CN1245716C - 光记录介质 - Google Patents

光记录介质 Download PDF

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Publication number
CN1245716C
CN1245716C CN02123101.XA CN02123101A CN1245716C CN 1245716 C CN1245716 C CN 1245716C CN 02123101 A CN02123101 A CN 02123101A CN 1245716 C CN1245716 C CN 1245716C
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China
Prior art keywords
optical recording
recording media
layer
thickness
overlayer
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Expired - Fee Related
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CN02123101.XA
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English (en)
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CN1391219A (zh
Inventor
齐藤真二
角田毅
石田寿男
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Fujifilm Corp
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Fujifilm Corp
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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
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • 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
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/256—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of layers improving adhesion between layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • 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
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • 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
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/258—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers
    • G11B7/259—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of reflective layers based on silver
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/21—Circular sheet or circular blank

Abstract

一种光记录介质，在基板上依次设有光反射层、记录层和覆盖层，通过自该覆盖层侧照射波长450nm以下的激光进行记录和再现，其特征在于，该光记录介质在上述记录层和上述覆盖层之间还设有厚度1nm以上80nm以下的溅射层，用粘结剂将该溅射层和上述覆盖层粘接。从而提供一种高密度且具有优良记录特性的补充记录型光记录介质。

Description

光记录介质
技术领域
本发明涉及具有由有机化合物构成的记录层，用特定波长的激光能够进行记录和再现的补充记录型光记录介质。
背景技术
以前广泛已知用激光仅可记录一次信息的补充记录型光记录介质被称为CD-R。其优点在于能用市售的CD播放机进行再现，另外，最近随着个人电脑的普及，其需要也增加。另外，作为能通过CD-R进行大容量记录的介质，用于与数字高清晰度电视的录像等对应的补充记录型数字多用光盘(DVD-R)也已实用化。
作为这些补充记录型光记录介质的一种结构，已知在圆盘状基板上依次层叠由Au等组成的光反射层、有机化合物组成的记录层、以及含有使之粘接在该记录层上用的粘接层的树脂层(以下有时适当称为覆盖层)。通过从上述树脂层侧照射激光，可以进行记录和再现。补充记录型光记录介质上的信息记录，可以通过记录层的激光照射部分吸收该光线而局部发热变形(例如形成凹坑等)进行。另一方面，信息的再现通常通过将与记录用激光波长相同的激光照射在补充记录型光记录介质上，检测出记录层发热变形部位(记录部分)与未变形部分(未记录部分)的反射率差异进行。
最近，因特网等网络和高画质TV迅速普及。另外，HDTV(高清晰度电视，High Definition Television)的放映也接近开始。在这种状况下，需要一种能简便、廉价地记录图像信息的大容量光记录介质。上述DVD-R现在充分起着大容量记录介质的作用，但是大容量化、高密度化的要求提高，另一方面，也需要开发出能适应这些要求的记录介质。因此，人们正在开发一种能用更短波长的光线进行高密度记录的更大容量的记录介质。特别是仅能记录一次信息的补充记录型光记录介质，由于作为大容量信息的长期保存或备份用的使用频率正在提高，所以对其开发的要求强烈。
光记录介质的高密度化，通常可以通过使记录和再现用激光短波长化、使物镜高NA化，从而减小电子束光点而实现。最近以来，迅速进行了从波长680nm、650nm和635nm的红色半导体激光器至能进行更超高密度记录的波长400～500nm的蓝紫色半导体激光器(以下称为蓝紫色激光器)的开发，而且还进行了与之相对应的光记录介质的开发。特别是自从蓝紫色激光器出售以来，人们研究开发了一种利用该蓝紫色激光器和高NA备份的光记录系统，具有相变化记录层的改写型光记录介质和光记录系统已经作为DVR系统(《ISOM2000》210～211页)发表。这样，对于改写型光记录介质的高密度化课题，已经获得一定成果。
利用上述那种蓝紫色激光器和高NA备份的光记录系统中使用的光记录介质在向记录层照射蓝紫色激光时，为了使高NA物镜焦点吻合，优选使激光入射的覆盖层薄层化。其中，作为覆盖层，例如使用薄的薄膜，用粘结剂将其粘接在记录层上。覆盖层的厚度通常包括粘结剂固化形成的粘接层在内约为100μm，可以利用照射的激光波长或NA使之最适化。
然而，通过利用蓝紫色激光器和高NA备份的光记录系统能进行记录和再现的补充记录型光记录介质中，记录层中使用有机化合物时，存在不能得到充分的记录特性的问题。其原因虽然尚不清楚，但是据推测是因为记录层中的有机化合物溶解在粘接层内的粘结剂中，因而在上述记录层中产生微小不均而造成的。
发明内容
因此，本发明是鉴于上述背景技术中存在的问题提出的，其目的在于提供一种高密度并具有优良记录特性的补充记录型光记录介质。
更详细的本发明目的可以利用以下方法实现。
<1>一种光记录介质，在基板上依次设有光反射层、记录层和覆盖层，通过从该覆盖层侧照射波长450nm以下的激光进行记录和再现，其特征在于，该光记录介质在上述记录层和上述覆盖层之间还设有厚度2nm以上80nm以下的溅射层，用粘结剂将该溅射层和上述覆盖层粘接，所述溅射层含有Si、Zn、Ag、Al、Ti、Sn或Ge的单质或其化合物的组合。
<2>如<1>所述的光记录介质，其特征在于，所述溅射层的厚度在2nm以上50nm以下。
<3>如<1>所述的光记录介质，其特征在于，所述溅射层使70％以上的用于记录和再现的上述激光透过。
<4>如<1>所述的光记录介质，其特征在于，所述溅射层的厚度在2～50nm的范围内。
<5>如<1>所述的光记录介质，其特征在于，所述由粘结剂构成的粘结层的厚度在1～1000μm的范围内。
<6>如<1>所述的光记录介质，其特征在于，所述粘结剂由放射线固化性树脂构成。
<7>如<1>所述的光记录介质，其特征在于，所述溅射层的厚度为2～20nm。
<8>如<1>所述的光记录介质，其特征在于，所述记录层含有在400nm以下具有极大吸收波长的有机化合物。
<9>如<8>所述的光记录介质，其特征在于，所述的有机化合物选自三唑、三嗪、花青、份菁、氨基丁二烯、酞菁、桂皮酸、氧化还原色素、偶氮、oxonol或苯并三唑。
<10>如<8>所述的光记录介质，其特征在于，所述的有机化合物选自花青、氨基丁二烯、苯并三唑或酞菁。
附图说明
图1是表示本发明一种光记录介质实例的剖面示意图。
其中，10-基板，20-光反射层，30-记录层，40-溅射层，50-覆盖层，100-光记录介质，200-物镜。
具体实施方式
以下参照附图，详细说明本发明光记录介质的实施方式。
图1是表示本发明光记录介质100的例示实施方式的剖面示意图。如图1所示，光记录介质100具有在基板10上依次层叠了光反射层20、记录层30、溅射层40和覆盖层50的结构。另外，本发明的光记录介质100必要时还可以包含其他层。以下就构成本发明光记录介质100的各要素进行详细说明。另外，本发明的光记录介质100能够利用具有450nm以下波长的激光进行记录和再现。
<基板>
基板10可以由例如玻璃，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系树脂，环氧树脂，无定形聚烯烃和聚酯等材料制成。上述材料根据需要也可以合并使用。其中，从耐湿性、尺寸稳定性和价格等方面考虑优选聚碳酸酯。基板10的厚度一般在0.4～1.5mm的范围内，优选在1.1～1.3mm的范围内。
在基板10表面上，优选形成跟踪用槽或表现地址信号等信息的凹凸(预槽)。优选在将聚碳酸酯等树脂材料注塑成型或挤压成型时直接在基板上形成这种预槽。
另外，预槽的形成也可以通过设置预槽层进行。作为预槽层的材料，可以使用丙烯酸的单酯、二酯、三酯及四酯中的至少一种单体(或低聚物)和光聚合引发剂的混合物。预槽层的形成例如可以通过首先在精密制造的母模(stamper，原模)上涂布上述丙烯酸酯和聚合引发剂组成的混合液，进而将基板10置于此涂布液层上后，通过基板10或母模照射紫外线，使涂布层固化，使基板与涂布层凝固附着。接着，从母模上剥离基板从而可以得到。预槽层的厚度一般处于0.01～100μm的范围内，优选处于0.05～50μm的范围内。
为了获得更高的记录密度，基板10优选采用形成了比CD-R或DVD-R磁道间距更窄的预槽的基板。基板10预槽的磁道间距为100～600nm。
另外，预槽的深度优选处于20～150nm的范围内，其半值宽度优选处于50～250nm的范围内。因此，本发明的光记录介质由于具有高感光度，所以即使用低激光器功率也能进行记录，从而具有可以使用价格低廉的激光器或者能够延长激光器使用寿命等优点。
另外，为了改善平面性和提高粘着力，优选在后述的设置光反射层20一侧的基板表面上形成底涂层。
作为该底涂层的材料，可以举出例如聚甲基丙烯酸甲酯、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、硝化纤维素、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，硅烷偶合剂等表面改质剂。
将上述材料溶解或分散在适当溶剂中制成涂布液后，用旋转涂覆法、浸涂法、挤压涂布法等涂布方法将此涂布液涂布在基板表面上，从而可以形成底涂层。底涂层的厚度一般处于0.005～20μm的范围内，优选处于0.01～10μm的范围内。
<光反射层>
光反射层20是为了提高信息再现时的反射率而设置的。作为光反射层20材料的光反射性物质，是对激光的反射率处于70％以上的物质，其具体实例可以举出例如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等金属或类金属或不锈钢。这些物质可以单独使用，或者两种以上组合使用，或制成合金使用。光反射层20优选含有Au、Ag中的任意一种，其含量越高越优选。光反射层20例如可以通过真空蒸镀、溅射或离子喷涂上述反射性物质在基板10上形成。光反射层20的厚度一般处于10～800nm的范围内，优选20～500nm的范围，更优选50～300nm的范围。
<记录层>
记录层30优选由在400nm以下具有极大吸收的有机化合物构成，使之可以用450nm波长的激光进行记录和再现。另外，也可以由在超过400nm的波长区域具有其它第二吸收带的有机化合物构成。
作为上述有机化合物，具体地说，优选在特开平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号公报和特开2000-158818号公报的各公报中记载的物质，或者三唑、三嗪、花青、份菁、氨基丁二烯、酞菁、桂皮酸、氧化还原色素、偶氮、oxonol苯并噁唑、苯并三唑等，更优选花青、氨基丁二烯、苯并三唑、酞菁。
将上述花青色素等有机化合物，进而根据需要将粘接剂溶解在溶剂中制成涂布液，然后将此涂布液涂布在光反射层20表面上形成涂膜后干燥，从而可以形成记录层30。
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、均质器处理、分散器处理、混砂机处理、搅拌器搅拌处理等方法。此外根据要求还可以在涂布液中再添加抗氧化剂、UV吸收剂、增塑剂及润滑剂等各种添加剂。
作为记录层30的涂布液的溶剂，可以举出例如乙酸丁酯、乙酸溶纤剂酯等酯类，甲基乙基酮、环己酮、甲基异丁基酮等酮类，二氯甲烷、1，2-二氯乙烷、氯仿等卤代烃类，二甲基甲酰胺等酰胺类，环己烷等烃类，四氢呋喃、乙醚、二氧六环等醚类，乙醇、正丙醇、异丙醇、正丁醇、双丙酮醇等醇类，2，2，3，3-四氟丙醇等氟系溶剂，乙二醇单甲基醚、乙二醇单乙基醚、丙二醇单甲基醚等二醇醚类等。考虑到使用的有机化合物的溶解性，上述溶剂可以单独使用或将两种以上适当合并使用。
作为粘接剂的例子，可以举出例如明胶、纤维素衍生物、葡聚糖、松香、橡胶等天然有机高分子物质，以及聚氨酯、聚乙烯、聚丙烯、聚苯乙烯、聚异丁烯等烃类树脂，聚氯乙烯、聚偏二氯乙烯、聚氯乙烯-聚醋酸乙烯酯共聚物等乙烯基系树脂，聚丙烯酸甲酯、聚甲基丙烯酸甲酯等丙烯酸树脂，聚乙烯醇、氯代聚乙烯、环氧树脂、丁缩醛树脂、橡胶衍生物、酚醛树脂等热固性树脂的初期缩聚物等合成有机高分子。作为记录层30的材料，合并使用粘接剂时，粘接剂的用量相对于100质量份有机化合物为0.2～20质量份，优选0.5～10质量份，更优选1～5质量份。通过使记录层30中含有粘接剂，也可以改善记录层的保存稳定性。
以此方法制备的涂布液中有机化合物的浓度一般在0.01～10质量％的范围内，优选在0.1～5质量％的范围内。
作为涂布方法，可以举出喷涂法、旋涂法、浸渍涂布法、辊涂法、刮涂法、刮刀辊法和丝网印刷法等。记录层30可以是单层，也可以是多层。记录层30的厚度一般处于20～500nm的范围内，优选50～300nm的范围。另外，记录层30不仅可以在基板的一面设置，而且还可以在两面进行设置。
另外，作为涂布温度，只要为23～50℃即可，并没有特别的问题，优选24～40℃，更优选25～37℃。
为了提高记录层30的耐光性，可使该记录层含有各种褪色防止剂。
作为褪色防止剂，一般可以使用单态氧猝灭剂。作为单态氧猝灭剂，可以使用已在公知的专利说明书等刊物上记载的物质。
作为其具体实例，可以举出在特开昭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号公报等各公报，以及德国专利350399号说明书、日本化学会志1992年10月号第1141页等中记载的物质。
上述单态氧猝灭剂等褪色防止剂的含量在记录层30总固态成分中-般占0.1～50质量％，优选占0.5～45质量％，更优选3～40质量％，特别优选占5～25质量％。
<溅射层>
溅射层40优选使用于记录和再现的激光70％以上透过，更优选90％以上透过。
作为溅射层40的材料，并没有特别限制，优选Si、Zn、Ag、Al、Ti、Sn、W、Cu、Ge、Mn、Sb、Zr等单质或化合物(氧化物、氮化物、硫化物等)，更优选Si、Zn、Ag、Al、Ti、Sn、Ge的单质或化合物。这些材料可以在考虑熔点和刚性等各种物性的条件下适当选择使用，因而既可以单独使用，也可以两种以上组合使用。
溅射层40可以使用例如Unakcis公司生产的RF溅射装置等公知溅射装置在记录层30上形成。溅射层40的厚度一般处于1～80nm的范围内，优选2～50nm的范围内，更优选3～20nm的范围内。
<粘接层>
在溅射层40上设置用于粘接后述的覆盖层50的未图示的粘接层。上述粘接层中使用的粘结剂例如优选由放射线固化树脂构成，其中，为了防止光盘翘曲，优选固化收缩率小的树脂。另外，粘接层的厚度为了使其保持弹性，优选处于1～1000μm的范围内，更优选在5～500μm的范围内，特别优选在10～100μm的范围内。
另外，上述放射线固化性树脂优选分子中具有两个以上放射线官能性双键的树脂。
作为上述放射线固化性树脂，可以举出例如丙烯酸酯类、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、乙烯基醚类、乙烯基酯类等。更优选两官能以上的丙烯酸酯化合物和甲基丙烯酸酯化合物。
作为放射线固化性树脂的具体实例，可以使用以乙二醇二丙烯酸酯、丙二醇二丙烯酸酯、丁二醇二丙烯酸酯、己二醇二丙烯酸酯、二甘醇二丙烯酸酯、三甘醇二丙烯酸酯、四甘醇二丙烯酸酯、新戊二醇二丙烯酸酯、二缩三丙二醇二丙烯酸酯、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、二甘醇二甲基丙烯酸酯、三甘醇二甲基丙烯酸酯、四甘醇二甲基丙烯酸酯、新戊二醇二甲基丙烯酸酯、二缩三丙二醇二甲基丙烯酸酯等为代表的使丙烯酸、甲基丙烯酸与脂肪族二醇加成得到的物质。
另外，还可以使用使丙烯酸、甲基丙烯酸与聚乙二醇、聚丙二醇、聚丁二醇等聚醚多元醇加成得到的聚醚丙烯酸酯、聚醚甲基丙烯酸酯，或者使丙烯酸、甲基丙烯酸与由公知的二元酸、二元醇得到的聚酯多元醇加成得到的聚酯丙烯酸酯、聚酯甲基丙烯酸酯。
还可以使用通过使丙烯酸、甲基丙烯酸与使公知的多元醇、二元醇和聚异氰酸酯反应得到的聚氨酯加成得到的聚氨酯丙烯酸酯、聚氨酯甲基丙烯酸酯。
也可以使用使丙烯酸、甲基丙烯酸与双酚A、双酚F、氢化双酚A、氢化双酚F或其烯化氧加成物加成得到的物质，或者异三聚氰酸烯化氧改性二丙烯酸酯、异三聚氰酸烯化氧改性二甲基丙烯酸酯、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。
以上说明了能构成粘接层的放射线固化性树脂，但是还可以适当使用市售的例如大日本油墨社制的“SD-640”、“SD-347”等UV固化性树脂(UV固化性粘结剂)。
作为使上述放射线固化性树脂固化用的放射线，可以适当使用电子射线和紫外线。另外，使用紫外线的场合下，必须在以下化合物中添加光聚合引发剂。
作为光聚合引发剂，可以使用例如芳香族酮。芳香族酮并无特别限制，产生通常作紫外线照射光源使用的汞灯的明线光谱。优选在254、313、865nm波长下吸光系数较大的化合物。作为其代表性实例，有苯乙酮、二苯甲酮、苯偶姻乙醚、苄基甲基缩酮、苄基乙基缩酮、苯偶姻异丁基酮、羟基二甲基苯基酮、1-羟基环己基苯基酮、2，2-二乙氧基苯乙酮、米蚩酮等，可以使用各种芳香族酮。
芳香族酮的混合比，相对于100质量份上述紫外线固化性树脂，占0.5～20质量份，优选占2～15质量份，更优选占3～10质量份。当然还可以使用作为紫外线固化型粘结剂事先添加有光引发剂的市售品。
作为紫外线光源，可以使用汞灯。汞灯可用20～200W/cm的灯泡，在0.3m/分钟～20m/分钟的速度下使用。基体和汞灯间的距离一般优选1～30cm。
作为电子射线加速器，可以采用扫描式、双扫描式或帘束式，优选能以较低价格获得大输出功率的帘束式。作为电子射线特性，加速电压为100～1000kV，优选150～300kV；吸收剂量为0.5～20Mrad，优选1～10Mrad。加速电压低于10kV时，能量的透过量不足，若超过1000kV，则存在用于聚合的能量效率降低，不经济的问题。
<覆盖层>
覆盖层50用上述粘结剂(借助于粘结剂)在溅射层40上形成。相对于记录和再现中使用的激光，优选透过率为80％以上，更优选为90％以上。另外，覆盖层50优选其表面粗度Ra在5nm以下的树脂片材，作为这种树脂片材，可以举出例如聚碳酸酯(帝人社出品的Piuaes，帝人化成社出品的Panrite)、三乙酸纤维素(富士胶片社出品的Phzidack)、PET(东re社出品的Lumira)，更优选聚碳酸酯、三乙酸纤维素。另外，覆盖层50的表面粗度Ra取决于树脂的种类、制膜方法和填料的有无等。另外，覆盖层50的表面粗度Ra例如可以用WYKO公司出品的HD2000进行测定。
覆盖层50的厚度可以根据为了记录和再现而照射的激光的波长或NA适当确定，优选处于0.005～1mm的范围内，更优选处于0.01～0.5mm的范围内。
<其他层>
本发明的光记录介质100还可以在上述覆盖层上设置保护层。保护层例如可以由紫外线固化性树脂形成。
保护层例如可以用旋涂法将紫外线固化性粘接剂涂布在覆盖层50的表面上，然后用UV照射灯照射紫外线，使UV固化性粘结剂固化而形成。
本发明光记录介质100的激光入射侧表面粗度可以由所用覆盖层50的表面粗度、基板10的表面粗度、光反射层20的形成条件、记录层30的种类、制膜条件、粘结层的种类、涂覆条件以及保护层种类和涂布条件等适当确定。
对于本发明的光记录介质100例如可以采用以下方式进行信息的记录和再现。首先，以给定的线速度(0.5～10米/秒)或给定的角速度一边使光记录介质100旋转，一边从覆盖层50侧通过物镜200照射蓝紫色激光(例如波长405nm)等记录用光线。通过这种照射光，记录层30吸收该光线局部温度上升，例如形成凹坑，使其光学特性改变，因而可以记录信息。以上述方式记录的信息的再现，可以通过一边使光记录介质100以给定的定线速度旋转，一边从覆盖层50侧照射蓝紫色激光，检出其反射光而进行。
实施例
以下利用实施例进一步详细说明本发明，但是本发明不受这些实施例的限制。
〔实施例1〕
(光记录介质的制作)
注塑成形聚碳酸酯树脂(帝人社出品的聚碳酸酯，商品名：PanriteAD5503)基板，其具有螺旋状槽(深度100nm，宽度0.120μm，磁道间距0.3μm)，厚度1.1毫米，直径120毫米。在得到基板的具有槽的面上溅射Ag，形成100nm厚的光反射层。
然后，将2g酞菁系有机化合物A(极大吸收：340nm)混合在148ml2，2，3，3-四氟丙醇中，进行2小时超声波处理，使之溶解，制成记录层形成用涂布液。在23℃、50％RH的条件下，一边使转数变化到300～4000rpm，一边用旋涂法将制备的涂布液涂布在光反射层上。接着，在23℃、50％RH下保持2小时使之干燥，形成记录层(厚度：100nm)。
在记录层上溅射ZnS-SiO2，使之厚度为20nm，形成溅射层。用旋涂法在200rpm的转数下，将UV固化粘结剂(大日本油墨化学社制，SD-347，在上述有机化合物中的溶解度为0.05wt％)涂布在溅射层上。使聚碳酸酯片材(帝人社制Piuaes，Ra：1nm)重叠在涂布的UV固化粘结剂上后，一边使转数变化到300～4000rpm，一边使UV固化粘结剂在整个记录层表面上扩展。然后用UV照射灯照射紫外线，使UV固化粘结剂固化，形成覆盖层。
而且，用旋涂法在200rpm的转数下将UV固化粘结剂(大日本油墨化学社制，SD-347)涂布在覆盖层上，然后，一边使转数变化到300～4000rpm，一边使UV固化粘结剂在整个覆盖层表面上扩展。接着，用UV照射灯照射紫外线，使UV固化粘结剂固化，形成保护层。这样制成实施例1的光记录介质。
(光记录介质记录特性的评价)
(1)C/N(载波噪声比)
使用搭载了405nm激光、NA：0.85备份的记录再现评价机(Parsteck社制：DDU1000)，在时钟频率66MHz/线速度5.6m/s的条件下利用单一频率的信号(2T＝0.13μm)对制作的光记录介质进行记录和再现，用光谱分析仪测定C/N。
(2)图像跳动(shutter)
使用搭载了405nm激光、NA：0.85备份的记录再现评价机(Parsteck社制：DDU1000)，在时钟频率66MHz/线速度5.6m/s的条件下利用1-7PP变频信号对制作的光记录介质进行记录和再现，用时间间隔分析仪测定图像跳动。
实施例1光记录介质的评价结果示于表1中。
〔实施例2〕
在实施例1中，除了用花青系有机化合物B(吸收波长373nm)代替酞菁系有机化合物A之外，与实施例1同样进行，制作实施例2的光记录介质。
对制成的光记录介质进行与实施例1同样的试验，评价记录特性。其结果示于表1中。
〔实施例3〕
在实施例1中，除了用氨基丁二烯系有机化合物C(吸收波长359nm)代替酞菁系有机化合物A之外，与实施例1同样进行，制作实施例3的光记录介质。
对制成的光记录介质进行与实施例1同样的试验，评价记录特性。其结果示于表1中。
〔实施例4〕
在实施例1中，除了用苯并三唑系有机化合物D(吸收波长373nm)代替酞菁系有机化合物A之外，与实施例1同样进行，制作实施例4的光记录介质。
对制成的光记录介质进行与实施例1同样的试验，评价记录特性。其结果示于表1中。
〔实施例5～8〕
在实施例1中，除了将溅射层厚度从20nm分别更改成80nm、50nm、10nm和2nm之外，与实施例1同样进行，制作实施例5～8的光记录介质。
对制成的光记录介质进行与实施例1同样的试验，评价记录特性。其结果示于表1中。
〔实施例9～13〕
在实施例1中，除了分别用AgO2、ZnS、GeO、Si和Ti代替构成溅射层的材料ZnS-SiO2之外，与实施例1同样进行，制作实施例9～13的光记录介质。
对制成的光记录介质进行与实施例1同样的试验，评价记录特性。其结果示于表1中。
〔比较例1〕
在实施例1中，除了在记录层和覆盖层间未形成溅射层之外，与实施例1同样进行，制作比较例1的光记录介质。
对制成的光记录介质进行与实施例1同样的试验，评价记录特性。其结果示于表1中。
〔比较例2〕
在实施例1中，除了将溅射层厚度由20nm改变成100nm之外，与实施例1同样进行，制作比较例2的光记录介质。
对制成的光记录介质进行与实施例1同样的试验，评价记录特性。其结果示于表1中。
表1
有机化合物   溅射层   C/N(dB)   图像跳动(％)
  材料   厚度(mm)
  实施例1   酞菁系化合物A   ZnS-SiO2   20   55   7.3
  实施例2   花青系化合物B   ZnS-SiO2   20   52   7.6
  实施例3   氨基丁二烯系化合物C   ZnS-SiO2   20   51   8.0
  实施例4   苯并三唑系化合物D   ZnS-SiO2   20   54   7.3
  实施例5   酞菁系化合物A   ZnS-SiO2   80   48   8.1
  实施例6   酞菁系化合物A   ZnS-SiO2   50   54   7.7
  实施例7   酞菁系化合物A   ZnS-SiO2   10   57   7.0
  实施例8   酞菁系化合物A   ZnS-SiO2   2   53   8.2
  实施例9   酞菁系化合物A   AgO2   20   53   7.5
  实施例10   酞菁系化合物A   ZnS   20   58   7.0
  实施例11   酞菁系化合物A   GeO   20   57   7.1
  实施例12   酞菁系化合物A   Si   20   57   7.2
  实施例13   酞菁系化合物A   Ti   20   56   7.6
  比较例1   酞菁系化合物A   -   -   28   12.1
  比较例2   酞菁系化合物A   ZnS-SiO2   100   37   9.9
表1的结果说明，通过在记录层和覆盖层间设置溅射层，记录特性的C/N和图像跳动良好。
另外，通过使溅射层处于80nm以下，优选处于50nm以下，记录层的分解热传递到覆盖层，能够促进该覆盖层的变形。覆盖层的变形由于能使入射的激光散射，所以能使调制度增高，并提高C/N。与此相对，如比较例2那样，在溅射层厚的场合下，推测产生分解热从溅射层放热的问题，或因溅射层本身刚性增高而难引起覆盖层变形的问题。
与蓝紫色激光和高NA备份对应的本发明的光记录介质，由于在记录层和覆盖层间设置溅射层，所以能够防止使记录特性降低的记录层不均现象的发生。因此，按照本发明，可以提供一种高密度且具有优良记录特性的补充记录型光记录介质。

Claims (10)

1、一种光记录介质，在基板上依次设有光反射层、记录层和覆盖层，通过从该覆盖层侧照射波长450nm以下的激光进行记录和再现，其特征在于，该光记录介质在上述记录层和上述覆盖层之间还设有厚度2nm以上80nm以下的溅射层，用粘结剂将该溅射层和上述覆盖层粘接，所述溅射层含有Si、Zn、Ag、Al、Ti、Sn或Ge的单质或其化合物的组合。
2、如权利要求1所述的光记录介质，其特征在于，所述溅射层的厚度在2nm以上50nm以下。
3、如权利要求1所述的光记录介质，其特征在于，所述溅射层使70％以上的用于记录和再现的上述激光透过。
4、如权利要求1所述的光记录介质，其特征在于，所述溅射层的厚度在2～50nm的范围内。
5、如权利要求1所述的光记录介质，其特征在于，所述由粘结剂构成的粘结层的厚度在1～1000μm的范围内。
6、如权利要求1所述的光记录介质，其特征在于，所述粘结剂由放射线固化性树脂构成。
7、如权利要求1所述的光记录介质，其特征在于，所述溅射层的厚度为2～20nm。
8、如权利要求1所述的光记录介质，其特征在于，所述记录层含有在400nm以下具有极大吸收波长的有机化合物。
9、如权利要求8所述的光记录介质，其特征在于，所述的有机化合物选自三唑、三嗪、花青、份菁、氨基丁二烯、酞菁、桂皮酸、氧化还原色素、偶氮、oxonol或苯并三唑。
10、如权利要求8所述的光记录介质，其特征在于，所述的有机化合物选自花青、氨基丁二烯、苯并三唑或酞菁。
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