。
下面,列举了本发明的阳离子化合物和阴离子性色素成盐形成的色素化合物的优选的具体例,但是本发明并不限于这些。
[表1]
    化合物No.D-1D-2D-3D-4D-5D-6D-7D-8D-9D-10D-11D-12D-13D-14D-15D-16D-17D-18D-19D-20D-21D-22D-23D-24D-25D-26   阴离子部分C-5C-5C-5C-5C-1C-2C-3C-4C-5C-6C-7C-8C-9C-10C-11C-12C-13C-14C-15C-16C-17C-18C-19C-20C-5C-9   阳离子部分V-1V-2V-3V-4V-5V-6V-7V-9V-8V-10V-11V-12V-13V-14V-15V-16V-17V-18V-19V-20V-21V-22V-23V-24V-25V-26   化合物No.D-27D-28D-29D-30D-31D-32D-33D-34D-35D-36D-37D-38D-39D-40D-41D-42D-43D-44D-45D-46D-47D-48D-49D-50D-51D-52   阴离子部分C-5C-9C-5C-9B-1B-20B-29B-37B-45B-49B-65B-71B-85B-91B-94B-99B-104B-114B-127B-138B-155B-164B-169B-191B-194B-201  阳离子部分V-27V-28V-29V-30V-1V-2V-1V-3V-4V-3V-3V-6V-1V-3V-4V-8V-9V-12V-15V-18V-21V-24V-25V-27V-28V-30
表2
  化合物No.   阴离子部分   阳离子部分   化合物No.   阴离子部分  阳离子部分
  D-53D-54D-55D-56D-57D-58D-59D-60D-61D-62D-63D-64D-65D-66D-67D-68D-69D-70D-71D-72D-73D-74D-75D-76   C-5C-9C-4C-9C-9C-11C-9C-9C-9C-5C-5C-9C-5C-9C-9C-11C-9C-5C-9C-5C-5C-5C-9C-5   V-31V-32V-33V-34V-35V-36V-37V-38V-39V-40V-41V-42V-43V-44V-45V-46V-47V-48V-49V-50V-51V-52V-53V-54   D-77D-78D-79D-80D-81D-82D-83D-84D-85D-86D-87D-88D-89D-90D-91D-92D-93D-94   C-5C-5C-5C-4C-5C-9C-5C-9C-5C-9C-5C-5C-5C-5C-5C-9C-5C-9  V-55V-56V-57V-58V-59V-60V-61V-62V-63V-64V-65V-66V-67V-68V-69V-70V-71V-72
作为上述阴离子性色素,除了上述氧杂菁色素以外,还可以使用具有离解性基(羟基、氨基等)作为发色团的离解性的偶氮色素、甲亚胺色素、或者次甲基色素或除了发色团以外取代有离解性基的偶氮色素、甲亚胺色素、次甲基色素、醌系色素、二芳基和三芳基甲烷系色素、酞菁系色素、靛蓝色素、稠环系色素、苯乙烯基系色素、螺环吡喃、螺环_嗪衍生物、二芳基乙烯衍生物、squalirium、クロコニゥム衍生物等。作为具体的结构例,可列举大河原信·松冈贤·平岛恒亮·北尾 悌次郎著(讲谈社)的“功能性色素”中记载的色素等。
本发明的色素化合物可以很容易通过将本发明的阳离子化合物的盐(盐酸盐等)进行阴离子交换获得。另外,得到的色素化合物也可以用公知的方法精制。此外,得到的本发明的色素化合物可以用NMR等公知的分析方法加以确认。
本发明的色素化合物由于调制色素涂布液时的溶解性、涂布液的溶解时效稳定性、使用高浓度涂布液时的涂布性(涂布膜平滑性)优异,所以将本发明的色素化合物用作光信息记录介质的记录层用色素时可以改善制造适宜性。
另外,本发明的色素化合物由于记录特性优异,用作光信息记录介质的记录层用色素时,可以获得记录感度和写入精度优异的光信息记录介质。本发明的色素化合物作为记录层用色素的使用方法的详细内容,如后述的有关本发明光信息记录介质的说明中所述。
[光信息记录介质]
本发明的光信息记录介质中,在基板上具有记录层,上述记录层中含有本发明的色素化合物。
上述记录层可以仅含有一种本发明的色素化合物,也可以二种以上组合含有。其含量优选为1-100%,更优选为5-100%,特别优选为10-100%。
上述记录层中的除了本发明的色素化合物以外的成分可以是有机物、无机物的任何一种,作为其具体例,可列举本发明的色素化合物以外的色素。作为并用的色素优选有机色素,具体地讲是偶氮色素、菁色素、氧杂菁色素、亚甲基吡咯色素、酞菁色素,更加具体地讲,是除了本发明的色素化合物以外的氧杂菁色素,进一步具体地讲,是特开平10-297103号公报、特开2000-108520号公报、特开2002-59652号公报、特开2002-249674号公报、特开2003-39831号公报、和特开2004-188968号公报记载的氧杂菁色素。当并用本发明的色素化合物和其它的色素作为记录材料时,从提高记录特性和制造适宜性的观点考虑,优选按照记录层中的所有色素成分中本发明的色素化合物的比例为60-100质量%、其它色素的比例为0-40质量%的比例进行混合。
本发明的光信息记录介质,只要是在记录层中含有本发明的色素化合物的即可,没有特别限制,优选追记型光信息记录介质。当将本发明的光信息记录介质适用于CD-R时,优选为在形成有磁道间距1.4-1.8μm的预置槽的厚1.2±0.2mm的透明圆盘状基板上,按顺序具有含有本发明的色素化合物的记录层、光反射层和保护层的结构。
另外,本发明的光信息记录介质也可以是追记型DVD,作为追记型DVD,有具有单层记录层的和具有双层记录层的,本发明可以是任何一种方式。此外,作为追记型DVD,有DVD-R和DVD+R,本发明可以适用于任何一种方式。
具有单层记录层的追记型DVD,可以采用在一对基板间具有记录层的层结构(例如,按顺序具有基板、记录层和保护基板(伪基板))。除此之外,优选适当形成反射层、保护层等。具有这种层结构的追记型DVD的一个例子如图1所示。
另外,作为具有单层记录层的DVD-R型光信息记录介质的优选方式,可列举以下的光信息记录介质。
一种光信息记录介质,其中,在形成有磁道间距0.6-0.9μm的预置槽的厚0.6±0.1mm的透明圆盘状基板上接合有层叠体和形状与该层叠体的圆盘状基板相同的透明圆盘状保护基板,所述层叠体中设置有含本发明的色素化合物的记录层和光反射层,所述记录层位于内侧,记录介质厚度为1.2±0.2mm。另外,上述DVD-R型光信息记录介质中,还可以在光反射层上进一步设置保护层。
作为在上述单层记录层中使用的本发明的色素化合物,优选为将通式(III)-(IV)表示的阳离子部分与通式(VI)表示的氧杂菁色素组合而形成的化合物。
另一方面,具有双层记录层的追记型DVD,可以采取在对置的一对基板间具有二层以上记录层的层结构(例如按顺序具有第一基板、第一记录层、第二记录层、第二基板)。具有双层记录层的追记型DVD的一个例子如图2所示。
图2示出的追记型DVD具有将具有第一记录层22的第一基板14和具有第二记录层28的第二基板18隔着中间层20进行贴合的结构。另外,在第一记录层22上设置有反射层24,在中间层20和第二记录层28之间设置有阻挡层30,在第二记录层28和第二基板18之间设置有反射层26。另外,由于从第一基板侧照射激光,在第一记录层22上形成的反射层24是半透明的。
图2示出的追记型DVD中,当对第一记录层22进行信息的记录时,沿从第一基板14的顶端14a向第一记录层22的方向照射记录用激光32,使激光32在第一记录层22上结像而形成信息(坑)。此时,信息会被记录在对应于第一预置槽12的槽34的部分。
另一方面,当对第二记录层28记录信息时,沿从第一基板14的顶端14a向第二记录层28的方向照射记录用激光,使激光32在第二记录层28上结像而记录信息(坑)。此时,信息被记录在第二记录层28中对应于第二预置槽16的槽脊36的部分。
另外,中间层20是用于防止在第一记录层22上记录的信息和在第二记录层28上记录的信息之间发生干扰的层,通过介入中间层20,可以由第一记录层22和第二记录层28获得良好的记录再现信号。
在如上所述的可以实施单面二层记录的追记型DVD中,第一记录层和第二记录层由于距离入射光源的距离、需要的热分解特性等不同,各层中使用的记录材料优选考虑响应特性等进行选择。作为在接近激光光源的记录层(图2中的第一记录层22)中使用的色素化合物,可举出优选的色素、上述具有单层记录层的追记型DVD的优选例子中列举的化合物。
另一方面,作为在远离激光光源的记录层(图2中的第二记录层28)中使用的色素化合物,优选的是组合通式(III)表示的阳离子部分和通式(VI)表示的氧杂菁色素形成的化合物。
另外,作为具有双层记录层的DVD-R型光信息记录介质的优选方式,可列举以下的光信息记录介质。
一种光信息记录介质,其中,在形成有磁道间距0.6-0.9μm的预置槽的厚0.6±0.1mm的透明圆盘状基板上接合有两层层叠体,所述层叠体是设置含有本发明的色素化合物的记录层和光反射层而形成的,上述接合中各记录层位于内侧,记录介质的厚度为1.2±0.2mm。
本发明的光信息记录介质例如可以用如下所述的方法制造。基板(也包括保护基板)可以从以往用作信息记录介质基板的各种材料中任意选择。作为基板材料,可以举出例如玻璃;聚碳酸酯,聚甲基丙烯酸甲酯等丙烯酸树脂;聚氯乙烯、氯乙烯共聚物等氯乙烯类树脂;环氧树脂;无定形聚烯烃以及聚酯等,也可以根据需要将这些材料并用。另外,这些材料可以以薄膜状或者具有刚性的基板的形式使用。在上述材料中,从耐湿性、尺寸稳定性和价格等方面考虑优选使用聚碳酸酯。
在设置记录层的一侧的基板表面上,还可以设置底涂层,以改善平面性、提高粘附力以及防止记录层变质。作为底涂层的材料,例如可以举出聚甲基丙烯酸甲酯、丙烯酸-甲基丙烯酸共聚物、苯乙烯-马来酸酐共聚物、聚乙烯醇、N-羟甲基丙烯酰胺、苯乙烯-乙烯基甲苯共聚物、氯磺化聚乙烯、硝酸纤维素、聚氯乙烯、氯化聚烯烃、聚酯、聚酰亚胺、醋酸乙烯酯-氯乙烯共聚物、乙烯-醋酸乙烯酯共聚物、聚乙烯、聚丙烯、聚碳酸酯等高分子物质;以及硅烷偶合剂等表面改性剂。将上述物质溶解或分散于适当的溶剂中,制成涂布液,然后采用旋涂法、浸涂法、挤涂法等涂布方法将该涂布液涂布在基板表面上,即可形成底涂层。
另外,在基板(或底涂层)上,形成有追迹用的沟槽或表示地址信号等信息的凹凸(预置槽)。该预置槽最好是在将聚碳酸酯等树脂材料注射成形或挤出成形时直接在基板上以上述磁道间距形成。另外,预置槽的形成还可以通过设置预置槽层来进行。作为预置槽层的材料,可以使用丙烯酸的单酯、二酯、三酯和四酯中的至少一种单体(或低聚物)与光聚合引发剂的混合物。预置槽层的形成例如也可以按下面所述的方法进行,首先,在精密制作的母模(原模)上涂布由上述丙烯酸酯和聚合引发剂构成的混合液,在该涂布液层上载置基板后,通过介由基板或母模照射紫外线,使涂布层固化,将基板和涂布层粘合固定,然后将基板从母模上剥离即可。
在基板(或底涂层)的形成了预置槽的表面上,设置含有本发明的色素化合物的记录层。记录层中还可以含有用于提高耐光性的各种防退色剂。所述防退色剂的有代表性的例子可以举出:特开平3~224793号中所述的通式(III)、(IV)或(V)表示的金属配位化合物、diimmonum盐、胺鎓盐以及特开平2~300287号和特开平2~300288号中所示的亚硝基化合物、特开平10~151861中所示的TCNQ衍生物等。
记录层的形成可以按下面所述进行,即,将本发明的色素化合物及根据需要使用的淬火剂(quencher)、结合剂等溶解在溶剂中制成涂布液,接着将该涂布液涂布在基板表面上形成涂膜,然后进行干燥。作为用于形成色素记录层的涂布液中的溶剂,可以举出乙酸丁酯、乳酸乙酯、乙酸溶纤剂等酯;甲基乙基酮、环己酮、甲基异丁基酮等酮;二氯甲烷、1,2-二氯乙烷、氯仿等氯化烃;二甲基甲酰胺等酰胺;环己烷等烃;四氢呋喃、乙醚、二噁烷等醚;乙醇、正丙醇、异丙醇、正丁醇、双丙酮醇等醇;2,2,3,3-四氟丙醇等含氟溶剂;乙二醇一甲醚、乙二醇一乙醚、丙二醇一甲醚等二醇醚类等。考虑到所使用的化合物的溶解性,上述溶剂可以单独使用1种或者2种以上组合使用。根据使用目的,还可以在涂布液中添加防氧化剂、紫外线吸收剂、增塑剂、润滑剂等各种添加剂。
作为结合剂的例子,例如可以举出明胶、纤维素衍生物、葡聚糖、松脂、橡胶等天然有机高分子物质;聚乙烯、聚丙烯、聚苯乙烯、聚异丁烯等烃类树脂;聚氯乙烯、聚偏氯乙烯、聚氯乙烯一聚醋酸乙烯共聚物等乙烯基树脂;聚丙烯酸甲酯、聚甲基丙烯酸甲酯等丙烯酸树脂;聚乙烯醇、氯化聚乙烯、环氧树脂、丁醛树脂、橡胶衍生物、苯酚甲醛树脂等热固性树脂的初期缩合物等合成有机高分子。当并用结合剂作为记录层的材料的情况下,相对于色素总量来说,结合剂的用量一般是0.01~50倍量(质量比)范围,优选的是0.1~5倍量(质量比)范围。这样制备的涂布液的色素浓度一般是0.01~10%(质量)范围,优选的是0.1~5%(质量)范围。
作为涂布方法,可以举出喷涂法、旋涂法、浸涂法、辊涂法、刮涂法、刮均辊法、丝网印刷法等。记录层可以是单层的,也可以是多层的。记录层的层厚度一般是20~500nm的范围,优选的是50~300nm的范围。
为了提高再现信息时的反射率,通常在上述记录层上设置反射层。作为反射层材料的光反射性物质,是对于激光的反射率高的物质,作为其例子,可以举出Mg、Se、Y、Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Co、Ni、Ru、Rh、Pd、Ir、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Si、Ge、Te、Pb、Po、Sn、Bi等金属和准金属或者不锈钢。其中优选的是Cr、Ni、Pt、Cu、Ag、Au、Al和不锈钢,特别优选的是Ag。这些物质可以单独使用,或者2种以上组合使用,或者也可以作为合金使用。例如,可以通过蒸镀、溅射或离子镀上述反射性物质,在记录层上形成反射层。反射层的层厚度一般是10~300nm的范围,优选的是50~200nm的范围。
为了以物理和化学方式保护记录层等,在反射层上还可以设置保护层。在基板的未设置记录层的一侧,为了提高耐划伤性和耐湿性的,也可以设置该保护层。作为保护层所使用的材料,例如,可以举出SiO、SiO2、MgF2、SnO2、Si3N4等无机物质、热塑性树脂、热固性树脂、UV固化性树脂等有机物质。保护层,例如可以通过在反射层上和/或基板上层叠通过塑料的挤出加工得到的薄膜的粘接层而形成,或者也可以采用真空蒸镀、溅射、涂布等方法设置。另外,在热塑性树脂、热固性树脂的情况下,还可以通过将它们溶解在适当的溶剂中制成涂布液,然后涂布该涂布液,进行干燥而形成。在UV固化性树脂的情况下,还可以通过将其直接涂布或者溶解于适当的溶剂中制成涂布液后涂布,然后照射紫外线使之固化而形成。根据使用目的,在这些涂布液中还可以添加防静电剂、抗氧化剂、紫外线吸收剂等各种添加剂。保护层的层厚度一般是0.1~100μm的范围。通过以上工序,可以制成在基板上设置了记录层和反射层以及必要时还有保护层的层叠体。如上所述,通过制作2片层叠体,并以使这2片层叠体各自的记录层朝内侧的方式用粘接剂将这些贴合,可以制造具有2个记录层的光信息记录介质。另外,将所得到的层叠体和与该层叠体的基板大致相同尺寸的圆盘状保护基板按照记录层朝内侧的方式用粘接剂贴合,可以制造具有单层记录层的光信息记录介质。
作为上述粘接层的材料,可列举热塑性树脂、热固化性树脂、电子射线固化性树脂、紫外线固化性树脂、压敏胶带等以及SiO2等无机材料等。另外,这些材料可以单独或混合,也可以不是一层而是形成多层膜来使用。这种粘接层可以通过旋涂法、浇注法、溅射法形成。粘接层的厚度优选为5-100μm,更优选为10-70μm。
本发明的光信息记录介质的信息记录方法,例如按下面所述进行。首先,使信息记录介质以一定的线速度或一定的角速度旋转,与此同时由基板一侧照射半导体激光等记录用的激光。经过该光照射,在记录层与反射层的界面上形成空洞(空洞是伴随记录层或反射层的变形或者这两层的变形而形成的),或基板突起变形,或者在记录层中由于变色、缔合状态的变化导致折射率改变,从而进行信息记录。作为记录光,对于CD~R型,使用具有770~790nm范围振荡波长的半导体激光束,对于DVD~R型,使用具有600~700nm(优选的是620~680nm,更优选的是630~660nm)范围振荡波长的半导体激光束。按上面所述记录的信息,可以通过使信息记录介质按与上述相同的恒定线速度旋转,同时由基板一侧照射具有与记录时相同波长的半导体激光并检测其反射光而进行信息再现。
实施例
下面,通过实施例进一步对本发明进行说明。但是,本发明并不限于实施例中所示的方式。
[实施例1]
色素化合物D-1的合成
(1)化合物例V-1的对甲苯磺酸盐的合成
按照以下的反应流程,在异丙醇300ml中加入氯化铵3g和还原铁30g,进行加热回流30分钟。接着,在加热回流下,慢慢地加入4-硝基苯基-1-咪唑25.8g。再加热回流2小时后,通过热时过滤,除去不溶成分。将得到的异丙醇溶液经浓缩干燥形成的物质用硅胶柱色谱法精制,获得中间体A 16.0g。然后,在二甲基甲酰胺20ml中加入中间体A 2.07g和DNPV(1,1’-双(2,4-二硝基苯基)[4,4’]联吡啶鎓二氯化物)3.36g,在90℃下加热搅拌2小时。
反应结束后,放置冷却,放置一夜。滤出析出的晶体,用二甲基甲酰胺洗涤后,进行减压干燥,获得中间体B 3.0g。接着,在中间体B 2.0g中加入对甲苯磺酸甲酯20ml,在120℃下加热搅拌6小时。放置冷却后,加入醋酸乙酯30ml,搅拌30分钟。滤出析出晶体,进行干燥,获得V-1的对甲苯磺酸盐2.75g。
1H-NMR数据
(d6-DMSO):9.99(s,2H),9.74(d,4H),9.10(d,4H),8.46(s,2H),8.28(dd,8H),8.05(s,2H),7.48(d,8H),7.12(d,8H),4.03(s,6H),2.30(s,12H)
(2)色素化合物的合成(成盐)
将上述得到的V-1的对甲苯磺酸盐0.58g加热完全溶解于甲醇30ml,向这样得到的溶液中加入下述色素原料1.24g,在60℃下搅拌30分钟。
接着,放置冷却后,在室温下搅拌2小时,滤出析出晶体,用甲醇洗涤,进行干燥后,获得色素化合物D-1(吸收λmax=561.6nm,ε=6.13×105/2,2,3,3-四氟丙醇(TFP))。
1H-NMR数据
(d6-DMSO):9.94(s,2H),9.78(s,4H),9.15(d,4H),8.44(s,2H),8.25(dd,8H),8.05(s,2H),(7.70~7.47(m,12H),7.20~7.08(m,8H),4.00(s,6H),1.98(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
Figure 0000631
[实施例2]
色素化合物D-2的合成
(1)化合物例V-2的Br-、Cl-的混合盐的合成
按照以下的反应流程,使中间体B和苄溴反应,合成化合物例V-2的Br-、Cl-的混合盐。
1H-NMR数据
(d6-DMSO):10.32(s,2H),9.80(d,4H),9.17(d,4H),8.53(s,2H),8.32(dd,8H),8.15(s,2H),7.60(d,4H),7.50~7.42(m,6H),5.60(s,4H)
(2)色素化合物的合成(成盐)
与实施例1相同,使其与下述色素原料反应,获得色素化合物D-2(吸收λmax=561.7nm,ε=6.08×105/TFP)。
1H-NMR数据
(d6-DMSO):10.16(s,2H),9.78(d,4H),9.13(d,4H),8.50(s,2H),8.27(dd,8H),8.12(s,2H),(7.70~7.41(m,22H),7.20~7.09(m,8H),5.55(s,4H),1.98(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
Figure 0000641
[实施例3]
色素化合物D-3的合成
(1)化合物例V-3的对甲苯磺酸盐的合成
按照以下的反应流程合成。首先,在_(mesitylene)50ml中加入苯并咪唑3.23g和碳酸铷17.3g、醋酸钯56mg、三叔丁基膦,在将这些100℃下进行搅拌形成的溶液中慢慢地加入1-碘-4-硝基苯6.23g。加热回流8小时后,放置冷却,加入醋酸乙酯、水,用醋酸乙酯进行萃取。将萃取液浓缩后,用柱色谱法精制,获得中间体C 2.4g。接着,进行与实施例1相同的操作,合成中间体D、中间体E,使其与对甲苯磺酸甲酯反应,合成化合物例V-3的对甲苯磺酸盐。
1H-NMR数据
(d6-DMSO):10.30(s,2H),9.81(d,4H),9.17(d,4H),8.39(d,4H),8.29(d,4H),8.22(d,2H),7.92~7.78(m,8H),7.49(d,2H),7.45(d,8H),7.10(d,8H),4.25(s,6H),2.28(s,12H)
(2)色素化合物的合成(成盐)
与实施例1相同,使其与下述色素原料反应,获得色素化合物D-3(吸收λmax=562.0nm,ε=5.76×105/TFP)。
1H-NMR数据
(d6-DMSO):10.30(s,2H),9.83(d,4H),9.19(d,4H),8.38(d,4H),8.28(d,4H),8.21(d,2H),7.91~7.80(m,6H),7.70~7.45(m,12H),7.20~7.08(m,8H),4.25(s,6H),1.98(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
Figure 0000661
[实施例4]
色素化合物D-4的合成
(1)化合物例V-4的Br-、Cl-的混合盐的合成
按照以下的反应流程,使中间体E和苄溴反应,合成化合物例V-4的Br-、Cl-的混合盐。
1H-NMR数据
(d6-DMSO):10.68(s,2H),9.88(d,4H),9.23(d,4H),8.40(dd,4H),8.13~8.10(m,2H),7.95~7.91(m,2H),7.83~7.77(m,4H),7.71(d,4H),7.50~7.40(m,6H),5.96(s,4H)
(2)色素化合物的合成(成盐)
与实施例1相同,使其与下述色素原料反应,获得色素化合物D-4(吸收λmax=562.0nm,ε=6.05×105/TFP)。
1H-NMR数据
(d6-DMSO):10.53(s,2H),9.84(d,4H),9.19(d,4H),8.38(dd,4H),8.12~8.09(m,2H),7.93~7.90(m,2H),7.80~7.77(m,4H),7.70~7.40(m,22H),7.20~7.08(m,8H),5.93(s,4H),1.98(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
Figure 0000671
[实施例5]
色素化合物D-53的合成
(1)化合物例V-31的盐酸盐的合成
按照以下的流程合成。
(i)中间体F的合成
将4,4’-联吡啶15g溶解于丙酮100ml,向这样得到的溶液中加入1-氯-2,4-二硝基苯13.2g,在室温下搅拌15分钟,再加热回流15小时。反应结束后,放置冷却至室温,将析出的晶体减压过滤而滤出。最后得到的晶体用丙酮洗涤,然后干燥,获得中间体F18.8g。
(ii)中间体G的合成
将中间体F14.4g悬浮于乙腈100ml,向这样得到的溶液中加入苯胺4.6g,加热回流7小时。反应结束后,放置冷却至室温,将析出的晶体滤出,用乙腈进行洗涤,干燥。向得到的粗晶体中加入甲醇20ml并加热使其完全溶解,向这样得到的溶液中加入醋酸乙酯200ml,在室温下搅拌1小时。将得到的晶体滤出,获得中间体G10.4g。
(iii)中间体H的合成
在中间体G 3g和1-氯-2,4-二硝基苯7g中加入N-甲基吡咯烷酮5ml,在外部温度110℃的油浴中加热9小时。反应结束后,放置冷却至室温,将析出的晶体滤出,用N-甲基吡咯烷酮进行洗涤(挂洗),再用醋酸乙酯进行洗涤(挂洗)并干燥,获得中间体H 3.7g。
(iv)化合物例V-31盐酸盐的合成
将中间体H 2.4g悬浮于二甲基甲酰胺30ml,向这样得到的溶液中加入4,4’-二氨基二苯醚0.4g,在100℃下加热搅拌6小时。反应结束后,放置冷却至室温,将析出的晶体滤出,用二甲基甲酰胺进行洗涤(挂洗),再用醋酸乙酯进行洗涤并干燥,获得化合物例V-31盐酸盐1.16g。
Figure S2006800111188D00641
化合物例V-31盐酸盐的1H-NMR数据
                            (CD3OD):9.62~9.56(m,8H),8.97~8.83(m,8H),8.10~8.06(m,4H),7.97~7.94(m,4H),7.83~7.80(m,6H),7.57~7.53(m,4H)
(2)色素化合物D-53的合成(成盐)
将上述得到的V-31的盐酸盐1.0g加热完全溶解于甲醇30ml,向这样得到的溶液中加入实施例1记载的色素原料3.1g,在60℃下搅拌30分钟。接着,放置冷却后,在室温下搅拌2小时,滤出析出晶体,用甲醇洗涤、进行干燥,获得1.8g化合物D-53(吸收λmax=561.8nm,ε=6.07×105/2,2,3,3-四氟丙醇(TFP))。
化合物D-53的1H-NMR数据
                   (d6-DMSO):9.70(s(br),8H),9.08(s(br),8H),8.08(s(br),4H),7.98(s(br),4H),7.81(s(br),6H),(7.70~7.46(m,16H),7.20~7.08(m,8H),1.99(s,16H),1.80~1.75(m,8H),1.52(s,12H),1.47~1.32(m,8H),0.88(t,12H)
[实施例6]
色素化合物的合成
用与上述相同的方法由化合物例V-27合成V-30、由化合物例V-32合成V-72的盐酸盐,对得到的盐酸盐的氯阴离子进行阴离子交换,可以合成具有各种阴离子的化合物。如上述实施例中所记载,使其与色素原料反应,可合成作为平衡阴离子具有氧杂菁色素的化合物。下面,对几个化合物,记载了鉴定NMR数据。
化合物例V-41盐酸盐的1H-NMR数据(CD3OD):9.58~9.55(m,8H),8.94~8.91(m,8H),7.96~7.94(m,4H),7.83~7.78(m,8H),7.73~7.70(m,4H),7.52(t,1H),7.47(d,2H),7.06~7.02(m,3H)
色素化合物D-63の1H-NMR数据(d6-DMSO):9.70(s(br),8H),9.07(s(br),8H),7.95(s(br),4H),7.80(s(br),8H),(7.70~7.45(m,19H),7.20~7.07(m,8H),7.02~6.98(m,3H),1.98(s,16H),1.81~1.75(m,8H),1.5(s,12H),1.47~1.33(m,8H),0.88(t,12H)
化合物例V-51盐酸盐の1H-NMR数据(CD3OD):9.64(dd,8H),8.98(dd,8H),8.53(d,2H),8.38(d,2H),8.18(d,2H),8.07(d,4H),7.97(t,2H),7.77(d,4H),7.57(d,4H),7.40(t,4H),7.20(t,2H)
色素化合物D-73の1H-NMR数据(d6-DMSO):10.53(s,2H),9.77(d(br),8H),9.12(s(br),8H),8.51(s(br),2H),8.39(s(br),2H),8.09(m(br),6H),7.80(d,4H),7.70~7.47(m,18H),7.42(t,4H),7.20~7.09(m,8H),1.98(s,16H),1.80~1.76(m,8H),1.52(s,12H),1.43~1.35(m,8H),0.89(t,12H)
化合物例V-54盐酸盐の1H-MR数据(CD3OD):9.68~9.55(m,8H),9.00~8.92(m,8H),8.42(d,2H),8.28(d,2H),8.17(d,2H),8.00(d,2H),7.71(t,2H),7.54(s,2H),7.48(d,2H),7.38(d,2H),3.97(s,6H)
色素化合物D-76の1H-NMR数据(d6-DMSO):10.98(s,1H),9.73(s(br),8H),9.09(s(br),8H),8.41(s(br),2H),8.20(s(br),4H),8.02(s(br),2H),7.71~7.47(m,18H),7.39(s(br),2H),7.20~7.09(m,8H),3.93(s,6H),1.99(s,16H),1.82~1.77(m,8H),1.53(s,12H),1.47~1.35(m,8H),0.89(t,12H)
化合物例V-57盐酸盐の1H-NMR数据(CD3OD):9.68~9.57(m,8H),9.00~8.92(m,8H),8.42(d,2H),8.29(d,2H),8.17(d,2H),8.02~7.93(m,6H),7.83~7.80(m,6H)
色素化合物D-79の1H-NMR数据(d6-DMSO):10.98(s,1H),9.72(s(br),8H),9.10(s(br),8H),8.41(s(br),2H),8.20(s(br),4H),7.99(s(br),6H),7.82(s(br),6H),7.71~7.47(m,12H),7.21~7.08(m,8H),1.99(s,16H),1.82~1.77(m,8H),1.53(s,12H),1.47~1.35(m,8H),0.89(t,12H)
评价方法
(1)旋涂涂布适宜性的评价
使表3记载的色素(0.3g)溶解于10ml的2,2,3,3-四氟丙醇(TFP),将这样得到的溶液旋涂在聚碳酸酯基板上,用肉眼观察涂布条纹。结果示于表3中。
(2)溶解时效稳定性试验
把表3记载的色素的5.0质量%的2,2,3,3-四氟丙醇溶液,在20℃下放置一周。用肉眼确认晶体析出的情况。结果示于表3中。
◎:完全没有观察到晶体析出。
○:没有观察到晶体析出。
△:稍微观察到一点晶体析出。
×:大量晶体析出。
(3)色素膜折射率测量
将色素溶液(表3示出的各色素10mg/1ml TFP)涂布在玻璃基板上,用椭圆计测量其折射率。结果示于表3中。
表3
色素化合物 涂布条纹 溶解时效变化稳定性 折射率(660nm)
D-1 没有看到 2.38
D-2 没有看到 2.36
D-3 没有看到 2.37
D-4 没有看到 2.33
D-53 没有看到 2.30
D-63 没有看到 2.30
D-73 没有看到 2.27
D-76 没有看到 2.31
D-79 没有看到 2.30
比较化合物A 稍微有点 2.24
比较化合物B 2.15
比较化合物C 稍微有点 × 2.29
由表3的结果可知,本发明的色素化合物不易形成涂布条纹,溶解时效稳定性优异。另外,具有高的折射率。该趋势在使用本发明的其它色素化合物也同样能观察到。
光信息记录介质的制作
采用注塑成形,将聚碳酸酯树脂成形为具有螺旋状凹槽(深130nm、宽310nm、磁道间距0.74μm)的厚度0.6mm、直径为120mm的基板。将比较化合物A 1.25g溶解于2,2,3,3-四氟丙醇100ml中,制成涂布液,采用旋涂法将该涂布液涂布在上述基板的形成凹槽的表面上,形成了色素层。
接着,在各色素涂布面上溅射银,形成膜厚度约150nm的反射层,然后作为粘接剂使用紫外线固化树脂(ダイキュァクリァS D 640,大日本油墨化学工业制造)与0.6mm厚度的伪基板贴合,制成DVD-R光盘。
光信息记录介质的评价
使用DDU 1000和多信号发生器(パルステック公司制造,激光波长=660nm、开口率0.60),在转送速度1倍速(11.08Mbps)、8倍速(88.64M)、10倍速(110.8Mbps)下记录8~16调制信号。
所使用的记录方案(strategy)示于表4中。1倍速记录、10倍速记录是用一种条件、8倍速记录是用脉冲幅度大不相同的两种条件进行记录的。
记录功率在各自的介质中,设定为跳动最小的记录功率。然后,使用与记录激光波长相同波长的激光进行再现,测量感光度和跳动。结果示于表5中。可以设定良好的记录策略。
[表4]
记录策略
Figure 0000731
Figure 0000732
表5
           实施例
记录速度 1X  8X  8X  10X
记录策略 A  B  C  D
最适合记录功率(mW) 10  26  32  32
反射率(%) 51.2  52.1  51.8  51.7
跳动(%) 6.7  6.8  6.9  6.9
14T调制度 0.52  0.71  0.77  0.78
PI误差 23  18  11  16
AR(%) 50  35  28  26
下面,与表4、表5相同地设定比较化合物A中12x的记录策略,接着,除了使用表6中示出的各色素代替比较化合物A以外,与上述相同地制作DVD-R光盘。使用这些光盘,在12x下进行记录再现试验。结果示于表6中。
[表6]
 色素化合物  感光度(mW)  跳动(%)
 D-1  32  6.0
 D-2  34  5.9
 D-3  33  6.2
 D-4  35  6.1
 D-53  30  5.8
 D-63  33  6.1
 D-73  33  5.9
 D-76  32  6.0
 D-79  31  5.8
比较化合物A  37  7.2
比较化合物B  42  7.5
比较化合物C  50  8.5
如表6中所示,把实施例中合成的色素化合物用作记录层用色素的DVD-R光盘的感光度和跳动优异。另外,如表3所示,也显示出了高的反射率。该反射率是在DL介质中属于可以实现充分的记录特性的水平。另外,如表3所示,实施例中合成的色素化合物具有优异的制造适宜性。
工业上的可利用性
本发明的光信息记录介质适合用作DVD-R型光信息记录介质。

Claims (19)

1.下述通式(I)所示的阳离子化合物,
Figure S2006800111188C00011
通式(I)中,Ar1和Ar2各自独立地表示可以具有取代基的芳基或者芳香族杂环基,L1表示单键或者二价的连接基,Ar1、Ar2和L1中的至少一个具有一个以上的鎓阳离子;R3和R4各自独立地表示取代基,也可以与所取代的苯环形成环;m3和m4各自独立地表示0-4范围的整数,m3、m4为2-4范围的整数时,存在的多个R3、R4分别可以相同或不同。
2.根据权利要求1所述的阳离子化合物,其中,所述通式(I)中,
Ar1如下式所示,
Figure S2006800111188C00012
Ar2如下式所示,
Figure S2006800111188C00013
上式中,R1和R2各自独立地表示取代基,也可以与所取代的苯环形成环;m1和m2的一方表示0-5范围的整数,另一方表示1-5范围的整数,m1、m2为2-5范围的整数时,存在的多个R1、R2分别可以相同或不同。
3.根据权利要求2所述的阳离子化合物,其中,所述通式(I)中,R1和R2中的至少一方表示具有氮阳离子的取代基。
4.根据权利要求3所述的阳离子化合物,其中,所述通式(I)中,L1是单键。
5.根据权利要求3或4所述的阳离子化合物,其中,所述氮阳离子是四取代氮原子阳离子或者含有氮原子的芳香族杂环阳离子。
6.根据权利要求5所述的阳离子化合物,其中,所述含有氮原子的芳香族杂环阳离子是吡啶鎓阳离子、咪唑鎓阳离子、噻唑鎓阳离子、_唑鎓阳离子或者亚胺鎓阳离子。
7.根据权利要求1或2所述的阳离子化合物,其中,通式(I)中,L1如下式所示,
Figure S2006800111188C00021
上式中,R5和R6各自独立地表示取代基;m5和m6各自独立地表示0-4范围的整数,m5、m6为2-4范围的整数时,存在的多个R5、R6分别可以相同或不同;La表示二价的连接基。
8.根据权利要求1所述的阳离子化合物,其中,所述通式(I)表示的化合物是下述通式(IV)表示的化合物,
Figure S2006800111188C00022
通式(VI)中,R51和R52各自独立地表示氢原子或者烷基;R53、R54、R55、R56、R57和R58各自独立地表示氢原子、烷基、芳基、或者芳香族杂环基,R55和R56、R57和R58可以通过连接形成五或六元环,R51、R52、R53、R54、R55、R56、R57和R58各自还可以具有取代基。
9.一种色素化合物,其中含有权利要求1-8中任何一项记载的阳离子化合物和可以中和所述阳离子化合物的电荷的量的阴离子。
10.根据权利要求9所述的色素化合物,其中所述阴离子是阴离子性色素。
11.根据权利要求10所述的色素化合物,其中,所述阴离子性色素是氧杂菁色素。
12.根据权利要求11所述的色素化合物,其中,所述氧杂菁色素如下述通式(V)所示,
Figure S2006800111188C00031
通式(V)中,Za25和Za26各自独立地表示形成酸性核的原子群;Ma27、Ma28和Ma29各自独立地表示取代或未取代的次甲基;Ka23表示0-3范围的整数,Ka23为2或3时,存在的多个Ma27、Ma28分别可以相同或不同。
13.根据权利要求11所述的色素化合物,其中,所述氧杂菁色素如下述通式(VI)所示,
Figure S2006800111188C00032
通式(V)中,Za21、Za22、Za23和Za24各自独立地表示形成酸性核的原子群;Ma21、Ma22、Ma23、Ma24、Ma25和Ma26各自独立地表示取代或未取代的次甲基;L表示不与两个键形成π共轭体系的二价连接基;Ka21和Ka22各自独立地表示0-3范围的整数,Ka21、Ka22为2或3时,存在的多个Ma21、Ma22、Ma25、Ma26分别可以相同或不同。
14.一种光信息记录介质,其中在基板上具有记录层,所述记录层含有权利要求9-13中任何一项记载的色素化合物。
15.根据权利要求14所述的光信息记录介质,其是追记型光信息记录介质。
16.根据权利要求15所述的光信息记录介质,其是DVD-R型光信息记录介质。
17.一种方法,其中把权利要求9-13中任何一项记载的色素化合物用作光信息记录介质的记录层用色素。
18.根据权利要求17所述的方法,所述光信息记录介质是追记型光信息记录介质。
19.根据权利要求18所述的方法,所述光信息记录介质是DVD-R型光信息记录介质。
CNA2006800111188A 2005-11-11 2006-11-09 阳离子化合物、色素化合物及其使用方法、以及光信息记录介质 Pending CN101166794A (zh)

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