CN100505055C - 光信息记录介质 - Google Patents

光信息记录介质 Download PDF

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Publication number
CN100505055C
CN100505055C CNB031201148A CN03120114A CN100505055C CN 100505055 C CN100505055 C CN 100505055C CN B031201148 A CNB031201148 A CN B031201148A CN 03120114 A CN03120114 A CN 03120114A CN 100505055 C CN100505055 C CN 100505055C
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CN
China
Prior art keywords
layer
optical information
recording medium
substrate
recording layer
Prior art date
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Expired - Fee Related
Application number
CNB031201148A
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English (en)
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CN1444216A (zh
Inventor
宇佐美由久
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Fujifilm Corp
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Fujifilm Corp
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Priority claimed from JP2002062175A external-priority patent/JP2003263782A/ja
Priority claimed from JP2002062173A external-priority patent/JP2003263785A/ja
Priority claimed from JP2002062174A external-priority patent/JP3742021B2/ja
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN1444216A publication Critical patent/CN1444216A/zh
Application granted granted Critical
Publication of CN100505055C publication Critical patent/CN100505055C/zh
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Abstract

一种盘状的光信息记录介质，在衬底上按顺序具有记录层、粘合剂层或结合剂层以及保护层，磁道间隔为250～400nm，沟深度为10～150nm，照射500nm以下的波长的激光来记录、再现信息，并且具有中心孔，所述衬底和所述保护层通过粘合剂层或结合剂层在内周附近以及/或外周附近的至少一部分的区域紧贴，并且该紧贴区域的直径方向长度的最大值是0.4mm以上。上述光信息记录介质，各层间的紧贴性高、具有稳定的记录再现特性。另外，本发明还提供保存性高、具有稳定的记录再现特性的光信息记录介质。

Description

光信息记录介质
技术领域
本发明涉及光信息记录介质，特别是涉及基于加热模式的追加记录型的光信息记录介质。
背景技术
以往，我们知道通过激光能只进行一次信息记录的光信息记录介质(光盘)。该光盘也被称作追加记录型CD(所谓的CD-R)，它的代表构造是在透明的圆盘状衬底上按顺序层叠由有机色素构成的记录层、由金等的金属构成的反射层、树脂制的保护层(覆盖层)。而且，向该CD-R记录信息是通过向CD-R照射近红外区域的激光(通常是780nm附近波长的激光)，记录层的照射部分吸收该光，局部地温度上升，通过物理或化学的变化(例如生成凹槽)，使该部分的光学特性变化，从而记录了信息。而信息的读取(再现)也通过使用与记录用的激光相同波长的激光照射CD-R而进行，通过检测记录层的光学特性变化了的部位(记录部分)和未变化的部位(未记录部分)的反射率的不同而进行。
近年，对记录密度更高的光信息记录介质有需求。为了满足这样的需求，提出了被称作追加记录型的数字通用盘(所谓的DVD-R)的光盘(例如“日经新媒体”增刊“DVD”，1995年发行)。该DVD-R具有：在透明圆盘状衬底上依次层叠含有机色素的记录层、反射层以及保护层后得到的2张盘，以记录层为内侧贴合在一起，或者该盘和具有同样形状的圆盘状保护衬底，以记录层为内侧贴合在一起的结构，其中在所述透明圆盘状衬底上形成的用于跟踪照射的激光的引导沟(预刻槽)的宽度小于CD-R的1/2(0.74～0.8μm)。而且，向该DVD-R的信息的记录和再现是通过照射可视激光(通常是630nm～680nm的范围波长的激光)而进行，能实现比CD-R更高密度的记录。
最近，因特网等网络和高清晰度电视迅速普及起来。另外，HDTV(HighDefinition Television)的放映的开始也迫在眉睫。在这样的状况下，就十分需要能以低价、简便地记录图像信息的大容量光信息记录介质。虽然DVD-R的现状已充分实现了作为大容量的光信息记录介质的功能，但是大容量化、高密度化的要求不断高涨，有必要开发能对应这些要求的光信息记录介质。因此，能够以比DVD-R更短波长的光进行高密度记录的更大容量的光信息记录介质的开发正在不断发展。
例如，提出了：把通过透过适合于高密度记录的高NA透镜的光而进行的记录作为前提，并在基盘上按顺序设置了金属反射层、记录层、比基盘还薄的保护层的记录介质，另外，提出了通过从记录层一侧向光反射层一侧照射波长低于550nm的短波长激光，进行信息的记录、再现的记录再现方法。而且，作为利用上述短波长激光的光信息记录介质的记录层形成色素，提出了卟啉化合物、偶氮色素、金属偶氮类色素、奎酞酮、三次甲基花青苷色素、二氰乙烯基苯基骨架色素以及香豆素化合物等(例如，特开平4-74690号报道、特开平7-304256号报道、特开平7-304257号报道、8-1271705号公报、特开平11-53758号公报、特开平11-334204号公报、特开平11-334205号公报、特开平11-334206号公报、特开平11-334207号公报、特开2000-43423号公报、特开2000-108513号公报、特开2000-149320号公报、特开2000-158818号报道、特开2000-228028号报道、特开2001-146074号报道等)。本行业的人士很容易想起即使是此外的化合物，如果是能吸收记录中使用的激光的化合物，原理上能作为记录层用色素使用。而且，作为记录再现用的激光，提出了蓝紫色(波长405nm或410nm)、蓝色(波长430nm或488nm)或青绿色(波长515nm)。
通过以上的短波激光能记录、再现信息的光信息记录介质一般在衬底上按顺序具有例如反射层、记录层、阻碍层、粘合剂层或结合剂层和保护层，与CD-R或DVD-R的层结构不同。因此，激光的照射方向与CD-R或DVD-R相反，有时在CD-R或DVD-R中不会成为问题的层的剥离会变为问题，要求了各层间的高的紧贴性。可是，有机物(记录层等)和无机物(反射层、阻碍层等)相邻的层结构上，存在容易剥离的界面，所以无法取得充分的粘贴强度，还有改善的余地。另外，根据该层结构，特别是在外周边缘，记录层露在外部，所以由环境温度、湿度而保存性恶化。
发明内容
本发明是鉴于所述问题点而提出的，它以实现以下目的为课题。
即本发明的目的在于：提供一种各层间的紧贴性高、具有稳定的记录再现特性的光信息记录介质。
本发明的另一个目的在于：提供一种保存性高、具有稳定的记录再现特性的光信息记录介质。
解决所述课题的方法如下所述。
即本发明之1是一种盘状的光信息记录介质，在衬底上按顺序具有记录层、粘合剂层或结合剂层以及保护层，其特征在于：磁道间隔为250～400nm，沟深度为10～150nm，照射500nm以下波长的激光来记录、再现信息，并且具有中心孔，所述保护层的厚度是0.01～0.2mm，所述记录层是含有色素化合物的层，所述衬底和所述保护层通过所述粘合剂层或所述结合剂层在内周附近和/或外周附近的至少一部分的区域紧贴，并且该紧贴区域的直径方向长度的最大值，在外周近旁是0.4～2mm，在内周近旁是0.4～15mm。
本发明之2是一种盘状的光信息记录介质，在衬底上按顺序具有记录层、阻碍层、粘合剂层或结合剂层以及保护层，其特征在于：磁道间隔为250～400nm，沟深度为10～150nm，照射500nm以下的波长的激光来记录、再现信息，并且具有中心孔，所述记录层是含有色素化合物的层，所述阻碍层围绕所述记录层的外周边缘部和/或内周边缘部，所述粘合剂层或结合剂层围绕所述记录层的外周缘部和/或内周缘部，该阻碍层外周直径与该记录层的外周直径之差为0.4～4mm，该阻碍层内周直径比该记录层的内周直径小0.4～15mm。
本发明之3是一种盘状的光信息记录介质，在衬底上按顺序具有记录层、阻碍层、粘合剂层或结合剂层以及保护层，磁道间隔为250～400nm，沟深度为10～150nm，照射500nm以下的波长的激光来记录、再现信息，并且具有中心孔，所述记录层是包含有机色素的层，所述衬底和所述阻碍层在内周附近和/或外周附近的至少一部分区域中紧贴，并且该紧贴区域的直径方向长度的最大值，在外周近旁是0.4～2mm，在内周近旁是0.4～15mm。
附图说明
图1是表示应用了本发明实施形式1的光信息记录介质的俯视图。
图2是沿着图1的II-II线的剖面的模式图。
图3是表示应用了本发明实施形式2的光信息记录介质的俯视图
图4是沿着图3的II-II线的剖面的模式图。
图5是表示应用了本发明实施形式2的光信息记录介质的变形例的与图4对应的图。
图6是表示应用了本发明实施形式2的光信息记录介质的变形例的与图4对应的图。
图7是表示本发明实施形式3的光信息记录介质的俯视图。
图8是沿着图7的II-II线的剖面的模式图。
具体实施方式
下面，就本发明的光信息记录介质的实施例加以说明。
本发明之1的盘状的光信息记录介质是在衬底上按顺序，根据需要具有反射层、记录层，根据需要还具有阻碍层、粘合剂层或结合剂层以及保护层，其特征在于：磁道间隔250～400nm，沟深度10～150nm，照射500nm以下波长的激光来记录、再现信息，并且具有中心孔，所述衬底和所述保护层通过粘合剂层或结合剂层在内周附近和/或外周附近的至少一部分的区域紧贴，并且该紧贴区域的直径方向长度的最大值是0.4mm以上。
本发明之2的盘状的光信息记录介质是在衬底上按顺序，根据需要具有反射层、记录层、阻碍层、粘合剂层或结合剂层以及保护层，其特征在于：磁道间隔为250～400nm，沟深度为10～150nm，照射500nm以下的波长的激光来记录、再现信息，并且具有中心孔，所述阻碍层围绕所述记录层的外周边缘和/或内周边缘。
本发明之3的盘状的光信息记录介质是在衬底上按顺序，根据需要具有反射层、记录层、阻碍层、粘合剂层或结合剂层以及保护层，其特征在于：磁道间隔为250～400nm，沟深度为10～150nm，照射500nm以下的波长的激光来记录、再现信息，并且具有中心孔，所述衬底和所述阻碍层在内周附近和/或外周附近的至少一部分区域中紧贴，并且该紧贴区域的直径方向的长度的最大值为0.4mm以上。
实施形式1
图1、图2分别是表示应用了本发明实施形式1的光信息记录介质的俯视图、模式剖视图。光信息记录介质10在衬底12上按顺序具有反射层14、记录层16、阻碍层18、粘合剂层20、保护层22，在中央部具有中心孔24。光信息记录介质10在图1中用虚线表示的外周附近和内周附近分别四处区域(以下，称作“紧贴区域”)中，通过粘合剂层20使衬底12和保护层22紧贴。设置在这些内周附近的和外周附近的各四处的紧贴区域的直径方向长度的最大值是0.5mm。而且，由于这些紧贴区域的存在，在衬底12上反射层14、记录层16和阻碍层18牢固地紧贴。因此，能防止光信息记录介质10的各层的剥离。须指出的是，在图1中，紧贴区域分别在外周和内周设置了四处，但是本发明并不局限于此。理想的是设置多个紧贴区域，或者在外周和内周的整个圆周上设置。
在本发明实施形式1中，所述紧贴区域的直径方向长度的最大值为0.4mm以上，但是该最大值不足0.4mm时，紧贴力不充分，有时产生层的剥离。更具体而言，该最大值在外周附近更理想的是0.6mm以上，最理想的是0.7mm以上。另外，外周附近的该最大值的上限是2mm。
另外，内周附近紧贴区域的直径方向长度的最大值更理想的是2.5mm以上，3mm以上更为理想，特别理想的是在4mm以上。另外，内周附近的该最大值的上限是15mm。
在本实施形式的光信息记录介质中，表示了在内周和外周具有紧贴区域的形态，虽然该形态是最理想的，但是也可以在内周和外周的任意一方上形成紧贴区域。
实施形式2
图3、图4分别是本发明实施形式2的光信息记录介质的俯视图、模式剖视图。如图4所示，光信息记录介质10a在衬底12a上按顺序具有反射层14a、记录层16a、阻碍层18a、结合剂层20a、保护层22a，在中央部具有中心孔24a。在图3中，外侧的虚线表示阻碍层18a的外周，内侧的虚线表示记录层16a的外周。即如图4所示，阻碍层18a形成到记录层16a外周的外侧。更具体而言，阻碍层18a在用外周边缘包围了记录层16a的状态下，通过结合剂层20a粘贴了保护层22a。因此，记录层16a不在外部露出，并且被阻碍层18a保护，所以在保存能力上优异。
光信息记录介质10a的保护层12a通过粘合剂层20a接合在反射层14a和阻碍层18a，但是，结合剂层20a和反射层14a的紧贴区域的直径方向长度的最大值理想的是0.4mm以上。通过使该最大值为0.4mm以上，能得到充分的紧贴力，难以发生剥离。更具体而言，该最大值在外周附近更理想的是0.6mm以上，最理想的是0.8mm以上。另外，在内周附近理想的是2.5mm以上，更理想的是3mm以上，特别理想的是4mm以上。
接着，表示了本发明实施形式2的光信息记录介质的两个(图5、图6)变形例。在图5、图6中，对与图3、图4所示的光信息记录介质10a相同的结构元件采用了相同的符号。图5所示的光信息记录介质10a’是到衬底12a的外周边缘形成了阻碍层18a的例子，图6所示的光信息记录介质10a”是到记录层16a的外周的外侧和内周的内侧形成了阻碍层18a的例子。在任意的例子中，阻碍层18a都围绕着记录层16a，所以保存能力优异，但是图6所示的例子中，记录层16a的内周边缘和外周边缘都被阻碍层18a覆盖，所以最好。
如上所述，阻碍层和记录层的外周直径和/或内周直径不同，但是所述阻碍层和所述记录层的外周直径的差理想的是0.4～4mm，更理想的是0.8～2mm。另外，所述阻碍层和所述记录层的内周直径的差理想的是0.4～15mm，更理想的是0.8～7mm。
实施形式3
图7、8分别是本发明实施形式3的光信息记录介质的俯视图、模式剖视图。光信息记录介质10b在衬底12b上按顺序具有反射层14b、记录层16b、阻碍层18b、结合剂层20b、保护层22b，在中央部具有中心孔24b。光信息记录介质20b在图7中用虚线表示的外周附近和内周附近的分别四处区域(以下，称作“紧贴区域”)中，衬底22b和阻碍层28b紧贴。设置在这些内周附近的和外周附近的各四处的紧贴区域的直径方向长度最大值是0.5mm。而且，由于这些紧贴区域的存在，在衬底22b上反射层24b和记录层26b牢固地紧贴。因此，能防止光信息记录介质10b的各层的剥离。须指出的是，在图7中，紧贴区域分别在外周和内周设置了四处，但是本发明并不局限于此。紧贴区域可以设置多个，或者在外周和内周的整个圆周上设置。
在本实施形式中，所述紧贴区域的直径方向长度的最大值为0.4mm以上，但是该最大值不足0.4mm时，紧贴力不充分，有时产生层的剥离。更具体而言，该最大值在外周附近更理想的是0.6mm以上，最理想的是0.7mm以上。另外，外周附近的该最大值的上限是2mm。
另外，内周附近紧贴区域的直径方向长度的最大值更理想为2.5mm以上，3mm以上更好，特别理想的是在4mm以上。另外，内周附近的该最大值的上限是15mm。
在本实施形式3的光信息记录介质中，表示了内周和外周具有紧贴区域的形态，虽然该形态是最希望的，但是也可以在内周和外周的任意一方上形成紧贴区域。
下面，就本发明的光信息记录介质的衬底和各层加以说明。
<衬底>
作为衬底，可以任意选择使用以往的作为光信息记录介质的衬底材料而使用的各种材料。具体而言，能列举出玻璃；聚碳酸酯、聚甲基丙烯酸甲酯等的丙烯酸树脂；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；聚酯；铝等金属等；根据需要，也能把这些同时使用。
在所述材料中，从耐湿性、尺寸稳定性和低价格等观点出发，理想的是聚碳酸酯、无定形聚烯烃，特别理想的是聚碳酸酯。另外，衬底的厚度理想的是0.5～1.4mm。
在衬底上形成了跟踪用的引导沟或代表地址信号等信息的凹凸(预刻槽)。为了实现更高的记录密度，最好使用与CD-R和DVD-R相比，形成了更窄的磁道间隔的预刻槽的衬底。预刻槽的磁道间隔是250～400nm。另外，预刻槽的深度(沟深度)是10～150nm的范围，理想的是15～100nm，更理想的是20～80nm，最理想的是20～60nm。
须指出的是，在设置了后述的反射层一侧的衬底表面上，为了改善平面性，提高粘合力，最好形成底涂层。
作为该底涂层的材料，能列举出聚甲基丙烯酸甲酯、丙烯酸·甲基丙烯酸酯共聚物、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、聚酯、聚酰亚胺、醋酸乙烯·氯乙烯共聚物、乙烯·醋酸乙烯共聚物、聚乙烯、聚丙烯、聚碳酸酯等高分子物质；硅烷耦合剂等表面改质剂。
底涂层可以通过把所述材料溶解或分散到适当的溶剂中，调配了涂敷液后，通过旋转镀膜、浸渍涂敷、挤压涂敷等的涂敷法，把该涂敷液涂敷在衬底表面而形成。底涂层的层厚一般是0.005～20μm的范围，最好是0.01～10μm的范围。
<反射层>
在反射层中使用了对激光反射率高的光反射性物质。作为该反射率，为70％以上。
作为反射率高的光反射性物质，能列举出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等金属以及半金属或不锈钢。可以单独使用这些光反射性物质，或者组合两种以上，或使用合金。它们当中，理想的是Cr、Ni、Pt、Cu、Ag、Au、Al和不锈钢。特别理想的是Ag、Au、Al或它们的合金，最理想的是Ag、Au或它们的合金。
通过在衬底上蒸镀、溅射或离子电镀所述理想的光反射性物质，能形成反射层。反射层的层厚一般为10～300nm的范围，理想的是50～200nm的范围。另外，在实施形式1和实施形式3中为了确保紧贴区域，使用掩模，设置了不形成反射层的区域。
当以下的记录层的反射率十分大时，就未必需要设置所述的反射层，这时，记录层实现了反射层的功能。
<记录层>
记录层是含有色素化合物的层，作为色素化合物，理想的是三唑类化合物、酞菁化合物、卟啉化合物、氨基丁二烯类化合物、花青苷类化合物的至少一种，作为酞菁化合物，理想的是烷氧基取代化合物、磺酰胺取代化合物、氨磺酰取代化合物、磺酸取代化合物的至少一种。
另外，也能并用特开平4-74690号公报、特开平8-127174号公报、特开平11-53758号公报、特开平11-334204号公报、特开平11-334205号公报、特开平11-334206号公报、特开平11-334207号公报、特开2000-43423号公报、特开2000-108513号公报以及特开2000-158818号公报等中描述的色素。
并不局限于所述色素，还可以适当使用三唑化合物、三嗪化合物、花青苷化合物、份菁化合物、氨基丁二烯化合物、酞菁化合物、肉桂酸化合物、氧化还原化合物、偶氮化合物、氧杂菁苯并噁唑、苯并三唑衍生物等有机化合物。在这些化合物中，特别理想的是苯并三唑衍生物、酞菁化合物。
把所述色素(有机物等)等记录物质与结合剂等一起溶解于适当的溶剂中，调配记录层涂敷液，接着把该记录层涂敷液涂敷在形成在衬底表面上的反射层上(当不设置反射层时，是衬底上)，形成涂敷膜后，通过干燥形成了记录层。而且，在实施形式1和实施形式3中为了设置紧贴区域，在涂敷后，把该区域用溶剂清洗并除去，而在实施形式2中为了以后述的阻碍层围绕记录层，在涂敷记录层涂敷液后，把外周部和/或内周部的区域用溶剂清洗并除去。
记录层涂敷液中记录物质的浓度一般是0.01～15质量％的范围，理想的是0.1～10质量％的范围，更理想的是0.5～5质量％的范围，最理想的是0.5～3质量％的范围。
另外，作为溶解处理记录物质等的方法，可以使用超声波处理、均质器、加热等的方法。
作为调配记录层涂敷液时的溶剂，能列举出乙酸丁酯、乳酸甲酯、乳酸乙酯、乙酸溶纤剂等酯；甲乙酮、环己酮、甲基异丁酮等的酮；二氯甲烷、1、2-二氯乙烷、三氯甲烷等的氯化烃；N，N—二甲基甲酰胺等酰胺；甲基环己烷等的烃；四氢呋喃、乙醚、二噁烷等的醚；乙醇、正丙醇、异丙醇、正丁醇、双酮乙醇等乙醇；2，2，3，3-四氟丙醇等氟类溶剂；乙二醇单甲醚、乙二醇单乙醚、丙二醇单甲醚等醇醚类等。
考虑所使用的记录物质的溶解性，能单独或组合两种以上使用。在涂敷液中还可以再根据目的添加防氧化剂、UV吸收剂、增塑剂、润滑剂等各种添加剂。
当使用结合剂时，作为结合剂的例子，能列举出明胶、纤维素衍生物、葡萄糖、松脂、橡胶等的天然有机高分子物质；聚乙烯、聚丙烯聚苯乙烯、聚异丁烯等的烃类树脂；聚氯乙烯、聚偏氯乙烯、聚氯乙烯·聚醋酸乙烯共聚物的乙烯类树脂；聚丙烯酸甲酯、聚甲基丙烯酸甲酯等的丙烯酸树脂；聚乙烯醇、氯化聚乙烯、环氧树脂、丁缩醛树脂、橡胶衍生物、苯酚·甲醛树脂等的热固化性树脂的初期缩合物等合成有机高分子。当同时使用结合剂作为记录层的材料时，结合剂的使用量一般对于记录物质是0.01倍量～50倍量(质量比)的范围，理想的是0.1～5倍量(质量比)的范围。这样调配的涂敷液中的记录物质的浓度一般是0.01倍量～10质量％的范围，理想的是0.1～5质量％的范围。
作为涂敷方法，能列举出喷涂法、旋转镀膜法、浸渍法、辊涂法、刀片镀膜法、括刀辊涂法、丝网印刷法等。记录层可以是单层，也可以是重叠层。另外，记录层的层厚一般是20～500nm的范围，理想的是30～300nm的范围，更理想的是50～100nm的范围。
另外，作为涂敷温度，如果是23～50℃，就不会有什么问题，但是理想的是24～40℃，更理想的是25～37℃。
为了控制粘度，涂敷温度理想的是23～50℃的范围，更理想的是24～40℃的范围，最理想的是25～37℃的范围。
为了防止盘的翘曲，理想的是使用脉冲型的光照射器(理想的是UV照射器)进行对涂敷膜的紫外线的照射。脉冲间隔理想的是在msec以下，更理想的是在μsec以下。虽然未特别限制一个脉冲的照射光量，但是理想的是在3kW/cm2以下，更理想的是在2kW/cm2以下。
另外，虽然并未特别限制照射次数，但是理想的是在20次以下，更理想的是在10次以下。
为了提高所述记录层的耐光性，可以在记录层中含有各种防退色剂。
作为防退色剂，一般使用单态氧猝灭剂。作为单态氧猝灭剂，能利用在公开的专利说明书等刊物中记载的。
作为具体例，能列举特开昭58-175693号公报、特开昭59-81194号公报、特开昭60-18387号公报、特开昭60-19586号公报、特开昭60-19587号公报、特开昭60-35054号公报、特开昭60-36190号公报、特开昭60-36191号公报、特开昭60-44554号公报、特开昭60-44555号公报、特开昭60-44389号公报、特开昭60-44390号公报、特开昭60-54892号公报、特开昭60-47069号公报、特开昭63-209995号公报、特开平4-25492号公报、特公平1—38680号公报、和特公平6-26028号公报、德国专利3503399号说明书，还有日本化学会杂志1992年10月号的第1141页等中记载的。
所述单态氧猝灭剂等的防退色剂的使用量对于用于记录的化合物的量，通常是0.1～50质量％的范围，理想的是0.5～45质量％的范围，更理想的是3～40质量％的范围，特别理想的是5～25质量％的范围。
<阻碍层>
阻碍层是在所述记录层和后述的粘合剂层或结合剂层之间，根据需要而形成的层。作为构成阻碍层的材料，如果是激光能透射的材料，就没有特别限制，但是理想的是电介质，更具体而言，列举ZnS、TiO2、SiO2、ZnS-SiO2、GeO2、Si3N4、Ge3N4、MgF2等的无机化合物、氮化物、硫化物，其中理想的是ZnS-SiO2或SiO2。阻碍层可以通过溅射、离子电镀等形成，它的厚度理想的是1～100nm。另外，为了确保紧贴区域，使用掩模，设置了不形成阻碍层的区域。
在本发明的光信息记录介质中，在以上的记录层或阻碍层上，通过以下所示的粘合剂层或结合剂层粘贴了后述的保护层。
<粘合剂层>
粘合剂层是用于粘合后述的保护层而形成的层，可以广泛使用以往公开的技术。作为粘合剂，可以适当选择使用丙烯酸类粘合剂、天然橡胶、苯乙烯-异戊二烯-苯乙烯共聚物(SIS)、苯乙烯-丁二烯-苯乙烯共聚物(SBS)等的橡胶类粘合剂。该粘合剂最好预先涂敷在保护层的粘合面上。粘合剂层的层厚为1～10μm，特别理想的是2～5μm的范围。
<结合剂层>
结合剂层与粘合剂层同样，是用于粘合后述的保护层而形成的层。作为构成结合剂层的材料，可以列举光固化性树脂、2液固化型结合剂，其中，理想的是光固化性树脂，为了防止盘的翘曲，理想的是固化收缩率小的材料。作为这样的光硬化性树脂，例如能列举大日本油墨化学工业(株式会社)制造的“SD-640”、“SD-661”、“SD-347”等的UV固化树脂(UV固化性结合剂)。另外，为了具有弹性，结合剂层的厚度理想的是1～1000μm的范围，更理想的是5～500μm的范围，最理想的是10～100μm的范围。
下面，列举形成结合剂层的其它材料例子。该材料是能通过放射线的照射而硬化的树脂，是在分子中具有两个以上的放射线官能度双键结合的树脂，可以列举出丙烯酸酯类、丙烯酰胺类、甲基丙烯酸酯类、甲基丙烯酰胺类、烯丙基化合物、乙烯醚类、乙烯基酯类等。理想的是2官能团以上的丙烯酸酯化合物、甲基丙烯酸酯化合物。
作为2官能团的具体例，可以使用在乙二醇二丙烯酸脂、丙二醇二丙烯酸脂、丁二醇二丙烯酸脂、己二醇二丙烯酸脂、二乙二醇二丙烯酸脂、三乙二醇二丙烯酸脂、四乙二醇二丙烯酸脂、季戊二醇二丙烯酸脂、三丙二醇二丙烯酸脂、乙二醇二甲基丙烯酸酯、丙二醇二甲基丙烯酸酯、丁二醇二甲基丙烯酸酯、己二醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、季戊二醇二甲基丙烯酸酯、三丙二醇二甲基丙烯酸酯等脂肪族二醇加成丙烯酸、甲基丙烯酸后的材料。
另外，也能使用在聚乙二醇、聚丙二醇、聚丁二醇等的聚醚多元醇中附加了丙烯酸、甲基丙烯酸而得到的聚醚丙烯酸酯、聚醚甲基丙烯酸酯和在由众所周知的二碱基酸、醇获得的聚酯多元醇加成丙烯酸、甲基丙烯酸而得到的聚酯丙烯酸酯、聚酯甲基丙烯酸酯。
还可以使用在使众所周知的多元醇、二醇和聚异氰酸盐反应而得到的聚亚安酯中附加了丙烯酸、甲基丙烯酸后得到的聚尿烷丙烯酸酯、聚尿烷甲基丙烯酸酯。
另外，也可以使用双酚A、双酚F、氢化双酚A、氢化双酚F或者是它们的烯基氧化物加成物与丙烯酸、甲基丙烯酸加成之后的产物；或者是三聚异氰酸烯基氧化物变性二丙烯酸酯、三聚异氰酸烯基氧化物变性二甲基丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、三环癸烷二甲醇二甲基丙烯酸酯等具有环状结构的物质。
作为上述放射线，可以使用电子线以及紫外线。使用紫外线时，必须在以下化合物中加入光聚合引发剂。光聚合引发剂可以使用芳香族酮。对于芳香族酮没有特别的限定，它将产生通常作为紫外线照射光源所使用的水银灯的发射光谱。理想的是在254nm、313nm、865nm波长下，吸光系数较大。作为其代表例有，乙酰苯、二苯甲酮、苯偶姻乙醚、苄基甲基缩酮、苄基乙基缩酮、苯偶因异丁酮、羟基二甲基苯基酮、1—羟基环己基苯基甲酮、2—2乙氧基乙酰苯、Michlers酮等，可以使用各种芳香族酮。芳香族酮的混合比率对于化合物(a)100质量部，为0.5～20质量部，理想的是2～15质量部，更理想的是3～10质量部。作为紫外线固化型结合剂而预先添加了光引发剂的材料是市场上有销售的，可以使用它。作为紫外线光源，使用了水银灯。水银灯使用20～200W/cm的灯，以速度0.3m/分钟～20m/分钟使用。基体和水银灯的距离一般理想的是1～30cm。
作为电子射线加速器，可以采用扫描方式、双扫描方式或幕帘束方式，但是理想的是以比较低的成本能取得大输出的幕帘束方式。作为电子射线特性，加速电压是100～1000kV，理想的是150～300kV，作为吸收量，是0.5～20Mrad，理想的是，1～10Mrad。当加速电压为10kV以下时，能量的透过量不足，如果超过1000kV，则聚合中使用的能量效率下降，在成本方面是不理想的。
<保护层>
作为形成保护层的材料，如果是透明的材料，就没有特别限定，但是作为材料，理想的是聚碳酸酯、三醋酸纤维、丙烯酸类聚合物。另外，理想的是在23℃、相对湿度50％下的吸湿率为5％以下的材料。理想的是保护层的表面粗糙度5nm以下，双折射率10nm以下。
须指出的是，“透明”是指对于记录、再现的激光，能使该光透射(透射率：80％以上)程度的透明。
保护层的厚度理想的是0.01～0.2mm的范围，更理想的是0.03～0.1mm的范围，最理想的是0.05～0.095mm的范围。
作为使用所述粘合剂层，把保护层粘贴到记录层或阻碍层上的方法，有在保护层上涂敷粘合剂，使溶剂干燥后，隔着该粘合剂，在中间层上放上保护层，通过用辊子加压，粘贴保护层的方法。
作为粘合剂的涂敷温度，为了控制粘度，理想的是23～50℃的范围，更理想的是24～40℃的范围，最理想的是25～37℃的范围。涂敷后，理想的是用50～300℃，更理想的是用80～200℃，最理想的是用100～150℃干燥。另外，作为粘贴保护层时的温度，理想的是0～100℃的范围，更理想的是15～50℃的范围。
另外，对于使用的粘合剂，在具有起模性的起模薄膜上涂敷粘合剂，使溶剂干燥后，粘贴保护层，再剥离起模薄膜，在保护层上设置粘合剂后，通过粘贴在记录层或阻碍层上，能粘贴保护层。特别是当粘合剂中含有的溶剂溶解保护层时，理想的是采用本方法。
当使用在起模薄膜上设置有粘合剂层的薄片时，只要作为基体材料而使用的薄膜不溶于粘合剂中包含的溶剂中，就未特别限制，例如使用了聚对苯二甲酸乙二醇酯、聚丙烯、聚乙烯、聚氯乙烯等的塑料薄膜或牛皮纸、高质量纸、粘土层纸、日本纸等、人造丝、聚酯等的无纺布、由聚酯、尼龙、丙烯酸等的合成纤维构成的织布、铝、铜、不锈钢等的金属箔，但是从在薄膜上连续、薄而均匀地涂敷起模剂层的角度出发，理想的是塑料薄膜。
另外，作为使用的起模剂，能适当选择使用硅类起模剂和长链烃类起模剂等从以往就使用的各种起模剂。
[实施例]
下面，详细说明本发明的实施例，但是本发明并不局限于此。
(实施例1)
在具有厚度1.1mm、外径120mm、内径15mm的螺旋状的凹槽(磁道间隔：340nm、沟深度：30nm、沟宽度15nm)的注射模塑成形的聚碳酸酯树脂衬底的具有凹槽的面上使用Unaxis公司制造的Cube，在Ar气氛下，溅射Ag，形成120nm的层厚的反射层。在该溅射时，为了确保紧贴区域，使用掩模，在图1的虚线部分所示的内周附近和外周附近的区域中不形成反射层。
接着，把2g用下面构造式1表示的色素A溶解于2，2，3，3-四氟丙醇100ml中，调配了色素涂敷液。通过旋转镀膜法，把涂敷液均匀地涂敷到衬底上，形成了沟内的厚度100nm、纹间表面部的厚度为70nm的记录层。然后，清洗没有形成所述反射层的内周和外周的一部分的区域。接着，使用净化炉，在40℃进行一小时的退火。这时，在用隔离块隔开间隔的状态下，把衬底支撑在垂直的叠杆上。
[化学式1]
Figure C03120114D00171
在退火后，通过RF溅射，在溅射功率4kW、压力2×10-2Pa、10秒的条件下，溅射ZnS-SiO2(8:2)，使变为50nm的厚度，形成了阻碍层。这时，使用在反射层的形成中使用的掩模，在内周和外周的一部分区域不形成阻碍层。
在使衬底和保护层的中心彼此一致的状态下，粘贴以15μm的厚度在表面涂敷了粘合剂的聚碳酸酯保护层(帝人公司制造的PURE ACE，厚度：85μm)。在外周和内周，通过粘合剂层使衬底和保护层紧贴的紧贴区域的直径方向长度的最大值是0.5mm。通过以上的步骤，取得了实施例1的光信息记录介质。
(比较例1—1)
在实施例1中，除了反射层的整个面形成到衬底的边缘部以外，与实施例1同样做，取得了比较例1—1的光信息记录介质。
(比较例1—2)
在实施例1中，除了记录层的整个面形成到衬底的边缘部以外，与实施例1同样做，取得了比较例1—2的光信息记录介质。
(比较例1—3)
在实施例1中，除了阻碍层的整个面形成到衬底的边缘部以外，与实施例1同样做，取得了比较例1—3的光信息记录介质。
(比较例1—4)
在实施例1中，除了通过粘合剂层使衬底和保护层紧贴的紧贴区域的直径方向长度为0.1mm以外，与实施例1同样做，取得了比较例1—4的光信息记录介质。
[评价]
对于在实施例1和比较例1—1～1—4中取得的光信息记录介质，进行了以下的(1)剥离测试、(2)落下测试以及(3)记录特性评价。
(1)剥离测试
在取得的光信息记录介质的保护层一侧的面上贴附橡胶带，进行剥离测试，根据以下的评价标准取得了以下的评价结果。表1中表示了结果。
[评价结果]
○：未产生剥离
×：产生剥离
(2)落下测试
从1m的高度使光信息记录介质20次落到混凝地板上，观察衬底的外侧端部的剥离，根据以下的评价标准取得了以下的评价结果。表1中表示了结果。
A：几乎观察不到衬底的外侧端部的剥离。
B：观察到了衬底的外侧端部的剥离。
(3)记录特性评价
通过DDU1000(Pulsetec(株式会社)制造)，以线速度4.9m/s、凹槽长度160nm下进行记录，测定了所述(1)剥离测试前后的C/N。表1中表示了结果。
表1
 
剥离测试 落下测试 C/N(dB)测试前 C/N(dB)测试后
实施例1 ○ A 46 46
比较例1—1 × B 46 42
比较例1—2 × B 46 41
比较例1—3 × B 46 42
比较例1—4 × B 46 42
根据表1，从所述(1)剥离测试、(2)落下测试以及(3)记录特性评价可知，实施例1的光信息记录介质不但具有高的紧贴性，而且具有高的记录特性。
从而根据本发明，能提供各层间的紧贴性高，具有稳定的记录再现特性的光信息记录介质。
(实施例2)
在具有厚度1.1mm、外径120mm、内径15mm的螺旋状的凹槽(磁道间隔：340nm、沟深度：30nm、沟宽度15nm)的注射模塑成形的聚碳酸酯树脂衬底的具有凹槽的面上使用Unaxis公司制造的Cube，在Ar气氛下，溅射Ag，形成120nm的层厚的反射层。
接着，把2g用上述化学式1所示的色素A溶解于2，2，3，3-四氟丙醇100ml中，调配了色素涂敷液。通过旋转镀膜法，把涂敷液均匀地涂敷到衬底上，形成了沟内的厚度100nm、纹间表面部的厚度70nm的记录层。然后，清洗没有形成所述反射层的内周和外周的一部分的区域。接着，使用净化炉，在40℃进行一小时的退火。这时，在用隔离块隔开间隔的状态下，把衬底支撑在垂直的叠杆上。
在退火后，通过RF溅射，在溅射功率4kW、压力2×10-2Pa、10秒的条件下，溅射ZnS-SiO2(8:2)，使变为50nm的厚度，形成了阻碍层。这时，形成的阻碍层的外周比所述记录层的外周还靠外侧1mm，使阻碍层围绕记录层的外周缘部。
把大日本油墨化学株式会社的ex8204(结合剂)分散(在固定喷嘴的状态下，使衬底旋转约1圈)为环状，然后，在使衬底和保护层的中心彼此一致的状态下，把聚碳酸酯保护薄膜(帝人公司制造的PURE ACE，厚度：85μm)安放在衬底上，以转速5000rpm旋转3秒，使结合剂全面扩散，并且使多余的结合剂飞散。然后，照射紫外线，使结合剂固化。如上所述，能够无气泡地形成层厚为25μm的结合剂层。把保护层和结合剂层的总厚度设定为100μm。根据以上的步骤，取得了实施例2的光信息记录介质。
(比较例2—1)
在实施例2中，除了使记录层的外周位于比阻碍层更靠外侧以外，与实施例2同样做，取得了比较例2—1的光信息记录介质。
另外，对于在实施例2和比较例2—1中获得的光信息记录介质，测定了保存前的初始状态和在80℃、相对湿度85％的气氛下放置了24小时后的外周部的C/N。须指出的是，使用DDU1000(Pulsetec(株式会社)，以线速度4.9m/s、凹槽长度160nm下进行记录，并进行了测定。表2中表示了结果。
表2
 
C/N(放置前) C/N(放置后)
实施例2 46dB 45dB
比较例2—1 46dB 40dB
根据表2，实施例2的光信息记录介质的C/N几乎未变化。而可知比较例2—1的光信息记录介质C/N下降，保存性低。
从而根据本发明能提供保存性高，具有稳定的记录再现特性的光信息记录介质。
(实施例3)
在具有厚度1.1mm、外径120mm、内径15mm的螺旋状的凹槽(磁道间隔：340nm、沟深度：30nm、沟宽度15nm)的注射模塑成形的聚碳酸酯树脂衬底的具有凹槽的面上使用Unaxis公司制造的Cube，在Ar气氛下，溅射Ag，形成120nm厚的反射层。在该溅射时，为了确保紧贴区域，使用掩模，在图7的虚线部分所示的内周附近和外周附近的区域中不形成反射层。
接着，把2g用上述的化学式1所示的色素A溶解于2，2，3，3-四氟丙醇100ml中，调配了色素涂敷液。通过旋转镀膜法，把涂敷液均匀地涂敷到衬底上，形成了沟内的厚度100nm、凸台部的厚度70nm的记录层。然后，清洗不形成所述反射层的内周和外周的一部分的区域。接着，使用净化炉，在40℃进行一小时的退火。这时，在用隔离块隔开间隔的状态下，把衬底支撑在垂直的叠杆上。
在退火后，通过RF溅射，在溅射功率4kW、压力2×10-2Pa、10秒的条件下，溅射ZnS-SiO2(8:2)，使变为50nm的厚度，形成了阻碍层。这时，使用在反射层的形成中使用的掩模，使内周和外周的一部分区域不形成阻碍层。
把大日本油墨化学株式会社的ex8204(结合剂)分散(在固定喷嘴的状态下，使衬底旋转约1圈)为环状，然后，在使衬底和保护层的中心彼此一致的状态下，把聚碳酸酯保护层(帝人公司制造的PURE ACE，厚度：85μm)安放在衬底上，以转速5000rpm旋转3秒，使结合剂全面扩散，并且使多余的结合剂飞散。然后，照射紫外线，使结合剂固化。如上所述，能够无气泡地形成层厚25μm的结合剂层。把保护层和结合剂层的总厚度设定为100μm。根据以上的步骤，取得了实施例3的光信息记录介质。
(比较例3—1)
在实施例3中，除了记录层的整个面形成到衬底的边缘部以外，与实施例3同样做，取得了比较例3—1的光信息记录介质。
另外，对于在实施例3和比较例3—1中取得的光信息记录介质，进行了以下的(1)剥离测试、(2)落下测试以及(3)记录特性评价。
(1)剥离测试
在取得的光信息记录介质的保护层一侧的面上帖附橡胶带，进行剥离测试，根据以下的评价标准取得了以下的评价结果。表3中表示了结果。
○：未产生剥离
×：产生剥离
(2)落下测试
从1m的高度使其20次落到混凝土板上，观察衬底的外侧端部的剥离，根据以下的评价标准进行评价。表3中表示了结果。
A：几乎观察不到衬底的外侧端部的剥离。
B：只观察到一点衬底的外侧端部的剥离。
C：观察到相当大的衬底的外侧端部的剥离。
(3)记录特性评价
通过DDU1000(Pulsetec(株式会社)制造)，以线速度4.9m/s、凹槽长度160nm下进行记录，测定了所述(1)剥离测试和(2)落下测试前后的C/N。表3中表示了结果。
表3
 
剥离测试 落下测试 C/N(dB)测试前 C/N(dB)剥离测试后 C/N(dB)落下测试
实施例3 ○ A 46 46 46
比较例3—1 × C 46 43 42
根据表3，从所述(1)剥离测试、(2)落下测试以及(3)记录特性评价可知，实施例3的光信息记录介质不但具有高的紧贴性，而且具有高的记录特性。

Claims (3)

1、一种盘状的光信息记录介质，在衬底上按顺序具有记录层、粘合剂层或结合剂层以及保护层，其特征在于，
磁道间隔为250～400nm，沟深度为10～150nm，照射500nm以下的波长的激光来记录、再现信息，并且具有中心孔，
所述保护层的厚度是0.01～0.2mm，
所述记录层是含有色素化合物的层，
所述衬底和所述保护层通过粘合剂层或结合剂层在内周附近和/或外周附近的至少一部分的区域紧贴，并且该紧贴区域的直径方向长度的最大值，在外周近旁是0.4～2mm，在内周近旁是0.4～15mm。
2、一种盘状的光信息记录介质，在衬底上按顺序具有反射层、记录层、阻碍层、粘合剂层或结合剂层以及保护层，其特征在于，
磁道间隔为250～400nm，沟深度为10～150nm，照射500nm以下的波长的激光来记录、再现信息，并且具有中心孔，
所述记录层是含有色素化合物的层，
所述阻碍层围绕所述记录层的外周边缘和/或内周边缘，
所述粘合剂层或结合剂层围绕所述记录层的外周缘部和/或内周缘部，
该阻碍层外周直径与该记录层的外周直径之差为0.4～4mm，该阻碍层内周直径比该记录层的内周直径小0.4～15mm。
3、一种盘状的光信息记录介质，在衬底上按顺序具有记录层、阻碍层、粘合剂层或结合剂层以及保护层，其特征在于，磁道间隔为250～400nm，沟深度为10～150nm，照射500nm以下的波长的激光来记录、再现信息，并且具有中心孔，
所述记录层是包含有机色素的层，
所述衬底和所述阻碍层在内周附近和/或外周附近的至少一部分区域中紧贴，并且该紧贴区域的直径方向长度的最大值，在外周近旁是0.4～2mm，在内周近旁是0.4～15mm。
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US20050073941A1 (en) 2005-04-07
US6961951B2 (en) 2005-11-01
US6959446B2 (en) 2005-10-25
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US20030210643A1 (en) 2003-11-13
US20050102694A1 (en) 2005-05-12

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