CN1213420C - 光记录媒体 - Google Patents

光记录媒体 Download PDF

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CN1213420C
CN1213420C CNB031076920A CN03107692A CN1213420C CN 1213420 C CN1213420 C CN 1213420C CN B031076920 A CNB031076920 A CN B031076920A CN 03107692 A CN03107692 A CN 03107692A CN 1213420 C CN1213420 C CN 1213420C
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dyestuff
wavelength
recording layer
optical recording
recording media
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CN1447324A (zh
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洞井高志
有冈博之
福泽成敏
塚本修司
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TDK Corp
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Abstract

本发明提供不仅维持高耐光性或良好的反射率且可用10m/s以上的高速线速度进行记录的光记录媒体。光记录媒体(10)的基材(21)上设含有薄膜状态下的极大吸收波长450nm以上、620nm以下的第1染料为主成分的记录层(22)，记录层(22)含记录波长下的消光系数0.5以上的第2染料。此时，第2染料的薄膜状态下的极大吸收波长优选是620nm以上、750nm以下。

Description

光记录媒体
技术领域
本发明涉及记录层使用染料的光记录媒体，尤其是涉及可高速记录的光记录媒体。
背景技术
现在，作为可数字记录的光记录媒体，在进行大容量补记型密盘(DVD-R)的商品化。该DVD-R在光透过性基材上具有记录层、反射层、保护层顺序层合的结构，作为用波长630～680nm的激光可记录与再生的媒体正标准化。该情况下，由于DVD-R是用激光记录信息，故在光透过性基材上形成必需的称为沟槽的导向槽，该导向槽的形状，考虑包括各记录再生特性或伺服信号特性等的综合信号品质而最优化。例如，该导向槽按0.6μm～0.7μm左右的间距形成。另一方面用各种的记录材料形成记录层，例如，用下述通式(I)表示的染料与金属的螯合化合物(含金属偶氮染料)形成记录层。
再者，该通式(I)中，A表示与其结合的碳原子及氮原子一起形成杂环的残基，B表示与其结合的二个碳原子一起形成芳香环或杂环的残基，X表示羟基、羧基、磺酸衍生物基团、或(NSO2Q)-，该Q表示也可用卤原子取代的C1～C6的烷基。
该情况不限于该含金属偶氮染料，DVD-R用的染料(例如含金属偶氮染料或花青染料)如图1的特性W所示，具有薄膜状态下的极大吸收波长是比记录再生用激光波长(630nm以上、680nm以下)短的450nm～620nm、记录再生用激光波长下的消光系数约为0.01～0.03的特性。因此，使用含该金属偶氮染料的前述染料100％构成的记录层由于也具有同样的特性，故在记录再生用激光波长中确保足够的反射率。其中，含金属偶氮染料由于具有高耐光性，故记录层也同样地具有高的耐光性。再者，图1的特性W在450nm～620nm的范围出现2个极大的吸收波长(约540nm和约590nm)，而本申请中，把如此地彼此接近而且两者间的消光系数的降低很小的多个极大吸收波长群作为整体按一个极大吸收波长处理。该情况下，所谓该一个极大吸收波长中的极大吸收波长，是指极大吸收波长群内消光系数最大的吸收波长。因此，图1的特性W，由于消光系数比约590nm波长大，故约540nm的波长成为极大吸收波长。以下同样。
然而，用含有含金属偶氮染料的前述染料100％构成记录层的光记录媒体，有以下应改善之处。即，DVD-R的基本规格中的线速度规定为3.49m/s(1倍速度)，该光记录媒体也可按该线速度记录进行设计。另外，更高速的2倍速度的记录也可由该光记录媒体确认。然而，最近希望DVD-R在10m/s以上的更高速的线速度(例如4倍速度)下的记录，根据发明者的实验证实，使用现状输出功率的记录用激光进行记录时，由于记录层的敏感度不足，故很难按10m/s以上的线速度在该光记录媒体上进行记录。另一方面，也由实验得到证实，通过提高记录用激光的输出功率弥补记录层的敏感度不足、或采用改变记录层的组成而提高敏感度等的方法可用4倍速度记录。然而，由于记录用激光的输出功率有限，故考虑其耐久性等时，作为记录用激光，优选其输出功率是规定的水平以下。因此提高记录用激光的输出功率而弥补记录层敏感度不足的方法是不现实的。另一方面，大大改变记录层组成的方法很难确保用前述DVD-R用的染料构成的记录层的电特性(高耐光性或良好的反射率)，很多情况下往往成为错误率增加或反射率降低等的原因。因此，现状的光记录媒体存在难以维持高耐光性或良好的反射率、同时又用高速的线速度进行记录的问题。
发明内容
本发明的主要目的在于提供维持高耐光性或良好的反射率、同时又可用10m/s以上的高速的线速度进行记录的光记录媒体。
(1)为达到上述目的，本发明的光记录媒体，是在基材上设置含有薄膜状态下的极大吸收波长450nm以上、620nm以下的第1染料为主成分的记录层而构成的光记录媒体，前述记录层含有记录波长下的消光系数0.5以上的第2染料。再者，所谓本发明中的薄膜状态下的极大吸收波长，意味着有机染料膜作为记录层成膜的状态下的极大吸收波长。该情况下，薄膜状态下的极大吸收光谱，与染料溶于溶剂中的溶液状态下的极大吸收光谱行为不同。该薄膜状态下的极大吸收光谱，例如，可如下地进行测定，但不限于此。即，一般来讲，首先，按1～20重量％的浓度把作为对象的染料溶解于有机溶剂中，在没有沟槽或凹陷等的PC(聚碳酸酯)平板上用旋涂器涂成60～200nm左右的膜厚，使之没有特定的取向性，在50℃～70℃干燥进行成膜。有机溶剂优选可使染料溶解、在大气中的沸点是50℃～150℃的溶剂。旋涂时的溶剂挥发时，若染料发生明显结晶化或产生缔合时，选择其他的溶剂。成膜后，使用分光光度计测定带所制染料薄膜的PC平板的透过吸收光谱。消光系数(光学常数)也可按上述的测定方法进行测定。即，例如，制作带上述染料薄膜的PC平板，同时制作在同样的带染料薄膜的PC平板上形成金反射膜的板。然后，使用分光光度计，以带染料薄膜的PC平板为测定对象物，测定所需波长下的透过率，以形成金反射膜的PC平板为测定对象物，测定所需波长下的反射率。然后，由测定的透过率与反射率计算消光系数。
根据该光记录媒体，通过含记录波长下的消光系数0.5以上的第2染料形成记录层，可提供既维持高耐光性或良好的反射率、又可用10m/s以上的高速的线速度记录的光记录媒体。
(2)该情况下，前述第2染料优选薄膜状态下的极大吸收波长是620nm以上、750nm以下。
(3)此外，前述记录层，波长660nm下的薄膜状态下的消光系数优选0.03以上、0.1以下。
(4)以外，前述记录层，优选按0.5以上、5以下的重量％含前述第2染料。
(5)此外，该光记录媒体的前述第1染料优选采用从下述通式(I)表示的染料和金属的螯合化合物(含金属偶氮染料)中选出的1种或2种以上构成。
Figure C0310769200061
式中，A表示与其结合的碳原子及氮泵子一起形成杂环的残基，B表示与其结合的两个碳原子一起形成芳香环或杂环的残基，X表示羟基、羧基、磺酸衍生物基团、或(NSO2Q)-，该Q表示也可用卤原子取代的C1～C6的烷基。
(6)另外，该光记录媒体的前述第2染料优选由下述通式(II)表示的五甲炔花青染料构成。
Figure C0310769200062
式中，R1、R2分别单独地表示取代或未取代的C1～C6的烷基、取代或未取代的C1～C6的链烯基。Z1、Z2分别单独地表示5员或6员的杂环或形成含5员或6员杂环的稠环的原子团。Y表示1价的阴离子。
特别是本发明的光记录媒体，其是在基材上设置记录层而构成，所述记录层含有由从下述通式(I)表示的染料和金属的螯合化合物中选出的1种或2种以上构成的第1染料和由从五甲炔花青染料、三甲炔花青染料和七甲炔花青染料中选出的1种构成的第2染料，其中所述第1染料作为主成分的在重量比为99.5∶0.5～95∶5的范围内，
Figure C0310769200071
式中，A表示与其结合的碳原子和氮原子一起形成杂环的残基，B表示与其结合的两个碳原子一起形成芳香环或杂环的残基，X表示羟基、羧基、磺酸衍生物基团、或(NSO2Q)-，该Q表示也可用卤原子取代的C1～C6的烷基。
再者，本公开涉及2002年3月26日申请的日本特许申请2002-085993中包括的主题，这些公开在此均作为参考写入以加深理解。
附图说明
参照附图更详细地说明本发明的这些及其他目的和特征。
图1表示本发明实施方案的光记录媒体10使用的含金属偶氮染料与五甲炔花青染料各激光波长与消光系数关系的特性图。
图2是表示DVD-R构成的局部截面图。
以下，参照附图，对本发明的光记录媒体的合适的实施方案进行说明。
本发明的光记录媒体(DVD-R)，是至少在基材上设含有第1染料作为主成分的记录层、同时在该记录层上设反射层而构成的光记录媒体，相对于该记录层中的染料总量按0.5以上、5以下的重量％配合第2染料。另外，本发明的光记录媒体，其构成适合用630nm以上、680nm以下波长的激光向记录层记录信息、及用10m/s以上的线速度向记录层记录信息。
该情况下，第1染料有作为决定记录层主要特性的染料的功能，如图1的特性W所示，具有薄膜状态下的极大吸收波长范围是比记录再生用激光波长(以下，称“记录波长”或“再生波长：具体地是630nm以上、680nm以下的波长)短的450nm～620nm，记录再生用激光波长下的消光系数约为0.01～0.03的特性。具体地，第1染料由下述通式(I)表示的染料(偶氮系有机染料)与金属的螯合化合物(含金属偶氮染料)之中选出的1种或2种以上构成。
式中，A表示与其结合的碳原子及氮原子一起形成杂环的残基，B表示与其结合的两个碳原子一起形成芳香环或杂环的残基，X表示羟基、羧基、磺酸衍生物基团或(NSO2Q)-，该Q表示也可用卤原子取代的C1～C6的烷基。
第2染料是为了可用线速度10m/s以上(例如4倍速度)记录、提高记录层的记录敏感度而配合(添加)的染料，如图1的特性X所示，具有薄膜状态下的极大吸收波长是620nm以上、750nm以下(该图中虽没有图示，但由于消光系数最大的波长约720nm，故该例中的极大吸收波长约720nm)、薄膜状态下的记录再生用激光波长下的消光系数为0.5以上的特性。具体地，作为第2染料，优选下述通式(II)表示的染料，再具体地，可采用下述式(III)表示的五甲炔花青染料。
Figure C0310769200091
再者，该式(II)中，R1、R2分别单独地表示取代或未取代的C1～C6的烷基，取代或未取代的C1～C6的链烯基，Z1，Z2分别单独地表示5员或6员的杂环，或形成含5员或6员杂环的稠环的原子团，Y表示1价的阴离子。
Figure C0310769200092
另外，除五甲炔花青染料以外，还可以采用下述式(IV)表示的三甲炔花青染料、或下述式(V)表示的七甲炔花青染料等作为第2染料，
另外，通过上述构成，记录层具有记录再生用激光波长(例如，660nm)下薄膜状态下的消光系数为0.03以上、0.1以下的特性。
该光记录媒体，在含金属偶氮染料为主成分构成的记录层，配合薄膜状态下的记录再生用激光波长下的消光系数高(0.5以上的消光系数)的染料，例如五甲炔花青染料作为第2染料。因此，该记录层可确保与用100％含金属偶氮染料构成的记录层同等的高耐光性、和记录再生用激光波长下的良好反射率，且利用配合的五甲炔花青染料，可提高对记录再生用激光波长的吸收率，结果提高记录再生用激光波长下的记录敏感度。即，该光记录媒体不仅维持高耐光性与良好的反射率，且可用10m/s以上的线速度(4倍速度：14m/s)记录信息。这里，作为第2染料采用消光系数低于0.5的染料时，为了获得目标记录敏感度，必须加大配合量，但加大第2染料的配合量时，由于第1染料的配合量减少，故因错误率增加、折射率降低而导致调制率的降低与反射率的降低，不能满足作为DVD-R的再生特性与高速记录特性。而作为第2染料采用消光系数0.5以上的染料时，由于可抑制第2染料的配合量在5重量％以下，可充分确保第1染料的配合量，结果可充分满足作为DVD-R的再生特性与高速记录特性。再者，作为第2染料可使用的染料的消光系数虽然没有理论上的上限，但配合少量且有明显效果的染料时，配合量的微妙的不同会带来记录敏感度偏差，很难进行稳定的生产。因此，作为光记录媒体用染料，优选使用消光系数2以下的染料，使配合量为0.5重量％以上。
具体实施方式
以下，列举实施例详细地说明本发明。
首先，参照图2说明本实施例使用的光记录媒体的基本构成。光记录媒体10是与DVD-R规格相对应的光记录媒体，通过用胶粘剂40将可记录的盘20与盘30(隔板)进行贴合而构成。此时，盘20是在形成有沟槽GR的基材(通过用聚碳酸酯树脂形成0.6mm左右的厚度)21上，顺序层合记录层22、反射层23与保护层24而构成。盘30，例如用与基材21相同的材料构成。胶粘剂40可选择紫外线固化性树脂或热固性树脂等任意的材料，采用该胶粘剂40的粘接层形成10μm～200μm左右的厚度。
基材21形成盘状，为了可以从内侧进行记录与再生，用对记录再生用激光(波长630nm～680nm左右)形成基本上透明(优选透过率88％以上)的树脂或玻璃作为材料。此时，作为树脂可采用聚碳酸酯树脂、丙烯酸树脂、非晶聚烯烃、TPX、聚苯乙烯树脂等的各种热塑性树脂。
记录层22形成30nm～300nm的厚度。反射层23把Au、Cu、Al、Ag、AgCu等的高反射率金属或合金作为材料形成。另外，反射层23的厚度优选是50nm以上，采用蒸镀、溅射等形成。保护层24，例如用紫外线固化树脂等的各种树脂材料，形成0.5μm～100μm左右的厚度。
在该光记录媒体10上记录或补记信息时，使记录再生用激光通过基材21成脉冲状照射。结果在记录层22的照射部位的光反射率发生变化，记录信息。
以下，说明本实施例采用的试验方法与评价方法。再者，试验先使用评价机DDU-1000(PULSTEC社制。波长661nm。NA0.60)，用线速度3.49m/s与线速度14.0m/s，逐渐顺序提高激光拾读(pickup)的记录激光功率，在记录层上记录信息。
<最适记录功率>
最适记录功率是使用DDU-1000(PULSTEC社制。波长650nm。NA0.60)，用线速度3.49m/s将用上述线速度14.0m/s记录的信息进行再生时的偏差值最小时的记录激光功率的输出值，有关该最适记录功率按下述的评价标准进行评价。
(评价标准)
○：最适记录功率24mW以下
×：最适记录功率超过24mW
<偏差>
偏差，使用DDU-1000(PULSTEC社制。波长650nm。NA0.60)，把用线速度3.49m/s与线速度14.0m/s的两种记录线速度记录的信息，用线速度3.49m/s进行再生，按下述评价标准进行评价。
<评价标准>
○：用线速度3.49m/s、14.0m/s的任一种，综合偏差均在8％以下
×：用任一种的线速度，综合偏差值超过8％
<反射率>
反射率，使用DDU-1000(PULSTEC社制。波长650nm，NA0.60)，把线速度3.49m/s与线速度14.0m/s的两种记录线速度记录的信息，用线速度3.49m/s进行再生，按下述的评价标准进行评价。
(评价标准)
○：用线速度3.49m/s，14.0m/s的任一种，反射率均在45％以上
×：用任一种的线速度，反射率低于45％
<调制率>
调制率，使用DDU-1000(PULSTEC社制。波长650nm，NA0.60)，把线速度3.49m/s与线速度14.0m/s的两种记录线速度记录的信息，用线速度3.49m/s进行再生，按下述的评价标准进行评价。
(评价标准)
○：用线速度3.49m/s，14.0m/s的任一种，调制率均在60％以上
×：用任一种的线速度，调制率低于60％
(错误)
错误，使用DDU-1000(PULSTEC社制。波长650nm，NA0.60)，把线速度3.49m/s与线速度14.0m/s的两种记录线速度记录的信息，用线速度3.49m/s进行再生。用DVD-译码器DR-3340(KENWOOD社制)按下述的评价标准进行评价。
(评价标准)
○：用线速度3.49m/s，14.0m/s的任一种，8ECC域的最大PI错误的错误统计数均在280以下
×：用任一种的线速度，8ECC域的最大PI错误的错误统计数超过280
(实施例1)
把下述式(VI)表示的含金属偶氮染料与上述式(III)表示的五甲炔花青染料(记录波长660nm下的消光系数：1.29)分别按98∶2的重量比混合后，采用旋涂法进行涂布干燥形成记录层22。另外，作为反射层23，用溅射法形成Ag反射层。再将紫外线固化型丙烯酸树脂DAICURE CLEAR SD318(大日本油墨化学工业公司制)作为材料形成保护层24。另外，胶粘剂40使用长效性阳离子聚合胶粘剂SK7000(索尼化学公司制)。
Figure C0310769200131
(实施例2)
除了把上述式(VI)表示的含金属偶氮染料与上述式(IV)表示的三甲炔花青染料(记录波长660nm下的消光系数：0.815)分别按97∶3的重量比进行混合以外，其他与实施例1同样地制作光记录媒体。
(实施例3)
除了把上述式(VI)表示的含金属偶氮染料与上述式(V)表示的七甲炔花青染料(记录波长660nm下的消光系数：0.5)分别按95∶5的重量比进行混合以外，其他与实施例1同样地制作光记录媒体。
(比较例1)
除了把上述式(VI)表示的含金属偶氮染料、和下述式(VII)表示的五甲炔花青染料与苯二硫酚金属配位化合物的盐形成染料(记录波长660nm下的消光系数：0.4)进行混合以使之满足记录敏感度(可在最适记录功率24mW以下进行记录)以外，其他与实施例1同样地制作光记录媒体。此时，第1染料与第2染料分别按90∶10的重量比进行混合。
Figure C0310769200141
(比较例2)
使用上述式(VI)表示的含金属偶氮染料和下述式(VIII)表示的Formazan染料(记录波长660nm下的消光系数：0.45)，与比较例1同样地制作光记录媒体。此时，第1染料与第2染料分别按92∶8的重量比进行混合。
Figure C0310769200151
(比较例3)
使用上述式(VI)表示的含金属偶氮染料和下述式(IX)表示的胺盐系(N，N，N′，N′-四(4-二丁氨基苯基)-对-苯二胺的二(高氯酸盐)(记录波长660nm下的消光系数：0.1)，与比较例1同样地制作光记录媒体。此时，第1染料与第2染料分别按80∶20的重量比进行混合。
对上述实施例1～3制作的光记录媒体、与比较例1～3制作的光记录媒体，按上述的方法，对各最适记录功率、偏差、调制率、反射率与错误(错误率)的电特性进行评价。将该评价结果示于表1。
表1
实施例1 实施例2 实施例3 比较例1 比较例2 比较例3
第1染料的重量％第2染料的重量％第2染料的消光系数 9821.29 9730.815 9550.5 90100.4 9280.45 80200.1
最适记录功率偏差调制率反射率错误 ○○○○○ ○○○○○ ○○○○○ ○○××× ○○×○× ○××××
根据表1可确认配合作为第2染料的记录波长660nm下的消光系数0.5以上的染料的光记录媒体明显地显示出良好的电特性。另外，可确认配合作为第2染料的记录波长660nm下的消光系数低于0.5的染料的光记录媒体，无论怎样改变第1染料与第2染料的配合比，均不能满足各评价项目。
(实施例4)
除了把上述式(VI)表示的含金属偶氮染料与上述式(III)表示的五甲炔花青染料分别按99.5∶0.5的重量比进行混合，使记录层22自身的消光系数为0.041以外，其他与实施例1同样地制作光记录媒体。再者，此时的消光系数是记录波长660nm的薄膜状态下的值(以下，实施例5～比较例6同样)。
(实施例5)
除了把上述式(VI)表示的含金属偶氮染料与上述式(III)表示的五甲炔花青染料分别按98∶2的重量比进行混合，使记录层22自身的消光系数为0.066以外，其他与实施例1同样地制作光记录媒体。
(实施例6)
除了把上述式(VI)表示的含金属偶氮染料与上述式(III)表示的五甲炔花青染料分别按95∶5的重量比进行混合，使记录层22自身的消光系数为0.10以外，其他与实施例1同样地制作光记录媒体。
(比较例4)
除了把上述式(VI)表示的含金属偶氮染料与上述式(III)表示的五甲炔花青染料分别按100∶0的重量比进行混合，使记录层22自身的消光系数为0.02以外，其他与实施例1同样地制作光记录媒体。
(比较例5)
除了把上述式(VI)表示的含金属偶氮染料与上述式(III)表示的五甲炔花青染料分别按92∶8的重量比进行混合，使记录层22自身的消光系数为0.13以外，其他与实施例1同样地制作光记录媒体。
(比较例6)
除了把上述式(VI)表示的含金属偶氮染料与上述式(III)表示的五甲炔花青染料分别按99.8∶0.2的重量比进行混合，使记录层22自身的消光系数为0.028以外，其他与实施例1同样地制作光记录媒体。
对上述实施例4～6制作的光记录媒体与比较例4～6制作的光记录媒体，按上述的方法，评价各最适记录功率、偏差、反射率与错误(错误率)的电特性，将该评价结果示于表2。
表2
实施例4 实施例5  实施例6 比较例4 比较例5 比较例6
第1染料的重量％第2染料的重量％混合染料的消光系数 99.50.50.03 9820.066 9550.10 10000.02 9280.13 99.80.20.028
最适记录功率偏差反射率错误 ○○○○ ○○○○ ○○○○ ×○○○ ○××× ××○○
根据表2，可以确认，记录层22的消光系数在0.03以上、0.1以下的光记录媒体明显表现出良好的电特性。另外，从该结果可知，具有相对于染料总重的第2染料配合量为0.5重量％以上、5重量％以下的记录层22的光记录媒体明显表现出良好的电特性。
再者，本发明不限于上述本发明的实施方案。例如，作为本发明的第1染料可采用下述式(X)的含金属偶氮染料。
Figure C0310769200181
另外，作为本发明的第1染料虽然对只使用1种螯合化合物的例子进行了说明，但也可以使用2种以上的螯合化合物。另外，作为本发明的第2染料，虽然对使用具有薄膜状态下的极大吸收波长是620nm以上、750nm以下，记录用激光波长的消光系数为0.5以上特性的染料的例子进行了说明，但不限于此，至少记录用激光波长下的消光系数0.5以上的染料均可。
当然，本发明的光记录媒体也可适用于各形成记录层与反射层并贴合的所谓两面的光记录媒体。

Claims (1)

1.光记录媒体，其是在基材上设置记录层而构成，所述记录层含有由从下述通式(I)表示的染料和金属的螯合化合物中选出的1种或2种以上构成的第1染料和由从五甲炔花青染料、三甲炔花青染料和七甲炔花青染料中选出的1种构成的第2染料，其中所述第1染料作为主成分的在重量比为99.5∶0.5～9 5∶5的范围内，
Figure C031076920002C1
式中，A表示与其结合的碳原子和氮原子一起形成杂环的残基，B表示与其结合的两个碳原子一起形成芳香环或杂环的残基，X表示羟基、羧基、磺酸衍生物基团、或(NSO2Q)-，该Q表示也可用卤原子取代的C1～C6的烷基。
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