CN1264153C - 光记录介质 - Google Patents

光记录介质 Download PDF

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Publication number
CN1264153C
CN1264153C CNB028107144A CN02810714A CN1264153C CN 1264153 C CN1264153 C CN 1264153C CN B028107144 A CNB028107144 A CN B028107144A CN 02810714 A CN02810714 A CN 02810714A CN 1264153 C CN1264153 C CN 1264153C
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CN
China
Prior art keywords
optical recording
recording layer
absorption coefficient
recording media
organic material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
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CNB028107144A
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English (en)
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CN1529884A (zh
Inventor
H·伯内斯
F·-K·布鲁德
W·黑泽
R·哈根
K·哈森吕克
S·科斯特罗米尼
P·兰登伯格
R·奥泽尔
T·索默曼
J·－W·施塔维茨
T·比林格尔
佐飞裕一
岩村贵
小山田光明
渡边英俊
玉田作哉
山本真伸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Sony Corp
Original Assignee
Bayer AG
Sony Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE10115227A external-priority patent/DE10115227A1/de
Priority claimed from DE10117462A external-priority patent/DE10117462A1/de
Priority claimed from DE10117461A external-priority patent/DE10117461A1/de
Priority claimed from DE10117464A external-priority patent/DE10117464A1/de
Priority claimed from DE10117463A external-priority patent/DE10117463A1/de
Priority claimed from DE10124585A external-priority patent/DE10124585A1/de
Priority claimed from DE10136063A external-priority patent/DE10136063A1/de
Priority claimed from DE2001136064 external-priority patent/DE10136064A1/de
Priority claimed from DE2001140165 external-priority patent/DE10140165A1/de
Priority claimed from DE2002100484 external-priority patent/DE10200484A1/de
Priority claimed from DE2002102571 external-priority patent/DE10202571A1/de
Application filed by Bayer AG, Sony Corp filed Critical Bayer AG
Publication of CN1529884A publication Critical patent/CN1529884A/zh
Application granted granted Critical
Publication of CN1264153C publication Critical patent/CN1264153C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/12—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring
    • C07D217/14—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with radicals, substituted by hetero atoms, attached to carbon atoms of the nitrogen-containing ring other than aralkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/12—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D455/00—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
    • C07D455/03—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
    • C07D455/04—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing quinolizine ring systems directly condensed with at least one six-membered carbocyclic ring, e.g. protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing a quinolizine ring system condensed with only one six-membered carbocyclic ring, e.g. julolidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/06—Cobalt compounds
    • C07F15/065—Cobalt compounds without a metal-carbon linkage
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    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol
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    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
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    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/045—Special non-pigmentary uses, e.g. catalyst, photosensitisers of phthalocyanine dyes or pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/085—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex substituting the central metal atom
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    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
    • C09B47/26—Amide radicals
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    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
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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
    • G11B7/004—Recording, reproducing or erasing methods; Read, write or erase circuits therefor
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    • G11B7/257—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 having properties involved in recording or reproduction, e.g. optical interference layers or sensitising layers or dielectric layers, which are protecting the recording layers
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    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
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Abstract

本发明提供一种具有形成在基材10上的至少一记录层11和一透光层13的光记录介质，其中，记录层11由用于吸收波长为360-460纳米的入射光并诱发物理变化或化学变化从而改变折射率的有机材料组成；透光层13的厚度为10-177微米；有机材料的吸收系数(k)和热解温度Tdec之间的关系为950(℃)＜(Tdec(℃)-20)/k＜4100℃...(1)，并且吸收系数“k”＞0.0。

Description

光记录介质
技术领域
本发明涉及具有由有机材料制成的记录层的光记录介质，如CD-R(可记录的光盘)和DVD-R(可记录的数字视频通用光盘)，以及涉及其制备方法。
背景技术
业已生产出各种各样的光记录介质，如具有在基材上形成的不同材料制成的记录层的光盘，用于通过照射光在记录层中记录和复制信息。在这些光记录介质中，通过利用更短波长的光源并提高物镜的数值孔径的方法，实现了更高的记录密度。
在这些光记录介质之中，CD-R和DVD-R的记录层用所谓有机物质的有机颜料制成，所述颜料吸收入射光并通过物理变化或化学变化而分解，并且改变折射率。上述的光记录介质与其它记录介质是相容的，并且易于制造且是廉价的，因此年复一年地销售量日益增加。在下一代光记录介质中，希望的是在记录层中利用上述有机颜料的所谓只写一次的介质。
本发明要解决的问题
由于记录密度变得更高并且聚焦的光点直径变得更小，因此要求有机颜料最优化。然而，有机颜料在光记录介质上的热解反应机理尚不完全清楚，并且CD-R和DVD-R实际上已通过重复试验而根据经验进行了最优化，而且，作为下一代高记录密度介质的最佳特性值还没有找到，因此，目前，对于在记录层中利用所述有机颜料开发下一代光记录介质，尚没有具体的指导原则。
特别是，有机颜料具有多样性，并且有机颜料的热传导率与相变材料或磁光材料相比相当低，而且仅披露了很少的数据，因此，对于在记录期间温度的上升几乎不可能获得准确的探测。
作为相应于下一代光记录介质的光学系统，蓝激光二极管(LD)已投入了实际使用，并且光源的波长被缩短，另一方面，还开发出了数值孔径(NA)大于约0.80的物镜，并且光点直径与常规光记录介质相比极小。也就是说，与现有技术相比光能极高，并且热学特性的最优化是最难的问题。
此外，由于记录和再现光源不同于常规的波长，因此，在材料方面需要光学特性的最优化，并且必须重新设计有机颜料的分子结构。也就是说，记录层材料必须具有再现光源的适当的折射率，以便使再现信号具有足够大的幅度。
同时，还必需在该波长时使吸收率最佳化。吸收率与记录时温度的升高有关，并且最佳值将随聚焦光点直径而改变，因此，吸收率的最优化基本上决定了记录特性。
因此，光源的波长是不同的并且物镜的数值孔径也是不同的，而且实际上几乎不可能原样使用常规的有机颜料，特别是在蓝LD光源和高NA结合的情况下，需要与常规材料完全不同的材料。
如上所述，在下一代光记录介质的记录和再现装置的光学系统中，使用蓝LD光源和NA约等于0.8或更大的数值孔径的物镜。在这种情况下，与常规光记录介质特别不同的是透光层的厚度。
在常规的CD和DVD中，记录层和其它层分别以约1.2毫米和0.6毫米的厚度形成在透光的基材上，并且基材侧是光入射侧。另一方面，在适用于NA约0.80-0.95的透镜的下一代光记录介质中，需要保证实际的偏斜裕度(skew margin)，也就是说，需要保证介质基材侧与光学摄像管光学系统偏斜的允许误差，并且当产生偏斜时将发生彗形象差。因此，为了解决彗形象差增加的问题，存在着在1o微米-177微米范围内选择透光层厚度的趋势。
目前，所述透光层本身的制造就是开发的课题，但换句话说，透光层厚度降低的介质的目的在于高NA光学系统应用方面的高密度记录。
鉴于上述的情况，本发明的目的在于选择具有适当光学常数和热学特性的有机材料作为记录层，并通过利用上述材料进行高密度记录而提供用于实现有利记录和再现特性的光记录介质。
发明内容
本发明提供一种具有形成在基材上的至少一记录层和一透光层的光记录介质，其中，记录层由用于吸收波长为360-460纳米的入射光的有机材料组成，并诱发物理变化或化学变化，从而改变折射率；透光层的厚度为10-177微米；有机材料的吸收系数(k)和热解温度Tdec之间的关系为950(℃)＜(Tdec(℃)-20)/k＜4100℃...(1)，并且吸收系数“k”＞0.0。
因此，Tdec大于20℃，优选大于50℃，最优选大于100℃。
如上所述，在本发明中，通过选择记录层的有机材料以满足式(1)中确定的吸收系数(k)和热解温度Tdec之间的关系，并且具有0.0以上的吸收系数；通过短波长的蓝光源和高数值孔径NA的光学摄像管，改善了记录和再现特性，因此，能够实现在高密度下能够记录的实际的光记录介质。
具体实施方式
现在参考附图，下面将详细地描述本发明的优选实施方案，但必须注意的是，本发明并不局限于下面的各实施方案，在不脱离本发明的精神和范围下，可以对本发明作出各种改变和改进。
因此，本发明打算在记录层热学特性最佳化中给出记录层材料吸收系数和热解温度的最佳范围。该最佳组合物适于利用如上所述用于下一代光记录介质的光学系统的光记录介质，并且优选的是，通过利用波长360纳米-460纳米的所谓的蓝光源并选择10-177微米厚度的透光层，在光学摄像管物镜的数值孔径NA为0.80或更大的光学系统中进行记录和再现。
当记录层由通过吸收入射光而物理变化或化学变化的所谓热解而记录的有机材料组成时，记录特性和再现稳定性在一定程度上由吸收系数和热解温度之间的关系确定。特别是，记录层从恒定光能量吸收的热量主要与吸收系数成比例。该机理将解释如下。
在记录层中的温度分布可通过利用导热率公式(例如，O.W.Shih，J.Appl.Phys.75(1994)4382)来计算。导热率公式的解取决于不同的参数，如薄膜组成，每一层的导热率，记录光脉冲图形，线速度，和入射光点的尺寸。
在光记录介质的参数中，当有机颜料用于记录层中时，由于记录层的导热性极低，因此，向外界的热传导速度较慢，例如约为铝薄膜的1/500，或约为玻璃基材的约1/5。因此，达到极限的温度，即在该点中最热区域的温度最大地依赖于记录层的热吸收，也就是说，由点矢量<S>计算得到的吸热量(-·<S>)。
就点矢量而论，由于记录层是薄膜，因此必须考虑多重干扰的影响，但是，吸收系数“k”越高，吸热量就越多，并且基本上可假设其与吸收系数“k”成比例。也就是说，在记录前的温度为室温，约20℃，但当吸收系数变得更高时，达到极限的温度往往会准线性地升高。
在有机材料的记录中，热解是记录的原理。作为反应和通过热解所致分子离解的结果，在记录之后的光学常数将变更，并且通过再现光对其进行检测。因此，当记录层部分地达到点中热解起始温度时，将进行记录。热解温度Tdec越高，在记录中所需的热量就越多，但在其中刻痕光强度限制在一定范围内的目前的光学记录装置中，希望达到的温度通过如上所述适当地选择吸收系数而达到。
作为有机材料，染料和/或颜料是优选的。上述的染料和颜料尤其是属于下列类别：偶氮，尤其是杂环偶氮，部花青，半花青，花青，链花青，零花青，烯胺，腙，香豆素和酞菁。这些染料或颜料还可是聚合的或粘结至聚合物骨架上的。实施方案1-12属于最优选的那类染料和颜料。
考虑到吸收系数和热解温度之间的上述关系，在下面列出了可记录的实施例和不可记录的实施例，并且列出了吸收系数和热解温度的有利范围。
在下面的实施方案中，热解温度Tdec通过差示扫描量热计(DSC)测量并由所谓的DSC曲线来计算。为了从DSC曲线中溶解温度的峰分离出来，还进行热重分析(TGA)，并且将质量没有改变的峰判定为溶解峰，将TGA中质量下降5％或更多的区域中的DSC曲线的峰判定为热解温度Tdec。
在每一实施例中，通过用包含波长405纳米的蓝光源和数值孔径NA为0.85的光学摄像管的物镜来评估记录特性和再现特性。在本发明优选的实施方案中，光记录介质的反射率大于10％。
在光记录介质中，特别优选的C/N值不是特定的，但约为45dB。在正开发的记录材料中，在本发明中，考虑到通过薄膜形成条件和记录条件的最优化，C/N仅有2-3dB的波动，因此，目前，将能够取得(C/N优选为43dB或更大的材料假定为良好的可记录有机材料。也就是说，当C/N为43dB或更大时，作为记录层的最佳设计，估计满足了最优化优选的条件。
本申请C/N值的测量方法是利用具有30kHz分辨谱带的光谱分析仪。
顺便提一句，如果记录层的热学特性不适于用于记录装置中所用的光学系统的话，C/N将明显下降，因此，通过检测是否获得约43dB的优选C/N，差不多可以弄清楚材料的特性。
第一实施方案
如图1中放大的剖视示意图所示，在该实施例中，顺序地将记录层11，介电层12，和透光层13层压至基材10上，并形成光记录介质。基材10是聚碳酸酯基材，并且，尽管没有示出，但在基材内以0.64微米的轨距形成了导向槽，并且导向槽的宽度约为轨距的50％，以便数据能够记录在导向槽和导向槽之间的槽脊中。也就是说，实际上的轨距约为0.32微米。槽的深度为40纳米。
记录层11的材料是三苯基胺四聚体。更具体地说，它是N，N＇-二(4-二苯基氨基-4-联苯基)-N，N′二苯基联苯胺，并且Ca sNo.为167218-46-4。薄膜成形方法为汽相沉积法，并且薄膜厚度为40纳米。作为光学常数，对405纳米光源的折射率“n”在记录前为2.31，吸收系数“k”为0.13，热解温度Tdec为480℃。
介电层12是SiO2，其是通过溅射法形成的40纳米厚的薄膜。介电层12的用途是保护记录层11。
透光层的厚度为100微米。通过用压敏粘结剂(PSA)胶合聚碳酸酯片而形成该层，并且复合厚度设置在100微米。
在如此制造的光记录介质中，基材的折射率“n”约为1.6，且压敏粘结剂的折射率″n″约为1.5，因此，记录层11上下侧界面处所发生的反射将引起多次反射，并且对405纳米波长光的反射率将变成15％。由其中记录层的折射率高于基材折射率的材料组成的光记录介质在下文中称为L型。
在记录中，线速度为5.72m/s，再现光功率为0.3mW，并且记录试样为单一载波，其记号长度为0.69微米。为记录单一标记，以脉冲/空间比50％输入七个同样宽度的脉冲列，峰功率为5.0mW，并且C/N(载波/噪声比)通过光谱分析仪测量，并对记录和再现特性进行评估。光谱分析仪是Takeda Riken的TR4171，并且将RBW设置在30kHz。
作为上述测量的结果，在本实施方案的光记录介质中，获得了54.0dB的值。该有机材料已知将赋与足够优异的记录和再现特性。
第二实施方案
在该实施例中，式(I)的有机材料用作记录层的材料。该材料的吸收系数(k)为0.12，热解温度Tdec为322℃。折射率(n)为1.30，并且由于该材料单独使用时的反射率太低，如图2放大的简要剖视图所示，因此，将第一Ag层21，记录层22，第二Ag层23，和透光层24顺序地层压至基材10上。
在此，基材10和透光层24的材料，厚度，构型，以及形成薄膜的方法与第一实施方案相同。第一Ag层21的厚度为12纳米，第二Ag层的厚度为10纳米，并且记录层的厚度为50纳米。第一和第二Ag层21和23通过DC溅射方法形成。记录层21通过旋涂方法形成。在该构型中，反射率为20％。
在该实施例中，C/N周与实施例1中相同的记录和再现条件来测量，并且结果为45.5dB。
因此，由于记录层22与金属层(Ag层)接触，因此担心由于热学特性的差异所致的问题，不过实际上，由于Ag层21和23的厚度极小，为10-12纳米，因此，导热性实际上没有不同于第一实施方案中介电层的导热性，此外，由于记录层本身的导热性极低，因此，在记录层中心部分的温度上升几乎与第一实施方案相同。
在该构型中，由于入射光穿过第二Ag层23并达到记录层22，因此光量被减少，尽管记录层22具有被第一和第二Ag层21和23包围的谐振器的结构，并且引发多次反射，结果是，在记录层22中的热吸收量与第一实施方案中的热吸收量没有很大的差异。因此，如果薄膜组合物与第一实施方案不同的话，在相同的记录条件下，在记录期间达到的温度似乎基本相同。实际上，通过第一实施方案中作为记录层材料使用的三苯基胺四聚体，当记录层如图2所示夹在Ag层之间时，将获得几乎相同的记录灵敏性，并测得类似的C/D值。
在第二实施方案中，在记录之前材料的折射率为1.3，并且在热解之后折射率接近1.5，并检测到一信号。在记录前其折射率低于记录后折射率的上述材料在下文中称为S-型。
正如在上述第一和第二实施方案中所述的那样，在每一材料中，根据折射率将薄膜组合物分成L型和S型；将光记录介质制备成适当的组合物；并在与第一实施方案相同的条件下测量记录和再现特性。
更具体地说明这些薄膜组合物，在L型中，基本上使用第一实施方案中的薄膜组合物。就S型材料而论，基本上使用第二实施方案中的薄膜组合物，并且当初始折射率为1.2或更低时，为了简化起见，以40纳米的厚度形成第一实施方案的结构、即将SiN用作介电层和薄膜材料。结果获得了约15％的足够的反射率。
这些材料的吸收系数“k”，热解温度和C/N的测定结果与第一和第二实施方案中结果一起列于表1中。
表1
在图3中，粗体圆点标记示出了涉及第一至第十二实施方案中吸收系数和热解温度的C/N为43dB或更高的优选值。如上所述，尽管作为光记录介质实际的信号值特别优选的是45dB，但必须考虑取决于薄膜形成条件和记录条件可能会发生的2-3dB波动，因此，当C/N值至少为43dB或更高时，通过改善形成薄膜的条件可以预期有利的结果，因此，将43dB选作优选的最小值。
在此测量的有机材料的体系和分子结构是各种各样的(参见表1)并且由图3可以看出，仅仅通过吸收系数“k”和热解温度Tdec的物理参数表达了记录和再现特性明确的趋势。也就是说，已知的是，粗体圆点标记区域A在记录和再现特性方面是优异的。
如上所述，达到极限的温度主要与吸收系数“k”成比例。记录中的环境温度为室温，并且通过选择从室温开始的直线的范围，能够澄清在记录和再现特性方面优异的吸收系数“k”和热解温度Tdec的区域。所述直线在图3中以“a”和“b”表示。
被这些线“a”和“b”包围的区域C的范围可表示为：950℃＜(Tdec℃-20)/k＜4100℃。
当然，吸收系数“k”为大于0的值。这是因为对记录层材料进行了适当选择，以便通过吸收光并诱发物理变化或化学变化而使折射率改变。
当基底材料为聚碳酸酯时，当温度超过1000℃时可能会熔融，因此，希望的热解温度Tdec为1000℃或更低。
作为仔细选择的结果，获得了图3所示的材料，以便在记录之前充分降低噪音水平，并保持评估的高质量，以便可评估热学特性。相反，只要有机材料具有在本发明范围内的吸收系数和热解温度的关系，当记录之前的噪音水平低且满足基本特性要求时，就能够获得良好的C/N。
高噪音水平的例子是由于记录层的结晶所致而形成粗粒范围的情况，或由于高流动性所致在介电层中形成扩散或裂缝的情况。除上述的特例之外，只要适当地形成记录层，作为噪音水平，由于基材的凹槽和槽脊所致的所谓磁盘噪音，源自比如激光光源的散射噪声，以及检测器的热噪声的组合是主要的，并且对记录层材料的依赖性小。
因此，本发明提供一种用于高记录密度的实用光记录介质的记录材料，所述材料优选用于利用光学系统的装置，所速光学系统具有所谓的360-460纳米波长的蓝光源和数值孔径NA为0.80或更大的物镜。
然而本发明并不局限于实施方案中的材料组合物。
附图说明
图1是光记录介质实施例的放大简要剖视图。
图2是光记录介质实施例的放大简要剖视图。
图3是显示光记录介质各实施例中与吸收系数和热解温度有关的记录和再现特性评估结果的图。
参考号说明
10：基材
11：记录介质
12：介电层
13：透光层
21：第一Ag层
22：记录层
23：第二Ag层
24：透光层

Claims (3)

1.一种具有形成在基材上的至少一记录层和一透光层的光记录介质，其特征在于，记录层由有机材料组成，该材料吸收波长为360-460纳米的入射光，并诱发物理变化或化学变化，从而改变该材料的折射率；透光层的厚度为10-177微米；有机材料的吸收系数k和热解温度Tdec之间的关系为950℃＜(Tdec℃-20)/k＜4100℃，并且吸收系数k＞0.0；
所述光记录介质其载波、噪音比C/N大于43dB；
其中有机材料为选自以下的染料或颜料：偶氮，部花青，半花青，花青，链花青，零花青，烯胺，腙，香豆素和酞菁；并且
其中通过利用波长约360纳米-约460纳米的蓝光源，在光学摄像管物镜的数值孔径NA为0.80或更大的光学系统中进行记录和再现。
2.根据权利要求1的光记录介质，其中有机材料为下列通式中的至少一种化合物：
Figure C028107140002C1
Figure C028107140004C1
以及
3.根据权利要求1的光记录介质，其中吸收系数k＞0.11。
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