CN1194347C - 光信息记录媒体 - Google Patents

光信息记录媒体 Download PDF

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CN1194347C
CN1194347C CNB00134806XA CN00134806A CN1194347C CN 1194347 C CN1194347 C CN 1194347C CN B00134806X A CNB00134806X A CN B00134806XA CN 00134806 A CN00134806 A CN 00134806A CN 1194347 C CN1194347 C CN 1194347C
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optical information
information recording
anthocyanidin
wavelength
cyclonite
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CN1300062A (zh
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原风美
藤井徹
兴津勳
根岸良
浜田惠美子
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Taiyo Yuden Co Ltd
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    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/12—Heads, e.g. forming of the optical beam spot or modulation of the optical beam
    • G11B7/125—Optical beam sources therefor, e.g. laser control circuitry specially adapted for optical storage devices; Modulators, e.g. means for controlling the size or intensity of optical spots or optical traces
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
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    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
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    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
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Abstract

本发明提供一种可由DVD-R用的波长大于640nm激光进行记录及再生的光信息记录媒体。本发明的光信息记录媒体具有含色素层的光干涉层，此色素层为含有在三次甲基链的两侧具有对称的苯并二氢吲哚环结构的色素、适合以640nm以上的激光记录且能够再生的色素层。

Description

光信息记录媒体
本发明特别涉及一种可藉由DVD-R等的短波长区域的激光进行记录及再生的热模式的覆写型的光信息记录媒体。
记录和再生文字、图形等图像或影像或声音等数据的手段例如具有记录层的光盘，即所谓CD-R，其中该记录层含有可对应波长770～830nm的记录及再生的记录材料例如五次甲基系花青色素。
但最近借助比此CD-R所用激光更短的短波长例如620～690nm的红色激光进行高密度记录及再生的DVD-R(digital.video.disc recordable或digitalversatile.disc recordable)等已作为担任下一世代多媒体使用。
但是，激光记录波长愈靠近长波长侧时，记录层对激光的吸收会降低，感度降低，因此，例如特开平7-251477号公报或特开平10-217664号公报所具体记载的使用三次甲基系芯青色素时光信息记录媒体的感度在640nm以上的波长需要较大的记录功率，到达11mW时其记录功率，可说是非常高，但超过此记录功率时也因感度不足，故有时无法记录。
这种性能仍不足，更要求感度高、反射率和调变度等光学特性符合要求，颤动(Zitter)更低的光信息记录媒体。
本发明的第一个目的系提供一种特别是对于DVD记录用短波长激光的写入感度高，记录功率低，可得到充分调制度的光信息记录媒体。
本发明的第二个目的系提供一种颤动非常低，可更稳定再生的光信息记录媒体。
本发明的第三个目的系提供一种通过适度调整色素对溶剂的溶解度可形成均匀的色素膜，可得到充分调制度的光信息记录媒体。
本发明人等为了解决上述问题而提供一种具有在基板上含有色素层光干涉层的光信息记录媒体，其中所述色素层含有如下通式(化1)表示的三次甲基二苯并二氢吲哚系花青色素，该光干涉层适合波长长于640nm的激光的记录，且可由选自波长620nm～690nm波长区域的激光进行再生的光信息记录媒体。
Figure C0013480600041
(R表示n为1～7的直链或支链的CnH2n+1，n为1～5的CnH2nOC6H5或CnH2nC6H5，X-表示选自ClO4 -，BF4 -，ClO3 -，PF6 -及SbF6 -的阴离子群的阴离子)。
本发明中，光干涉层系由有机色素材料所构成的色素层，由其它有机材料或无机材料所构成的层所构成，含有一层或多层可以激光照射形成凹坑的色素层的记录层，或除了此记录层以外为了调整光信息记录媒体的光学物性而调整折射率、膜厚的例如由树脂材料所构成的加强层，进一步也包括基板与色素层，色素层为多层时其间所设中间层等的统称。
上述通式(化1)中，R表示n为1～7的直链或支链CnH2n+1，即碳原子数1～7的直链或支链的烷基，n为1～5的CnH2nOC6H5，即碳原子数1～5的苯氧烷基，n为1～5的CnH2nC6H5，即碳原子数1～5的苯基烷氧基。
使用此通式(化1)表示的色素可得到由相同波长激光的记录、再生光信息记录媒体，此光信息记录媒体可达成上述目的是因为该色素化合物在三次甲基链的两侧具有对称的苯并二氢吲哚环结构，可使吸收波长形成大于640nm(640nm以上)的波长区域的长波长化。如上述可形成长波长化时，以640nm以上之激光的记录时，能提高该记录波长的折射率n(n＝2～3)，使消光系数k形成适当的数值(k＝0.02～0.1)，结果可提高感度，降低记录功率至例如11mW以下(不超过11mW的数值)。
如上通式(化1)表示的化合物可使使用此化合物的光干涉层的吸收波长形成长波长化但维持其物性的状态下，进一步改变R、X-的种类可改变色素物性，可微调整所得制品光信息记录媒体的电气特性。例如制造光信息记录媒体调制色素溶液时，为了得到以通式(化1)表示的化合物对溶剂的适当溶解性，当X-为PF6 -、SbF6 -时，R系n为3～7的直链或支链CnH2n+1(烷基)较理想，X-为ClO4 -、BF4 -、ClO3 -时，n为1～5的直链或支链CnH2n+1(烷基)较理想。
上述化合物的色素溶解性太低(＜10g/l)时，成膜化困难，不易制作具有色素膜的光盘，相反，色素溶解性太高(＞70g/l)时，成膜化所得色素膜形状杂乱，不均匀，不易有良好的记录，结果溶解性为20～50g/l范围内时可得到最佳状态的色素膜，达到最佳的记录。
关于热特性解温度，当分解温度太低时热稳定性不良，相反地，分解温度太高时记录困难。换言之，分解温度在240～290℃范围内时形成最佳凹坑，得到良好的记录。
上述通式(化1)色素的合成法例如可利用《合成染料化学》第14卷(TheChemistry of Synthetic Dyes Vol 14)所载的方法。
制造本发明的光信息记录媒体时，调制溶解上述通式(化1)表示的花青色素的色素溶液，将此溶液涂布于透光性基板上。此色素溶液可使用氯仿、二氯乙烷、氟化醇、氟化烃等氟系溶剂，丁酮，二甲基甲酰胺，甲醇，甲苯，环己酮，乙酰丙酮，二丙酮醇，甲基溶纤素等溶纤剂类，二噁烷等。此时花青色素的混合比例以1％～30％为宜(以下(％)系表示重量％)。
本发明所用基板有例如玻璃，或环氧树脂、甲基丙烯酸树脂、聚碳酸酯树脂、聚酯树脂、聚氯化乙烯树脂、聚烯烃树脂等塑料。此基板上可形成轨道沟或凹坑，也可具有地址信号所需之信号者。
将上述花青色素溶液涂布于基板时，使用旋转涂布法较佳。干燥后涂布层之厚度可使用以往所用者。
本发明中被涂布的记录层中可含有单态氧淬灭剂、光吸收剂、自由基捕捉剂等其它化合物。
反射层有例如经蒸镀、溅镀等所形成的Au，Al，Ag，Cu，Pt，这些金属的各种合金，添加这些金属外的微量成分的合金等金属膜之类高反射率材料膜；保护膜有例如以保护光信息记录媒体及提高耐候性为目的、经旋转涂布法等涂布紫外线硬化型树脂等的放射线硬化型树脂的溶液并使之硬化的涂布层。
如上所述，可得到在基板上设置含有色素层的光干涉层、反射层并进一步设置保护层等的光盘。贴合至少具有该光干涉层的其它相同构成或其他构成的光盘，或可对贴基板。
此贴合的材料、方法可使用紫外线硬化树脂，阳离子性硬化树脂，两面粘着薄片，热熔融法，旋转涂布法，分散法(挤压法)，网版印刷法，辊涂方式等。
以下用实施例详细说明，使用上述通式(化1)所示二苯并二氢吲哚系花青色素(R为低级烷基，特别理想为碳数4、5的直链或支链烷基，X-为选自ClO4 -，PF6 -，SbF6 -阴离子的色素)在聚碳酸酯基板上形成光干涉层的色素层。
由于色素层的色素在三次甲基链两侧的对称的二苯并二氢吲哚环结构，该光干涉层对于波长660nm的激光的折射率n高达2～3，消光系数k适当，为0.02～0.1，因此可提高感度。通过组合上述R与X-，可得到该色素对溶剂的适度溶解性，可形成良好的色素膜，因分解温度适当故可确保低颤动(Zitter)和充分的调制度。
实施例1
用射出成型法形成由厚0.6mm，外径(直径)120mm的聚碳酸酯所构成的透明基板，其表面形成宽0.32μm、深100nm、间距0.74μm的螺旋状沟。
接着将上述通式(化1)所示三次甲基系花青色素，即表1所示R为n-C4H7，X-为ClO4 -的色素(1，1’-二正丁基-3，3，3’，3’-四甲基-4，5，4’，5’-二苯并二氢吲哚花青素全氯酸酯)溶解于4-羟基-4-甲基-2-戊酮(关东化学公司制，以下简称DAA)，成为15mg/ml，以旋转涂布法将该花青蓝色素溶液涂布于上述基板的表面，形成由膜厚50nm的感光色素膜所构成的光干涉层。
用溅镀法在基板的44mm～117mm的区域全面形成膜厚80nm的Au膜，在此光干涉膜上形成反射层。
将紫外线硬化树脂SD-211(大日本油墨化学工业公司制)旋转涂布于此反射层上，紫外线照射于该涂膜上，使之硬化形成膜厚5μm的保护膜。
进一步将紫外线硬化树脂SD-640(大日本油墨化学工业公司制)滴至此基板的保护膜及未形成该保护膜的光干涉层上，然后将与上述同样成形的其它基板置于其上，以旋转涂布法将树脂扩散于其间隙内，然后在重叠基板侧再度照射紫外线，使之硬化，在原先基板的32mm～120mm区域形成由树脂所构成的厚度25μm的粘着层贴合重叠的基板，制作贴合型光盘。
以NA(开口率(numerical aperture)＝0.6、激光波长＝655nm的DDU＝1000(Pulstec公司的记录机)，按3.5m/秒线速将EMF信号记录于如上所制光盘上，以相同记录机再生。
其评价结果如表1所示。
实施例2，3
除了使用实施例1的以上述通式(化1)所示三次甲基系花青色素(其中分别如表1的实施例2，3各栏所示，R，X-分别使用各官能团)外，其余相同，制作各实施例的光盘，使用各光盘进行与实施例1相同的记录后，再生，测定的结果如表1所示。
比较例1～5
除了使用如下述通式(化2)所示三次甲基系花青色素(如表1比较例1～5各栏所示，A，R，X-使用各官能基)取代实施例1的上述通式(化1)所示三次甲基系花青色素外，同样制作光盘，使用各光盘进行与实施例1相同之记录后，再生，测定的结果如表2所示。
Figure C0013480600071
                                       (表1)
  实施例     通式[化1]的化合物   评价结果
    R   X-   记录功率(mW)     颤动(％)     调制度(％)
  1     n-C4H9   PF6 -   9.5     9.5     59.4
  2     n-C5H11   PF6 -   9.8     9.3     58.7
  3     n-C5H11   SbF6 -   9.5     9.5     51.1
                                          (表2)
  比较例   通式[化2]的化合物  评价结果
  A     R     X-  记录功率(mW)   颤动(％)     调制度(％)
  1     i-C5H11     ClO4 -               因感度不足无法记录
  2     i-C5H11     PF6 -               因感度不足无法记录
  3     n-C5H11     ClO4 -  12.0     12.8     45.3
  4     n-C4H9     ClO4 -  11.9     18.9     74.0
  5     n-C4H9     ClO4 -  11.8     21.0     59.8
由表1结果得知，实施例与比较例比较，记录功率、DC Zitter％前者分别为10mW以下(除了实施例2未超过9.5mW(9.5mW以下))，未超过9.5％(9.5％以下)，而后者分别为10mW以上，12.5％以上，很明显前者优于后者，使用实施例所用三次甲基链的两侧具有对称苯并二氢吲哚环结构的花青色素的效果显著。调制度平均值虽无法说明实施例较优异，但也未较差，可说是适当的调制度。调制度高，低颤动是表示再生感度佳。
由这些结果及其它上述说明，本发明中可追加「记录功率为10mW以下(更理想为不超过9.5mW)，颤动不超过9.5％」中的至少一个限定。
上述本发明中，可将「通式(化1)」限定为上述通式各种组合的一部分，或限定为实施例、优选实施例所列花青色素的一部分或全部，同时所有这些中可追加其它上述限定事项。
本发明也可以是光信息记录媒体的制造方法，所述光信息记录媒体具有在基板上含有色素层的光干涉层，所述色素层含有所述通式(式1)所示三次甲基二苯并二氢吲哚系花青色素，所述光干涉层经波长大于640nm的激光来记录，且可经选自波长620nm～690nm波长区域的激光进行再生而完成记录。
本发明可提供一种设置具有色素层的光干涉层的光信息记录媒体，该色素层含有如上通式(化1)所示二苯并二氢吲哚系花青色素，故可提供一种特别是对于DVD记录用短波长激光的写入感度非常高、记录功率低、调制度充分、且颤动非常低、可更稳定再生的光信息记录媒体。
特别是通过对上述通式(化1)中R、X-种类的选择，可选择对于溶剂具有适度溶解性的色素，可得到均匀的色素膜，因此可确保低颤动和充分的调制度。

Claims (6)

1.一种光信息记录媒体，其具有在基板上含有色素层的光干涉层，其特征为该色素层含有三次甲基系二苯并二氢吲哚系花青色素，所述光干涉层适于以波长大于640nm的激光来记录，且可由选自波长620nm～690nm波长区域的激光进行再生，所述三次甲基系二苯并二氢吲哚系花青色素为通式[化1]所示色素：
Figure C001348060002C1
R表示n为3～7的直链或支链CnH2n+1，X-表示选自PF6 -及SbF6 -的阴离子群的阴离子。
2.如权利要求1所述的光信息记录媒体，其中三次甲基系二苯并二氢吲哚系花青色素对于波长650nm的激光的折射率为2～3。
3.如权利要求1或2所述的光信息记录媒体，其中三次甲基系二苯并二氢吲哚系花青色素对于波长650nm的激光的消光系数为0.02～0.1。
4.如权利要求1、2或3所述的光信息记录媒体，其中三次甲基系二苯并二氢吲哚系花青色素的溶解度为20～50g/l。
5.如权利要求1、2、3或4所述的光信息记录媒体，其中三次甲基系二苯并二氢吲哚系花青色素的分解温度为240～290℃。
6.一种光信息记录媒体的再生方法，其特征在于由波长大于640nm的激光记录于具有在基板上含有色素层的光干涉层的光信息记录媒体，其中所述色素层含有三次甲基系二苯并二氢吲哚系花青色素，且由选自波长620nm～690nm波长区域的激光进行再生，所述三次甲基系二苯并二氢吲哚系花青色素为通式[化1]所示色素：
R表示n为3～7的直链或支链CnH2n+1，X-表示选自PF6 -及SbF6 -的阴离子群的阴离子。
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