CN1906681A - 光记录介质 - Google Patents

光记录介质 Download PDF

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Publication number
CN1906681A
CN1906681A CNA2005800018907A CN200580001890A CN1906681A CN 1906681 A CN1906681 A CN 1906681A CN A2005800018907 A CNA2005800018907 A CN A2005800018907A CN 200580001890 A CN200580001890 A CN 200580001890A CN 1906681 A CN1906681 A CN 1906681A
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CN
China
Prior art keywords
layer
transparent resin
thickness
resin layer
optical recording
Prior art date
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Granted
Application number
CNA2005800018907A
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English (en)
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CN100470649C (zh
Inventor
风吕本滋行
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.)
CMC Magnetics Co
Original Assignee
Mitsubishi Chemical Corp
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Publication date
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Publication of CN1906681A publication Critical patent/CN1906681A/zh
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Publication of CN100470649C publication Critical patent/CN100470649C/zh
Expired - Fee Related legal-status Critical Current
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Abstract

一种双层光记录介质100的制备,它是通过粘合在基层(1)101上顺序层叠反射层(1)102和记录层(1)103而成的盘基(倒置层叠结构11)和在透明基层(2)109上以中间插入有透明树脂层105的方式顺序层叠记录层(2)108和反射层(2)107而成的盘基(常规层叠结构12)而形成的,其中所述透明树脂层的厚度(t)和25±5℃下的弹性模量(E)的乘积(E×t)落在不小于2.0×104MPa·μm且不大于30.0×104MPa·μm的范围内,使得能够抑制因在倒置层叠结构11的记录层(1)103上记录光信息而导致的包括相邻轨道部的过度的形变,从而在高速记录应用中降低串扰并提供满意的记录和/或读取特性。

Description

光记录介质
                                技术领域
本发明涉及一种光记录介质,尤其涉及一种能够进行高速记录并具有满意的记录和/或读取特性的光记录介质。
                                背景技术
众所周知,各种类型的光记录介质如CD-R、CD-RW和MO能够存储大量数据。此外,可随机存取介质如DVD-RAM最近被开发出来并普遍作为信息处理设备如计算机的外存储器。一个典型的例子,如CD-R,其具有包含有机色素的记录层,是通过将色素记录层和反射层顺序叠在透明盘基上再放置一层保护层以覆盖记录层和反射层而形成的层状结构。记录和/或读取是通过激光穿过基层来实现的。此外,为了增加光记录介质的记录容量,开发出在单个介质中设置有多层记录层的多层光记录介质。例如,专利文献1中报导了具有两个色素记录层的双层光记录介质,两层色素记录层形成在透明的第一盘状基层上,其间插入有由可紫外线固化的树脂形成的中间层。
已知这种双层光记录介质是使用透明压模机采用2P法(光聚合法)制成的,包括形成两个其上分别叠有记录层和反射层的盘基,并用光固化树脂层插入到两个盘基之间而将它们粘合起来。更具体地说,2P法包括:在形成有第一记录层和第一反射层的第一基层上施涂光固化树脂材料,在涂覆有树脂的表面上安装具有不规则形状的透明压模机,使光固化树脂材料固化,移去透明压模机使得不规则形状转印给光固化树脂的表面,顺序地在不规则表面上形成第二记录层和第二反射层,最后粘附第二基层。通过入射到第一基层上的记录和/或读取光,在两个记录层上记录或从其上读取光信息。
在粘合两个分别堆叠有记录层和反射层的盘基的方法中,双层光记录介质是按照如下步骤制造的:在形成有作为记录轨道的导槽的基层上顺序层叠记录层和反射层以形成第一盘基(下文中有时称“常规层叠结构”),在基层上顺序层叠反射层和记录层以形成第二盘基(下文中有时称“倒置层叠结构”),在每个盘基上施涂光固化树脂,将他们结合使得涂覆树脂的表面彼此相对,最后使光固化树脂固化。通过入射到第一基层上的记录和/或读取光,在两个记录层上记录或从其上读取光信息。与2P法不同,这种粘附两个盘基的方法不要求转印透明压模机的凹凸形状的步骤。因此该方法在提高生产率和降低成本方面被认为很优秀。
专利文献1:日本专利公开No.2000-311384,第0008-0019栏。
                                发明内容
本发明要解决的问题
在具有包含有机色素的记录层的光记录介质中,有一个在高速记录中进一步抑制串扰的要求。
更具体地说,通常在包含有机色素的记录层中,有机色素吸收集聚的记录激光然后分解。结果是,色素存在的地方的膜厚会降低;同时,压力增加。由于围绕记录层的部分曝露在高温下,该部分发生形变以形成记录部。在这种情况下,如果变形的记录部扩张到相邻轨道区域,并且如果在多个轨道中进行了记录,串扰就趋向于增加,导致难以获得满意的抖动的问题。
在本发明中,MT(%)表示在多个轨道上记录以及读取在轨道相邻两侧轨道上记录的信号时的抖动。此外,ST(%)表示读取两边相邻轨道均为空的单个轨道上记录时的抖动。MT(%)包括串扰的影响,但ST(%)不包括串扰的影响。
此外,在高速记录中,由于记录脉冲缩短了,因此需要比低速记录时更高的激光功率来使色素分解。结果是,使记录层曝露在比低速记录时更高的温度下,串扰趋向于显著增加。
在由两个盘基粘合形成的双层光记录介质中,位于远离记录和/或读取光的入射表面一侧的第二层上观察到明显的串扰。如上所述,通过粘合两个盘基的方法形成的双层光记录介质中的第二深的记录层位于倒置层叠结构的盘基内,其中反射层和记录层层叠在基层之上。当在这种倒置层叠结构的基层的槽间部记录光信息时,必须增加槽间部的记录层厚度以确保记录调幅。在这种情况下,由于记录部的相邻轨道对应于基层的槽,在槽部的记录层膜厚很可能比槽间部的增加。因此,当槽的记录层膜厚增加时,记录标记横向地扩张,很容易增加串扰。在有机色素溶液的旋转涂布中,槽部和槽间部的记录层厚度会不同。
在双层光记录介质中远离记录和/或读取光的入射表面一侧的第二基层中,导槽的深度设置得比常规的要浅,以确保记录和/或读取光的反射率。结果是,降低了导槽的物理势垒效应,并导致记录过程中树脂流动引起的如基层的过度形变。因此,容易增加串扰。
本发明致力于解决这些问题。
更具体地说,本发明的目的在于提供一种光记录介质,其在高速记录中能够提供满意的记录和/或读取特性。
解决问题的手段
为解决上述问题,在本发明中,与倒置层叠结构接触的透明树脂层具有弹性模量(E)和厚度(t)在一定范围内的乘积(E×t)。
更具体地说,根据本发明,提供了一种光记录介质,它包含顺序层叠有基层、反射层和记录层的倒置层叠结构,以及设置在倒置层叠结构的记录层一侧的透明树脂层,该透明树脂层在25±5℃下的弹性模量(E)与厚度(t)的乘积(E×t)为2.0×104MPa·μm或更大。
在本发明中,透明树脂层在25±5℃下的弹性模量(E)与厚度(t)的乘积(E×t)优选为30.0×104MPa·μm或更小。
形成透明树脂层的树脂在25±5℃下的弹性模量(E)进一步优选为不小于3.0×103MPa且不大于6.0×103MPa。
在本发明的光记录介质中,形成倒置层叠结构的记录层优选含有有机色素。尤其是,在如图1(在下文中描述)所示的双层光记录介质中,当在由基层、反射层和记录层构成的倒置层叠结构上进行记录时串扰得以减少,从而改善了MT(%)。注意,基层和反射层之间或者反射层和记录层之间还可适当的设置另一个层。
在本发明的光记录介质中,优选在形成倒置层叠结构的记录层和与记录层接触的透明树脂层之间进一步设置一个中间层。所提供的中间层能够防止从透明树脂层渗透的组分污染和溶解与透明树脂层相接触的记录层。
此外,在本发明的光记录介质中,通过将第二反射层、第二记录层和透明基层顺序设置在与倒置层叠结构相接触的透明树脂层与倒置层叠结构相对的一侧,就有可能制成多层光记录介质。
另一方面,本发明也可理解为一种光记录介质,它包含:记录层,通过光照射在其上记录或读取光信息;设置在记录层的光入射表面上的透明树脂层;以及设置在记录层与光入射表面相对一侧上的反射层,其中透明树脂层在25±5℃下的弹性模量(E)与厚度(t)的乘积(E×t)为2.0×104MPa·μm或更大。
更具体地说,在光记录介质中,通过在记录层(其光入射表面的相对一侧上设置有反射层)的光入射表面上设置具有比值(E×t)的透明树脂层,能够抑制包括相邻轨道部在内的过度形变,从而降低了高速记录时的串扰并改善了抖动。这种改进不仅体现在膜表面入射型光记录介质上,更显著地体现在远离光入射一侧的记录层上。
在本发明中,透明树脂层优选由玻璃化转变温度为150℃或以上的透明树脂组成。通过形成这样的透明树脂层,透明树脂层的刚性得以增大,从而能够想象到对抖动的改善。
根据本发明,提供了一种光记录介质,它包括顺序层叠的基层、反射层、记录层和透明树脂层,其中反射层含有以Ag为主要成分的金属,其膜厚不低于30nm且不高于80nm。
本发明的光记录介质具有一种倒置层叠结构,包括顺序层叠的基层、反射层、记录层和透明树脂层,其中反射层含有以Ag为主要组分的金属,其膜厚不低于30nm且不高于80nm。以这种结构,部分从记录层照射来的光束可以穿过反射层。在这种情况下,用以在记录层上记录信息的能量发生扩散,有可能抑制所谓的串扰现象(即在记录标记形成在含有有机色素的记录层中的一次性写入型光记录介质中,记录标记突出到相邻轨道中)。结果是,改善了抖动。
在这种情况下,反射层的Ag含量优选在50%或以上,除主要组分Ag之外,进一步优选包含0.1原子%~15原子%的选自Ti,Bi,Zn,Cu和Pd以及稀土金属中的一种或多种元素。
发明效果
如上所述,根据本发明,提供了一种光记录介质,其在高速记录中能够提供满意的记录和/或读取特性。
                                附图说明
图1是说明本发明的光记录介质的第一实施方式的示意图;
图2是说明本发明的光记录介质的第二实施方式的示意图;
图3是说明透明树脂层厚度(t)的示意图:图3(a)是由单个树脂形成的透明树脂层的示意图,图3(b)是由多个树脂层形成的透明树脂层的示意图;
图4是说明试样1~10的(E×t)和MT(%)值之间的关系图;
图5是说明反射层的膜厚和透射率(T)之间的关系,以及反射层的膜厚和反射率(R)之间的关系的示意图;以及
图6基于表2所示的结果的(MT(%)-ST(%))值与反射层(1)的膜厚之间的关系图。
附图中标号和符号说明
11...倒置层叠结构,            106...保护涂层,
12...常规层叠结构,            107...反射层(2),
100,200...光记录介质,        108...记录层(2),
101...基层(1),                109...基层(2),
102...反射层(1),              110,210...激光,
103...记录层(1),              201...基层,
104,204...中间层,            202...反射层,
105,205...透明树脂层,        203...记录层
                                具体实施方式
下面解释用以实施本发明的最佳实施方式(以下称实施方式)。注意,本发明不局限于下面的实施方式,并可在发明要点的范围内做各种方式的改进和应用。
(第一实施方式)
图1显示了根据本发明的光记录介质的第一实施方式,即单面入射型双层DVD。图1显示了双层光记录介质100,它包括:盘基(倒置层叠结构11),其通过在透明基层上层叠反射层和记录层而形成;以及盘基(常规层叠结构12),其通过在透明基层上顺序层叠记录层和反射层而形成。
如图1所示,光记录介质100具有倒置层叠结构11,该结构包括:具有沟槽(groove)、岸台(land)或预制凹坑(prepit)的盘状可透光基层(1)101,设置在基层(1)101的激光110入射表面一侧上的反射层(1)102,含有色素的记录层(1)103,以及中间层104。此外,光记录介质100具有常规层叠结构12,该结构包括:具有沟槽、岸台或预制凹坑的盘状可透光基层(2)109,含有色素并形成在基层(2)109之上的记录层(2)108,用以分散从基层(2)109照射来的激光110的能量的半透明反射层(2)107,以及设置在反射层(2)107上的保护涂层106。倒置层叠结构11和常规层叠结构12以它们中间插入有透明树脂层105的形式层叠,这样中间层104和保护涂层106彼此相对而形成双层光记录介质100。在记录层(1)103和记录层(2)108中,光信息的记录和/或读取是通过从常规层叠结构12的基层(2)109照射来的激光110来进行的。
(倒置层叠结构)
下面将说明形成光记录介质100的倒置层叠结构11的各层。如图1所示,倒置层叠结构11由基层(1)101和层叠在基层(1)101上的反射层(1)102、记录层(1)103和中间层104(这三层在下文中有时被称作“L1层”)所构成。
(基层(1))
形成基层(1)101的材料要求具有透射率和优秀的光学特性,如小的双折射。此外,还要求具有优秀的成型性如易于注射成型,以及具有低的吸湿性。此外,该材料要求具有形态稳定性,以使光记录介质100获得一定的刚度。这样的材料的例子包括但不限于,丙烯酸树脂,甲基丙烯酸树脂,聚碳酸酯树酯,聚烯烃树脂(尤其是非晶态聚烯烃),聚酯树脂,聚苯乙烯树脂,环氧树脂,以及玻璃。此外,在玻璃基层上还可使用含有由辐射固定树脂如光固定树脂形成的树脂层的材料。它们当中,就光学特性,诸如成型性、性能价格比、低吸湿性、形态稳定性等高的生产性而言,优选聚碳酸酯。此外,从耐化学性、低吸湿性等考虑,优选非晶态聚烯烃。此外,从高速响应等考虑优选玻璃基层。
基层(1)101不必光透明。因此,可以附贴由合适材料制成的背衬以增加机械稳定性和刚度。这种材料的例子可以包括:铝(Al)合金基层如以Al作为主要组分的Al-Mg合金,Mg合金基层如以Mg作为主要组分的Mg-Zn合金,以及如硅,钛,陶瓷,纸及其组合的基层。
形成倒置层叠结构11的基层(1)101的导槽的深度通常为λ/100或以上,优选为2λ/100或以上,更优选3λ/100或以上,其中λ是记录和/或读取波长;但是,该深度优选为λ/6或更小。更具体地说,当记录和/或读取光的波长λ(记录和/或读取波长)为660nm时,基层(1)101的沟槽深度通常为6.6nm或以上,优选为13nm或以上,并进一步优选为20nm或以上。
在这种情况下,基层(1)101的槽深的上限优选设定为110nm或更小。尤其对于本实施方式的光记录介质100而言,穿过基层(2)109和透明树脂层105入射到记录层(1)103上的激光110的光通量和反射光通量被记录层(2)108和反射层(2)107减弱了,降低了反射率。因此,槽深的上限优选为7λ/100或更小。更具体地说,如果记录和/或读取波长(λ)是660nm,基层(1)101的槽深优选设置为46.2nm或更小,更优选为6λ/100或更小。
倒置层叠结构11的基层(1)101的沟槽宽度通常为T/100或以上,优选为2T/10或以上,更优选为3T/10或以上,其中T是轨道间距;但通常为8T/10或更小,优选为7T/10或更小,更优选为6T/10或更小。如果基层(1)101的槽宽在上述范围内,可令人满意地进行寻轨以获得足够的反射率。更具体地说,如果轨道间距是740nm,基层(1)101的槽宽通常设定为74nm或以上,优选为148nm或以上,更优选为222nm或以上。这种情况下,其上限通常为592nm或更小,优选为518nm或更小,更优选444nm或更小。基层(1)101最好具有一定厚度。基层(1)101的厚度通常优选为0.3mm或以上;但通常为3mm或更小,优选为1.5mm或更小。
(反射层(1))
对倒置层叠结构11的反射层(1)102的材料没有特别限定;但可以单独或以合金形式使用金属或半金属,如Au,Al,Ag,Cu,Ti,Cr,Ni,Pt,Ta,Pd,Mg,Se,Hf,V,Nb,Ru,W,Mn,Re,Fe,Co,Rh,Ir,Zn,Cd,Ga,In,Si,Ge,Te,Pb,Po,Sn,Bi和稀土金属。其中,优选Au,Al和Ag,从低成本和高反射率考虑,特别优选Ag含量为50%或更大的金属材料。
此外,优选Ag作为主要成分,至少一种选自Ti,Zn,Cu,Pd,Au和稀土金属的元素的含量为0.1原子%~15原子%。当含有两种或更多中选自Ti,Bi,Zn,Cu,Pd,Au和稀土金属的元素时,每种元素的含量可在0.1原子至15原子%的范围内;但是这些元素的总量优选在0.1原子%~15原子%的范围内。
进一步优选的合金组合物包含Ag作为主要组分,和含量在0.1原子%~15原子%的至少一种选自Ti,Bi,Zn,Cu,Pd和Au的元素,以及如有必要,还包含至少一种含量在0.1原子%~15原子%的稀土金属。在稀土金属中,尤其优选钕(Nd)。合金组合物的具体例子包括AgPdCu,AgCuAu,AgCuAuNd,AgCuNd,AgBi和AgBiNd。本实施方式中使用的这些合金的组分比在上述范围内。
注意,术语“Ag作为主要组分”是指合金组合物中Ag的含量通常在50%或以上,优选70%或以上,更优选80%或以上。或者,可使用纯银。
对于反射层(1)102,优选仅由Au组成的层,因为Au具有较小的晶粒和优异的耐腐蚀性。或者,反射层(1)102也可使用由Si组成的层。此外,可以使用分别由非金属材料制成的低反射薄膜和高反射薄膜交替层叠形成的多层膜作为反射层。
形成反射层(1)102的方法,可以是溅射法,离子电镀法,化学气相沉积法以及真空气相沉积法等等。
倒置层叠结构11的反射层(1)102要求具有高反射率和高耐久性。为确保高反射率,反射层(1)102的厚度通常在30nm或以上,优选为40nm或以上,更优选为50nm或以上;但通常为400nm或更小,优选为300nm或更小,以缩短制造时间以降低成本。
在本实施方式的光记录介质100中,当倒置层叠结构11的反射层(1)102含有以Ag作为主要组分的金属时,反射层(1)102的膜厚进一步优选在30nm~80nm的范围内。尤其是,当含有Ag作为主要组分的反射层(1)102的膜厚在30nm~80nm的范围内时,反射层(1)102的反射率的降低与其透射率的增加相平衡,导致能量扩散,结果是改善了串扰。
在倒置层叠结构11中,当反射层(1)102含有以Ag作为主要组分的金属且膜厚在上述具体范围内时,串扰会因下述原因而得到改善。这是因为反射层(1)102的膜厚越薄,反射层(1)102的反射率(R)越低,透射率(T)则越高。反射层的膜厚与透射率(T)之间的关系,以及反射层的膜厚与反射率(R)之间的关系如图5所示。更具体地说,图5(a)显示了反射层的膜厚与透射率(T)之间的关系,图5(b)显示了反射层的膜厚与反射率(R)之间的关系。如图5(a)所示,反射层的膜厚从大约80nm处开始下降,透射率(T)则随之上升。当膜厚低于约30nm时,透射率(T)超过5%。如图5(b)所示,反射层的膜厚从大约80nm处开始下降,反射率(R)随之下降。当膜厚低于约30nm时,反射率(R)小于85%。注意在图5中,反射率(R)和透射率(T)是针对单层Ag反射层(折射率(n)为0.05,消光系数(k)为4.25)在施加650nm波长的光的条件下计算得到的。
同样地,随着反射层(1)102的透射率(T)的增加,发生了能量扩散。然后,在记录层(1)103上进行记录时,记录标记内部及记录标记之间的热干扰下降了。结果是,记录层(1)103中的过度热积聚或变化(形变)得到了抑制,减少了串扰。
此外,当所形成的反射层(1)102的膜厚比常规的薄时,反射层(1)102能够精确地仿照(追踪)基层的沟槽的形状。因此,即使当轨道间距狭窄时,沟槽和槽间部可被可分辨的分离。因此,有可能降低串扰。
然而,反射层(1)102的膜厚不是越薄越好,因为这样会使反射率(R)急剧下降。因此,记录层(1)103的膜厚优选为30nm或以上,更优选为40nm或以上。通常,反射层包括以银为主要组分的金属并具有100nm或以上的膜厚。在这种情况下,透射率(T)很低,因此能量扩散很少发生。因此,记录层(1)103的膜厚优选为80nm或更小。
当反射层(1)102的膜厚采用通常的小于100nm时,不但能减少溅射时间,而且还能降低基层(1)101在溅射过程中温度的升高,从而缓和了溅射过程中原子的迁移。结果是,可以形成粒度小、表面粗糙度小、性能价格比好的优质反射层(1)102。
(记录层(1))
倒置层叠结构11的记录层(1)103通常含有同单面记录介质如CD-R,DVD-R和DVD+R具有相同灵敏度的的色素。这种色素的最大吸收波长(λmax)优选在可见光至近红外(约从350nm至900nm)范围内,适合于蓝色到近微波激光的记录。它们之中,进一步优选适合于波长约从770nm至830nm(更具体说是780nm,830nm)的通常用在CD-R的近红外激光记录、波长约从620nm到690nm(更具体说是635nm,660nm和680nm)的用在DVD-R的红色激光记录,以及波长为410nm或515nm的蓝色激光记录的色素。注意,可使用相改变型材料。
用于记录层(1)103的色素没有特别限定;但通常使用有机色素。这种有机色素的例子包括大环氮杂轮烯色素(如酞菁色素,萘菁色素,卟啉色素),吡咯甲叉(pyrromethene)色素,聚甲炔色素(如花青色素,部花青色素,斯夸琳(squarylium)色素),蒽醌色素,甘菊(azulenium)色素,含金属偶氮色素,以及含金属吲哚苯胺色素。它们当中,含金属偶氮色素因其优秀的记录灵敏度,耐久性和耐光性而受到优选。这些色素可以单独使用或以两种或更多种的混合物形式使用。
此外,为改善记录层的稳定性和耐光性,记录层(1)103可以包含过渡金属螯合物作为单氧猝光剂(例如,乙酰丙酮螯合物,联苯二硫酚,水杨醛肟,双二硫-α-二酮)等。为改善记录灵敏度,层可以包含记录灵敏度改进剂如金属化合物。术语“金属化合物”是指含有金属如以原子、离子、簇等形式存在的过渡金属的化合物。这样的金属化合物包括有机金属化合物如乙二胺络合物,甲亚胺络合物,苯胲络合物,菲咯啉络合物,二羟偶氮苯络合物,二肟络合物,亚硝基氨基苯酚络合物,吡啶三嗪络合物,乙酰丙酮化物络合物,茂金属络合物,以及卟啉络合物。对金属原子没有特别限定;但优选使用过渡金属。
此外,如有必要,可在记录层(1)103上添加粘结剂、标识剂和消泡剂等。粘结剂的优选例子包括聚乙烯醇,聚乙烯基吡咯烷酮,硝化纤维素,醋酸纤维素,酮类树脂,丙烯酸(酯)树脂,聚苯乙烯树脂,聚氨酯树脂,聚乙烯醇缩丁醛,聚碳酸酯和聚烯烃。
记录层(1)103的沉积方法没有特别限定;但可以使用通常的薄膜成型方法,如真空气相淀积法,溅射法,刮涂法,流延涂布法,旋涂法和浸渍法。从大规模生产和性能价格比考虑,优选湿膜涂布法如旋涂法。另一方面,从获得均匀的记录层考虑,优选气相沉积法。
使用旋涂法进行沉积,旋涂最好以10rpm至15,000rpm的转速进行,然后通常还要进行热处理以除去溶剂。当记录层是用涂布法如刮涂法、流延涂布法、旋涂法或浸渍法形成时,所用涂布溶剂没有特别限定,任何不损坏基层的溶剂均可使用。这样的溶剂的例子包括:酮醇溶剂如双丙酮醇和3-羟基-3-甲基-2-丁酮;溶纤剂溶剂如甲基溶纤剂和乙基溶纤剂;链式碳氢化合物溶剂如正己烷和正辛烷;环形碳氢化合物溶剂如环己烷,甲基环己烷,乙基环已烷,二甲基环己烷,正丁基环己烷,叔丁基环己烷和环辛烷;全氟烷基醇溶剂如四氟丙醇,八氟戊醇和六氟丁醇;以及羟基羧酸酯系溶剂如乳酸甲酯,乳酸乙酯和2-羟基异丁酸甲酯。
用以移除这些溶剂的热处理通常在比该溶剂的沸点略低的温度下进行,使用简单设备移除溶剂,其温度通常是在60℃~100℃的范围内。对热处理方法没有特别限定。例如,可提及一种方法,其包括:在基层(1)101上施涂含有色素的溶液以形成记录层(1)103的薄膜,将该薄膜在预定温度下静置预定时间(通常为5分钟或以上,最好是10分钟或以上;但不超过30分钟,且最好不超过20分钟)。或者,也可对基层(1)101使用短时间(如5秒钟至5分钟)的红外线或远红外线照射进行加热。
若使用真空淀积法,将例如有机色素以及如有必要,记录层的组分如各种添加剂放入到真空室中的坩埚中,使用适合的真空泵将真空室的压力抽至约10-2至10-5Pa,加热坩埚使记录层组分气化,从而使组分沉积在面朝坩埚的基层上。
倒置层叠结构11的记录层(1)103的厚度通常在50nm或以上,优选60nm或以上;但通常为150nm或更小,优选为100nm或更小。如果记录层(1)103的厚度落在该范围内,则有可能抑制灵敏度的下降同时保证有充分的记录信号振幅。当记录层(1)103的厚度过厚时,灵敏度可能在某些情况下下降。
(中间层)
中间层104按要求设置在倒置层叠结构11上。通常,中间层104设置在记录层(1)103和透明树脂层105之间以防止从透明树脂层105渗透来的组分污染和溶解记录层(1)103。中间层104的厚度通常为1nm或以上,优选为2nm或以上。如果中间层104的厚度落在该范围内,则有可能有效防止从透明树脂层105渗透来的组分。然而,中间层104的厚度优选为2,000nm或更小,更优选为500nm或更小。如果中间层104的厚度在该范围内,则能够防止光透射的下降。此外,当中间层104由无机物形成时,有时形成薄膜较费时。为了防止生产率下降并使薄膜应力提高到满意范围内,形成的膜的厚度优选为200nm或更小。尤其是中间层104中使用金属时,中间层104的厚度优选设定为20nm或更小,以防止光透射的过度降低。
用以形成中间层104的材料可以提及的有介电材料如金属薄膜,二氧化硅,氮化硅,MgF2,SnO2和ZnS-SnO2
注意,由类似于中间层104所用的材料形成的层可以分别设置在基层(1)101和记录层(1)103之间,基层(2)109和记录层(2)108之间,以及记录层(2)108和反射层(2)107之间,等等。
(透明树脂层)
然后,下面说明在光入射一侧与倒置层叠结构(11)相接触的透明树脂层105。
本实施方式的双层光记录介质100的透明树脂层105是由能使入射到基层(2)109上的激光110到达记录层(1)103的可透光材料形成的。尤其是与倒置层叠结构11有如下关系。用(E)代表透明树脂层105的弹性模量(单位MPa),(t)代表透明树脂层105的厚度(单位μm),当在倒置层叠结构11的记录层(1)103上记录光信息时,如果将乘积(E×t)(MPa·μm)达到预定值或以上,则能够抑制扩大到相邻轨道上的过度形变。结果是,在光记录介质100中,高速记录时L1层中串扰的发生降低了,并改善了抖动。透明树脂层105中使用的术语“透明”是指入射到光记录介质100上的激光110没有发生散射。这里的“散射”是指对光记录介质100的记录和/或读取特性有明显影响的光散射。
在本实施方式的双层光记录介质100中,透明树脂层105的弹性模量(E)(单位MPa,在25±5℃下的测定值)与厚度(t)(单位μm)的乘积(E×t)(单位MPa·μm)为2.0×104MPa·μm或以上,优选为2.5×104MPa·μm或以上,更优选4.0×104MPa·μm或以上,进一步优选5.0×104MPa·μm或以上,尤其优选7.0×104MPa·μm或以上,更为特别优选9.0×104MPa·μm或以上,最优选10.0×104MPa·μm或以上。当(E×t)的值为2.0×104MPa·μm以上时,能够保证透明树脂层105的机械强度(刚度)。此外,当在L1层(图1)的记录层(1)103上记录光信息时,能够抑制记录扩大到相邻轨道中和过度的形变。
透明树脂层105的弹性模量(E)(单位MPa)和厚度(t)(单位μm)的乘积(E×t)(单位MPa·μm)的上限通常为30.0×104MPa·μm或更小,优选为21.0×104MPa·μm或更小,更优选17.5×104MPa·μm或更小,进一步优选13.5×104MPa·μm或更小。当乘积(E×t)的上限为30.0×104MPa·μm或更小时,很容易使双层光记录介质100的L1层(图1)进入焦点,因此,能够方便的在记录层(1)103进行记录和/或读取。此外,对膜表面入射型光记录介质而言,可以降低物镜的焦距,获得满意的高密度记录。
透明树脂层105所用的树脂的弹性模量(E)通常为1.0×103MPa或以上,优选为2.0×103MPa或以上,更优选为3.0×103MPa或以上,进一步优选为4.0×103MPa或以上。当透明树脂层105使用的树脂的弹性模量(E)为1.0×103MPa或以上以使乘积(E×t)为2.0×104MPa·μm或以上时,能够进一步改善在L1层(图1)上记录和/或读取时的所谓制约效应。注意,弹性模量(E)的上限通常为6.0×103MPa或更小。所使用的树脂的弹性模量(E)为6.0×103MPa或更小时,则有可能使用溶液法如涂布法形成透明树脂层105,这在工业上是有利的。
然后说明透明树脂层105的厚度(t)。图3显示了透明树脂层的厚度(t)。图3(a)显示了透明树脂层由单种树脂形成情况,而图3(b)显示了透明树脂层由多种树脂层形成的情况。更具体地说,下面将说明由单种树脂(情况a)形成的透明树脂层105的厚度(t)和由多种树脂层(情况b)形成的透明树脂层105的厚度(t)。
(情况a)
如图3(a)所示,当与倒置层叠结构接触的透明树脂层由单种树脂形成时,与倒置层叠结构相接触一侧那部分的薄膜厚度定义为透明树脂层的厚度(t),而此透明树脂层的厚度(t)确定为透明树脂层膜厚(h)的一半(h/2)。
当透明树脂层105是由单种树脂形成时,一般认为与倒置层叠结构11相接触的透明树脂层105的部分对倒置层叠结构11的L1层的串扰具有显著的作用。换句话说,当在L1层的记录层(1)103上记录光信息时,透明树脂层105不与倒置层叠结构11相接触的部分被认为不足以产生能够防止记录扩大到相邻轨道中的局部制约力。因此,当透明树脂层105由单种树脂组成时,透明树脂层105的厚度(t)对应于L1层和L0层之间距离的1/2(见图1),这里,与倒置层叠结构11接触一侧那部分的薄膜厚度定义为透明树脂层105的厚度(t)。
在如图1所示的双层光记录介质100中,透明树脂层105的膜厚(h)通常为200μm或更小,优选为100μm或更小,更优选为80μm或更小。尤其是,根据双层DVD光盘的标准,L1层和L0层的间距优选为从40μm到70μm。因此,在这种情况下,透明树脂层105的膜厚(h)优选为70μm或更小。例如,(情况a)中透明树脂层105的厚度(t)通常为20μm或以上。注意,如果透明树脂层105的膜厚(h)为5μm或更小,透明树脂层105的厚度(t)设定为5μm。相反,如果透明树脂层105的膜厚(h)为35μm或以上,透明树脂层105的厚度(t)设定为35μm。
在(情况a)中,当透明树脂层105的厚度(t)落在上述范围内时,有可能使双层光记录介质100的L1层聚焦,从而可以在离散光条件下满意的从L1层和L0层上进行读取;同时,能够适当的对记录层(1)103进行记录和/或读取操作。此外,如下文中将要描述,在如图2所示的膜表面入射型光记录介质中,物镜的焦距能被减小,从而能够令人满意的进行高密度记录。尤其是,在双层光记录介质100中,(情况a)中的透明树脂层105的厚度(t)最优选从20μm到28μm。当透明树脂层105的厚度(t)落在(情况a)中的范围内时,如果透明树脂层105的弹性模量(E)与透明树脂层105的厚度(t)的乘积(E×t)设为2.0×104(MPa·μm或以上,则能够在L1层上进行稳定的记录。
(情况b)
如图3(b)所示,当透明树脂层由多种树脂层(透明树脂层(1),透明树脂层(2)...透明树脂层(n))形成时,在这些树脂层中,将与倒置层叠结构相接触的树脂层的厚度定义为透明树脂层的厚度(t)。然而,当与倒置层叠结构接触的透明树脂层(1)的膜厚为35μm或以上时,透明树脂层的厚度(t)定义为35μm。
至于制造双层光记录介质100的方法,可提及有一种方法,它包括:在具有L1层的倒置层叠结构11上施涂可透光树脂A;另一方面,在具有L0层的常规层叠结构12上施涂树脂B,并使树脂A与树脂B接触以使其固化,从而制得双层磁盘。在这种情况下,如上所述,当在L1层的记录层(1)103上记录光信息时,在不与倒置层叠结构11接触的透明树脂层105一侧的树脂层(由树脂B形成)被认为不会有效的产生能够防止记录扩大到相邻轨道中的局部制约力。因此,不同于与倒置层叠结构11相接触的树脂层,在靠近具有L0层的常规层叠结构12的树脂层上可使用可UV(紫外线)固化树脂和可UV固化粘合剂。此外,透明树脂层105优选由能够降低整体应力的挠性树脂层和(E×t)值不小于某一预定值的树脂层层叠而成。
在(情况b)中,双层光记录介质100的透明树脂层105的整个膜厚通常为200μm或更小,优选为100μm或更小,更优选为80μm或更小。尤其是,根据双层DVD磁盘的标准,L1层和L0层的间距为从40μm到70μm。在这些形成透明树脂层105的多个类型树脂层当中,如果与倒置层叠结构11相接触的树脂层(图3(b)中的透明树脂层(1))的厚度为35μm或以上,透明树脂层105的厚度(t)就设定为35μm。与倒置层叠结构11相接触的树脂层(图3(b)中的透明树脂层(1))的厚度通常优选为3μm或以上,更优选4μm或以上,进一步优选为10μm或以上,特别优选为15μm或以上。当透明树脂层105的厚度(t)过小时,对串扰的降低作用不充分。
在形成透明树脂层105的多种类型树脂层当中,如果与倒置层叠结构11相接触的树脂层(图3(b)中的透明树脂层(1))的薄膜厚度为35μm或更小,厚度(t)就设定为5μm,乘积(E×t)则通过以下方法计算。更具体地说,假定透明树脂层是复合树脂层,即厚度(t)为5μm的透明树脂层(1)+(2)的复合树脂层,那么乘积(E×t)是将透明树脂层105的弹性模量(E)与透明树脂层105的厚度(t)相乘得到的。例如,如果与倒置层叠结构11相接触的树脂层(图3(b)中的透明树脂层(1))的弹性模量为E1,膜厚为1μm,以及与其相邻的树脂层(图3(b)中的透明树脂层(2))的弹性模量为E2,那么乘积(E×t)按照下式计算:E1×1+E2×4。在这种情况下,透明树脂层(1)和透明树脂层(2)的总膜厚假定为5μm或以上。例如,如果透明树脂层(1)+(2)+(3)的总薄膜厚度是5μm,可按照上述例子的式子计算乘积(E×t)。
现在,具体说明形成透明树脂层105的材料。
作为形成透明树脂层105的材料,可提及的有热塑性树脂,热固性树脂,电子束固定树脂,可UV固化树脂(包括延迟固化树脂)等等。形成透明树脂层105的材料可适当地从这些材料中选取。如有必要,可将树脂如热塑性树脂和热固性树脂溶解于合适的溶剂中以制备涂布溶液,然后将该溶液施涂到基层上,干燥(并加热)以形成透明树脂层105。可UV固化树脂可直接施涂到基层上,或溶解在合适的溶剂中以制备涂布溶液,然后将该溶液施涂在基层上,并用UV线固化,从而形成透明树脂层105。这些材料可以单独使用或以混合物形式使用。
涂布方法可以使用旋涂法和流延法等。其中优选旋涂法。可使用丝网印刷法将高粘树脂施涂在基层上以形成树脂层。对于可UV固化树脂,优选20℃到40℃的液态可UV固化树脂,因为可不使用溶剂进行涂布,从而提高生产率。涂布液的粘度优选在20mPa·s到1.0×103mPa·s之间调整。
在形成透明树脂层105的材料中,优选可UV固化树脂,因为其透明度高且固化时间短,因此对生产有利。作为可UV固化树脂,可提到的有自由基型可UV固化树脂和阳离子型可UV固化树脂。上述树脂中任一种均可使用。自由基型可UV固化树脂是以可UV固化化合物和光致聚合引发剂为主要组分的组合物。作为可UV固化化合物,可使用含有单官能团(甲基)丙烯酸酯和多官能团(甲基)丙烯酸酯作为聚合单体单元的化合物。它们可以单独使用或以两个或更多个组合使用。丙烯酸酯和甲基丙烯酸酯在这里均称为“(甲基)丙烯酸酯”。
单官能团(甲基)丙烯酸酯的例子包括具有取代基的(甲基)丙烯酸酯,这些取代基例如有甲基,乙基,丙基,丁基,戊基,2-乙基己基,辛基,壬基,十二基,十六基,十八基,环己基,苄基,甲氧乙基,丁氧乙基,苯氧乙基,壬基苯氧乙基,氢糠基,缩水甘油基,2-羟乙基,2-羟丙基,3-氯-2-羟丙基,二甲氨乙基,二乙氨乙基,壬基苯氧乙基氢糠基,己内酯,改性氢糠基,异冰片基,二环戊烷基,二环戊烯基,以及二环戊烯氧乙基。
多官能团(甲基)丙烯酸酯的例子包括1,3-丁二醇,1,4-丁二醇,1,5-戊二醇,3-甲基-1,5-戊二醇,1,6-己二醇,新戊二醇,1,8-辛二醇,1,9-壬二醇,三环癸二甲醇,乙二醇,聚乙二醇,丙二醇,一缩二丙二醇,三丙二醇和聚丙二醇等的二(甲基)丙烯酸酯;以及三(2-羟乙基)异氰脲酸酯的二(甲基)丙烯酸酯。
另外可提及的有:通过在1mol新戊二醇中加入不少于4mol的环氧乙烷或环氧丙烷而制得的二醇的二(甲基)丙烯酸酯;通过在1mol双酚A中加入2mol环氧乙烷或环氧丙烷而制得的二醇的二(甲基)丙烯酸酯;通过在1mol三羟甲基丙烷中加入不少于3mol环氧乙烷或环氧丙烷制得的三醇的二或三(甲基)丙烯酸酯;通过在1mol双酚A中加入不少于4mol环氧乙烷或环氧丙烷制得的二醇的二(甲基)丙烯酸酯;三(甲基)丙烯酸三羟甲基丙酯,三(甲基)丙烯酸季戊四醇酯,二季戊四醇的聚(甲基)丙烯酸酯,用环氧乙烷改性的磷酸(甲基)丙烯酸酯,用环氧乙烷改性的烷基化磷酸(甲基)丙烯酸酯,等等。
与聚合物的单体一同使用的物质可以由低聚物如聚酯(甲基)丙烯酸酯,聚醚(甲基)丙烯酸酯,环氧(甲基)丙烯酸酯和氨基甲酸乙酯(甲基)丙烯酸酯。
此外,自由基型可UV固化树脂通常与光致聚合引发剂一起使用。优选的光致聚合引发剂可以有分子裂解型引发剂和氢移除型引发剂。用作光聚合引发剂的分子裂解型引发剂的例子包括二苯乙醇酮异丁醚,2,4-二乙基噻吨酮,2-异丙基噻吨酮,苄基,2,4,6-三甲基苯甲酰基二苯氧膦,2-苄基-2-二甲氨基-1-(4-吗啉苯基)-丁-1-酮,二(2,6-二甲氧苯甲酰基)-2,4,4-三甲基戊基氧膦等。
此外,可以组合使用1-羟基环己基苯酮,二苯乙醇酮乙醚,苄基二甲基缩酮,2-羟基-2-甲基-1-苯基丙-1-酮,1-(4-异丙基苯基)-2-羟基-2-甲基丙-1-酮,以及2-甲基-1-(4-甲基苯硫基)-2-吗啉基丙-1-酮等。对于氢移除型光致聚合引发剂,可以有二苯甲酮,4-苯基苯二甲酮,间苯二苯酮,4-苯甲酰基-4-甲基-二苯硫醚等。
此外,感光剂可以与光致聚合引发剂一同使用。对于感光剂,可以有三甲胺,甲基二甲醇胺,三乙醇胺,对二乙氨基苯乙酮,对二甲氨基苯甲酸乙酯,对二甲氨基苯甲酸异戊酯,N,N-二甲基苄胺,以及4,4-二(二乙氨基)二苯甲酮等。
作为阳离子型可UV固化树脂,可提到的有含有阳离子型聚合光致聚合引发剂的环氧树脂。这种环氧树脂的例子包括双酚A(表氯醇型),脂环族环氧树脂,长链脂环族环氧树脂,溴化环氧树脂,缩水甘油酯型环氧树脂,缩水甘油醚型环氧树脂和杂环族环氧树脂。这些环氧树脂中,优选游离氯和氯离子含量低的环氧树脂。氯含量优选为1wt%或更少,更优选0.5wt%或更少。
作为阳离子型聚合光致聚合引发剂,可提及的有锍盐,碘翁盐,重氮翁盐等等。碘翁盐的例子包括六氟磷酸二苯碘翁,六氟锑酸二苯碘翁,四氟硼酸二苯碘翁,硼酸二苯碘翁四(五氟苯)盐,六氟磷酸二(十二苯)碘翁,六氟锑酸二(十二苯)碘翁,四氟硼酸二(十二苯)碘翁,以及硼酸二(十二苯)碘翁四(五氟苯)盐。
此外,可以有六氟磷酸4-甲基苯基-4-(1-甲基乙基)苯基碘翁,六氟锑酸4-甲基苯基-4-(1-甲基乙基)苯基碘翁,四氟硼酸4-甲基苯基-4-(1-甲基乙基)苯基碘翁,硼酸4-甲基苯基-4-(1-甲基乙基)苯基碘翁四(五氟苯)盐等。
相对于100重量份阳离子型可UV固化树脂,阳离子型聚合光致聚合引发剂的比例通常为0.1~20重量份,优选从0.2~5重量份。注意,可与已知的光敏剂组合使用,以更有效地利用紫外线区、近紫外线区和可见光波区域的波长。这样的光敏剂例子包括蒽,吩噻嗪,苄基甲酮缩醇,二苯甲酮和苯乙酮。
如有必要,可在可UV固化树脂中加入其它添加剂,包括热聚合抑制剂,氧化抑制剂如受阻酚、受阻胺和亚磷酸盐,增塑剂,以及硅烷偶联剂如环氧硅烷、巯基硅烷和(甲基)丙烯酰基硅烷,以改善各种性质。它们之中,选择并使用那些在可UV固化化合物中具有极优的溶解性且不会抑制紫外线透过的添加剂。
在本实施方式的光记录介质100中,对使乘积(E×t)(其中E是透明树脂层105的弹性模量,t是透明树脂层105的厚度)的值不小于2.0×104MPa·μm的方法没有特别限定。然而,在最适当的薄膜厚度范围内制备具有合适刚度的树脂中,为了加宽膜厚范围,可采用以下方法。这些方法包括:增加在作为上述可UV固化树脂的分子内部的单体组分的含量,该单体组分具有两个或更多个,优选三个以上的异丁烯酰基;增加与直链聚合物二醇混合的含有聚合物二醇如聚酯二醇的侧链的含量;通过降低作为主链为硬链段的低聚物组分的侧链的分子量来增加分子内键;加入预定量的交联剂如聚异氰酸酯化合物、氨基树脂、环氧化合物、硅烷化合物和金属螯合物。凭借这些手段,透明树脂层105的弹性模量本身能够增加,从而使形成透明树脂层105的树脂的玻璃化转变温度(Tg)增加到超过约150℃。
在可UV固化树脂中,优选阳离子型可UV固化树脂,因为它具有低的光散射特性和便于旋涂的低粘度。此外,当透明树脂层105的厚度为10μm或以上时,就无需考虑抗固化的氧抑制。因此,优选使用自由基型可UV固化树脂,因为它可从多种树脂中选取,且在组合物中混合比的自由度大。
注意,用于光记录介质(商品)的透明树脂层可通过下列方法检验。
(1)将光盘破碎成若干片,取其横截面并置于二次电子显微镜(SEM)下做显微观察。用这样的方式,可以观察透明树脂层的微观结构(形态)。如果厚度方向上的微观结构不同,可以发现透明树脂层是由多种类型的树脂层形成。
(2)透明树脂层的横截面用微观FT-IR法分析以获得透明树脂层的红外吸收光谱。与用上述方法测定的参考树脂的红外吸收光谱做比对,可基于参考谱图对(透明树脂层的)树脂的组合物进行一定程度上的识别。如果红外吸收光谱在透明树脂层的厚度方向上互不相同,可证实透明树脂层是由多种类型的树脂层形成。这些组合物能够经过与上述参考样品的谱图相比较而被识别。
(3)当使用热分解GC-MS法(气相色谱-质谱法)分析透明树脂层时,能够识别树脂的组合物。
(4)当透明树脂层被剥离和取出时,可使用动态粘弹性模量测定设备直接测定Tg和弹性模量。
(常规层叠结构)
现在说明形成本实施方式的光记录介质100的常规层叠结构12。如图1所示,常规层叠结构12是由具有作为记录和/或读取光的激光110的入射表面的基层(2)109,以及顺序层叠在基层(2)109上的记录层(2)108、反射层(2)107和保护涂层106(这些堆积层有时被称为“L0层”)形成的。
常规层叠结构12的基层(2)109是由与倒置层叠结构11的基层(1)101所用材料相类似材料所组成。然而,基层(2)109必须是可透光的。基层(2)109的槽宽(半值宽度)通常为2T/10或以上,优选3T/9或以上,这里T表示轨道间距。当槽宽落在该范围内时,能够充分确保反射率。更具体地说,如果轨道间距是740nm,基层(2)109的槽宽则为148nm或以上,优选为246nm或以上;但基层(2)109的槽宽通常为7T/10或更小,优选为6T/10或更小。例如,当轨道间距为740nm时,基层(2)109的槽宽通常为518nm或更小,优选为444nm或更小。由于槽几何形态的可转印性得到改善,因此该示范性情况受到优选。
基层(2)109的槽深通常优选设定为λ/10或以上,因为能够充分确保反射率,这里λ是记录和/或读取光的波长。槽深更优选设定为λ/8或以上,进一步优选λ/6或以上。例如,当记录和/或读取光的波长λ(记录和/或读取波长)为660nm时,基层(2)109的槽深通常为66nm或以上,优选为83nm或以上,并进一步优选为110nm或以上。然而,基层(2)109的槽深的上限优选设定为2λ/5或更小,更优选为2λ/7或更小,因为槽的几何形态能被满意地转印。更具体地说,如果记录和/或读取波长是660nm,槽深通常为264nm或更小,优选为189nm或更小。
(记录层(2))
常规层叠结构12的记录层(2)108含有与倒置层叠结构11的记录层(1)103所类似色素。党规层叠结构12的记录层(2)108的合适的的厚度根据记录方法等而变。因此没有特别限定;然而,通常为20nm或以上,优选30nm或以上,尤其优选40nm或以上,以获得充分的调节振幅。然而,由于光必须能透过,记录层(2)108的厚度通常为200nm或更小,优选180nm或更小,更优选150nm或更小。注意,记录层(2)108的厚度是指较厚部分的膜厚(也就是说,基层(2)109的槽部的记录层(2)108的厚度)。
(反射层(2))
常规层叠结构12的反射层(2)107是由与倒置层叠结构11的反射层(1)102所用材料相类似的材料所组成。常规层叠结构12的反射层(2)107必须吸收少量入射到基层(2)109上的作为记录和/或读取光的激光110,其光透射率通常在40%或以上,合适的光反射率为30%或以上。例如,如果使用具有高反射率的金属薄膜,能够获得合适透射。此外,反射层(2)107要求具有一定程度的耐腐蚀性,并进一步具有阻塞特性,用来阻断从反射层(2)107(这里的透明树脂层105)上层渗透来的组分对位于反射层(2)107之下的记录层(2)108造成影响。
反射层(2)107的厚度通常为50nm或更小,优选为30nm或更小,更优选为25nm或更小,以确保40%或更多的光透射;但通常为3nm或以上,优选5nm或以上,这样就可使记录层(2)108不会受到从反射层(2)107的上层渗透来的组分的影响。
(保护涂层)
常规层叠结构12的保护涂层106设置在面向透明树脂层105的反射层(2)107的表面上,用以防止反射层(2)107被氧化,受粉尘污染和损坏等。对保护涂层106的材料没有特别限定,只要能够保护反射层(2)107即可。作为有机材料,可以是热塑性树脂,热固性树脂,电子束固定树脂和可UV固化树脂等。作为无机材料,可以有介电材料如二氧化硅,氮化硅,MgF2和SnO2等。尤其优选层叠可UV固化树脂层。注意保护涂层106并非总是需要的。也就是说,透明树脂层105可以直接形成在反射层(2)107上。
(第二实施方式)
图2显示了本发明光记录介质的第二实施方式。图2显示了薄膜表面入射型光记录介质200,它是通过记录和/或读取光照射到与基层相对侧的介质上来记录和读取光信息的。如图2所示,光记录介质200为倒置层叠结构,其包括基层201,形成在基层201上的反射层202,层叠在反射层202上的记录层203,以及用来保护记录层203的中间层204;此外还有在激光210入射表面处的介质上的透明树脂层205。在光记录介质200中,激光210穿过透明树脂层205照射到记录层203来进行记录和读取信息。注意,如有必要,可设置中间层204,换言之中间层204并非是必不可少的。
形成倒置层叠结构的基层201是由与根据第一实施方式的光记录介质100中的倒置层叠结构11的基层(1)101所用的相类似的材料所形成。此外,形成反射层202、记录层203和中间层204的材料可以是与根据第一实施方式的光记录介质100中的倒置层叠结构11的反射层(1)102、记录层(1)103和中间层104所用的相类似的材料。其他条件如单个层的厚度都落在之前对光记录介质100所述的相同范围内。
此外,透明树脂层205由类似于上述光记录介质100的透明树脂层105所用的材料组成。透明树脂层205的弹性模量(E)和透明树脂层205的厚度(t)的乘积的(E×t)调整在与根据第一实施方式的光记录介质100的透明树脂层105的相同的范围内。更具体地说,当透明树脂层205是类似于根据第一实施方式的光记录介质100的透明树脂层105所用材料由单个类型的树脂所形成时,透明树脂层205的厚度(t)定义为透明树脂层205的膜厚(h)的一半(h/2)。透明树脂层的厚度(t)定义为与倒置层叠结构相接触的透明树脂层205的一半(h/2)的膜厚。当透明树脂层205由多个类型的树脂层所形成时,透明树脂层205的厚度(t)定义为多个树脂层中与倒置层叠结构相接触的单个树脂层的膜厚。然而,当与倒置层叠结构接触的树脂层的膜厚为35μm或以上时,透明树脂层205的厚度(t)设定为35μm。
实施例
下面通过所述的实施例来更具体地说明本发明的实施方式。注意,只要不超过本发明要旨的范围,本发明的实施方式并不局限于这些实施例。
(实施例1~7)
具有倒置层叠结构的双层光记录介质按照如下方法制备,并测定记录在形成倒置层叠结构的记录层(1)上的光信息的MT(%)和ST(%)。
(光记录介质的制备)
(1)(倒置层叠结构的制备)
首先,使用表面具有沟槽的Ni压模机,注射聚碳酸酯模塑形成0.60mm厚、直径为120mm的基层(1),其上槽宽为330nm,槽深为30nm,槽间距为0.74μm。其次,通过溅射Ag-Bi-Nd合金在基层(1)上形成80nm厚的反射层(1)。接着,制备2wt%浓度的四氟丙醇溶液,色素A和色素B(A∶B=60∶40wt%)的混合物,以作为有机色素化合物。由下面的化学式所表示的色素A和色素B是含金属偶氮色素。将溶液滴加到反射层(1)上,进行旋转涂布,并在70℃下干燥30分钟以形成记录层(1)。记录层(1)的厚度,即槽部的膜厚(记录层在倒置层叠结构的槽部中的膜厚,如图1所示)和槽间部的膜厚(记录层在倒置层叠结构的槽间部中的膜厚,如图1所示)均为约80nm。
Figure A20058000189000261
(色素A)
(色素B)
随后,在记录层(1上),通过溅射ZnS-SiO2(组分比为80∶20原子%)而形成130nm厚的中间层。用这样的方式,制备得到具有倒置层叠结构的盘1。
(2)(常规层叠结构的制备)
制备聚碳酸酯基层(2),其具有160nm深、300nm宽和间距740nm的导槽。在形成有导槽的基层(2)的表面上,滴加包含有含金属偶氮色素(即上述以A∶B=60∶40wt%混合的色素A和色素B)的混合物的四氟丙醇溶液(浓度1~2wt%),进行旋转涂布,并在70℃下干燥30分钟以形成记录层(2)。记录层(2)的厚度(记录层在常规层叠结构的槽部中的膜厚,如图1所示)约为100nm。接着,在记录层(2)上溅射Ag-Bi合金(Bi:1.0原子%)以形成厚17nm的反射层(2)。此外,使用旋涂法在反射层(2)上施涂可UV固化树脂(SD347),固化后形成3μm膜厚的保护涂层。用这样的方式,制备得到具有常规层叠结构的盘2。
(3)(双层光记录介质的制备)
在具有用上述方法制备的倒置层叠结构的盘1的中间层上,旋转涂布树脂A(自由基型可UV固化树脂,其弹性模量(E)为4.0×103MPa,玻璃化转变温度(Tg)为174℃,由Dainippon油墨化学品公司制造),调节旋涂转速以获得23μm的膜厚。此外,在具有常规层叠结构的盘2的保护涂层上,旋转涂布树脂F(自由基型可UV固化树脂SD-6036,其弹性模量(E)为680MPa,玻璃化转变温度(Tg)为50℃,由Dainippon油墨化学品公司制造),调节旋涂转速以获得23μm的膜厚。随后,使各自涂有树脂表面的盘1和盘2彼此相对设置。然后,使用紫外线照射盘2(常规层叠结构)的基层(2)附近一侧,以使树脂A和树脂F固化。用这样的方式,制备得到具有由透明树脂A层和透明树脂F层形成的透明层的双层光记录介质(试样1)。
随后,在具有常规层叠结构的盘2的保护涂层上,以与在试样1中相同的方法涂布树脂F,以获得23μm的膜厚。另一方面,对于倒置层叠结构的盘1,将表1中所示的具有预定弹性模量(E)的树脂B,C和D施涂到倒置层叠结构的中间层上,并使其达到表1所示的预定厚度(t)。涂覆有这些树脂的盘1和涂覆有树脂F的盘2相互重叠,并使得树脂涂覆表面以与试样1相同的方式彼此相对。随后,通过使用紫外线照射具有常规层叠结构的盘2靠近基层(2)的一侧来固化每个涂覆的树脂,从而制备由两种类型树脂形成的透明树脂层。用这样的方式制备双层光记录介质(试样3、5、6和7)。
此外还制备了没有涂覆树脂的具有常规传统层叠结构的盘2。另一方面,通过在中间层上施涂树脂B和C制备了倒置层叠结构的盘1,以获得如表1所示的预定厚度(t)。将涂覆有树脂的盘1与未涂覆树脂的盘2相重叠。随后,通过使用紫外线照射盘2(传统层叠结构)靠近基层(2)的一侧来固化其上施涂的树脂,从而形成由单种树脂形成的透明树脂层。用这样的方式制备双层光记录介质(试样2和4)。
对于透明树脂层是由两种类型树脂形成的试样1、3、5、6和7的光记录介质,如表1所示的透明树脂层的厚度(t)对应于与倒置层叠结构相接触的树脂层(情况b)的厚度。对于透明树脂层是由单种树脂形成的试样2和4的光记录介质,整个透明树脂层(情况a)的膜厚的一半作为厚度(t)。注意,每个试样1~7的光记录介质的透明树脂层的整体膜厚均为46μm。
光信息在如下的高速记录条件下被记录在每个如此制备的光记录介质(试样1~7)中形成倒置层叠结构的记录层(1)上,并读取如此记录的光信息,然后测定MT(%)和ST(%)。结果如表1所示。
光信息的高速记录条件如下。
评价设备:DDU-1000(波长662nm,NA=0.65),Pulstech工业有限公司制造;
记录速度:DVD的4倍速度(线速度:15.3m/s);
记录脉冲方案:根据DVD-R规格2.1版执行;
记录功率:26~27.5mW;
记录功率余量:3mW以上;以及
抖动测量:在1倍速度下读取。
(参照例1~3)
制备如下所示的倒置层叠结构的双层光记录介质,以与实施例1相同的方法测定光信息的MT(%)和ST(%)。
以与实施例1对试样1同样的方法,通过在保护层上涂覆树脂F来制备常规层叠结构的盘2,以获得23μm的膜厚。另一方面,通过在倒置层叠结构的中间层上施涂分别具有如表1所示的预定弹性模量(E)的树脂E和C来制备倒置层叠结构的盘1,以获得如表1所示的预定厚度(t)。将施涂有这些树脂的盘1和施涂有树脂F的盘2按试样1的方式相互重叠,使得施涂有树脂的表面彼此相对。随后,通过使用紫外线照射每个盘2(常规层叠结构)靠近基层(2)的一侧来固化施涂其上的树脂,从而形成由两种类型树脂形成的透明树脂层。用这样的方式制备双层光记录介质(试样8和9)。
此外还制备了没有涂覆树脂的具有常规层叠结构的盘2。另一方面,通过在中间层上施涂如表1所示的树脂F来制备倒置层叠结构的盘1,以获得如表1所示的预定厚度(t)。将涂覆有树脂F的盘1与未涂覆树脂的盘2相重叠。随后,通过使用紫外线照射盘2(常规层叠结构)靠近基层(2)的一侧来固化施涂其上的树脂,以形成由单种树脂形成的透明树脂层。用这样的方式制备双层光记录介质(试样10)。
下面说明试样8~10的透明树脂层的厚度(t)。对于具有由不同树脂形成的两种透明树脂层的试样8和9的光记录介质,将与倒置层叠结构相接触的树脂层的厚度作为厚度(t)(情况b)。对于透明树脂层是由单种树脂形成的试样10的光记录介质,将整个透明树脂层的膜厚的一半作为膜厚(t)(情况a)。注意,每个试样8~10的光记录介质的透明树脂层的整体厚度均为46μm。
对于每个如此制备的光记录介质(试样8~10),以与实施例1中相同方式的高速记录条件下,在形成倒置层叠结构的记录层(1)上记录光信息,并读取如此记录的光信息,然后测定MT(%)和ST(%)。结果如表1所示。
注意,用于制备试样1~10的透明树脂层的树脂的弹性模量(E(单位Mpa))、透明树脂层的厚度(t(单位:μm))、玻璃化转变温度(Tg(单位℃))一同显示在表1中。弹性模量(E)是使用动态粘弹性测试器(DDV系列,Leo Vibron公司制造)在3.5Hz的测量频率和3℃/min的升温速率的条件下测定的。
透明树脂层的厚度是基于扫描电子显微镜下观察到的二次电子显微图(SEM图像)或基于透射电子显微镜下观察到的切面显微图来测定的。厚度(t)是5点测量值的平均值。
表1
用于制备表1的透明树脂层的树脂如下所示:
树脂A:自由基型可UV固化树脂(弹性模量:1.4×103MPa/(150℃)),Dainippon油墨和化学品公司制造;
树脂B:自由基型可UV固化树脂(弹性模量:1.05×103MPa/(150℃)),Dainippon油墨和化学品公司制造;
树脂C:自由基型可UV固化树脂SD-347(弹性模量:340MPa/(150℃)),Dainippon油墨和化学品公司制造;
树脂D:自由基型可UV固化树脂SD-394(弹性模量:66MPa/(150℃)),Dainippon油墨和化学品公司制造;
树脂E:自由基型可UV固化树脂SD-318(弹性模量:280MPa/(150℃)),Dainippon油墨和化学品公司制造;
树脂F:自由基型可UV固化树脂SD-6036(弹性模量:0MPa/(150℃)),Dainippon油墨和化学品公司制造;
尤其是,针对上述方法,通过结合能够改善交联密度的丙烯酸单体和在交联结构中具有刚性结构的丙烯酸单体,来调节树脂A和B,以达到预定模量(E)和玻璃化转变温度(Tg)。
现在对表1所示的结果加以解释。
图4分别为试样1~10的(E×t)和MT(%)值之间的关系图。在图4中,基于表1所示的结果,以与倒置层叠结构相接触的透明树脂层的弹性模量(E)和透明树脂层的厚度(t)的乘积(E×t)作为横坐标进行绘制,并且绘制了基于从记录在倒置层叠结构的记录层(1)上的光信息的读取信号得到的MT(%)值。
从图4可明显看出,当(E×t)值超过2.0×104MPa·μm或以上时,MT(%)成为8%或更小。当(E×t)值超过4.0×104MPa·μm时,MT(%)约为7.5%,当(E×t)值为6.0×104MPa·μm时,MT(%)约为7%。此外,当(E×t)超过6.9×104MPa·μm时,MT(%)约为6.5%,当(E×t)超过9.0×104MPa·μm或以上时,MT(%)达到一较好值,稳定在6.5%附近。此外还可看出,(E×t)值为10.0×104MPa·μm或以上时,MT(%)达到理想状态,其维持在最小值。
对于如表1所示的树脂的玻璃化转变温度,与倒置层叠结构相接触的透明树脂层的玻璃化转变温度优选为150℃或以上。这是因为,一般认为,树脂的玻璃化转变温度越高,得到的透明树脂层越硬。
注意,优选的评定方法的条件如下所述。使用半导体激光波长为662nm和物镜口径(NA)为0.65的评定设备在DVD的4倍速度下(记录线速度15.3m/s)进行记录,使用同一评定设备在与DVD速度相同(1倍的速度)进行修正。最短的记录记号长度为0.44μm。
当与倒置层叠结构接触的透明树脂层的弹性模量(E)和厚度(t)的乘积(E×t)具有某一如图4所示的值或更大值时,在倒置层叠结构的记录层(1)上进行高速记录时会出现以下问题。当在单个轨道上而不在相邻轨道上记录时得到的ST(%)与在没有空轨道的连续轨道上记录时得到的MT(%)相比较时,MT(%)劣于ST(%)。这种问题能按上述所克服。
换句话说,通过对刚度和强度作为一体(用与倒置层叠结构相接触的透明树脂层的弹性模量(E)和厚度(t)的乘积(E×t)表示)进行调节使其落入一定范围内,就有可能在高密度记录过程中,在抑制倒置层叠结构中过度的形变扩大到相邻轨道区域中的同时,获得具有较低的串扰和满意的抖动的光记录介质。如果能够获得高密度记录,就能在以最短的0.44μm或更小的记录标记长度进行记录的情况下确保良好的记录特性。
由于记录在一般的光盘产品中不留下非记录轨道,MT(%)表示光盘的信号品质。MT(%)通常必须小于10%,优选为8%或更少,更优选7%或更少。当MT(%)超过10%时,错误数量会增加。
在对试样1~10进行评价中,如果使用评价设备进行记录和/或读取不需要考虑任何波动因素,如安装在通常市场上可买到的驱动的拾音装置上的半导体激光器的个体差异,那么MT(%)通常为8%或更少,优选为7.5%或更少,更优选7%或更少。当MT(%)超过8%时,有时不能确保制造毛利。
同样地,当记录和/或读取是使用上述评价设备进行时,ST(%)通常需设定为7%或更少。当ST(%)超过该值时,MT(%)容易在连续记录中为8%或以上。
MT(%)的功率余量越大越好。例如,MT(%)在9%或更小时的功率余量优选为2.5mW或以上,更优选为3mW或以上,进一步优选为4mW或以上。当功率余量过小时,激光源的光量随温度变化的波动会比功率余量大,从而难以获得满意的记录特性。注意试样1~10中每个都显示出3mW或以上的满意的记录功率余量。
(实施例8)
具有倒置层叠结构的双层光记录介质按照如下方法制备,并测定记录在形成倒置层叠结构的记录层(1)上的光信息的MT(%)和ST(%)。
首先,使用表面具有沟槽的Ni压模机,注射聚碳酸酯模塑形成0.60mm厚、直径为120mm的基层(1),其上槽宽为330nm,槽深为30nm,轨道槽间距为0.74μm。然后,在基层(1)上溅射Ag-Bi(0.35原子%)-Nd(0.2原子%)合金以形成80nm厚的反射层(1)。随后,制备含有类似于实施例1中使用的偶氮色素的色素混合物(重量配合比50∶50)的四氟丙醇溶液(浓度2wt%)。将四氟丙醇溶液滴加到反射层(1)上,进行旋转涂布,并在70℃下干燥30分钟以形成记录层(1)。记录层(1)的厚度,即槽部的膜厚(记录层在倒置层叠结构11槽部的膜厚,如图1所示)和槽间部的膜厚(记录层在倒置层叠结构11槽间部的膜厚,如图1所示)均为约80nm。随后,由无机物质形成的中间层形成在记录层(1)上。用这样的方式,制备得到具有倒置层叠结构的盘1。
此外,用与实施例1相同的方法制备常规层叠结构。
在具有用上述方法制备的倒置层叠结构的盘1的中间层上,旋转涂敷树脂B(自由基型可UV固化树脂,其弹性模量(E)为3.0×103MPa,玻璃化转变温度(Tg)为181℃,由Dainippon油墨化学品公司制造),调节旋涂转速以获得25μm的膜厚。此外,在具有常规层叠结构的盘2的膜表面上旋转涂布树脂B,调节转速以获得同盘1一样的25μm的膜厚。其后,将各自涂有树脂的盘1和盘2以其涂覆树脂的表面彼此相对的方式层叠。随后,通过紫外线照射盘2(常规层叠结构)靠近基层(2)的一侧来固化树脂B,以形成透明树脂层。用这样的方式制备双层光记录介质。
光信息在下列条件下被记录在如此制备的形成光记录介质的倒置层叠结构的记录层(1)上,并读取所记录的光信息,然后测定MT(%)和ST(%)。注意,光信息的记录条件如下所述。
评价设备:
2.4倍速记录/DDU-1000(波长662nm,NA=0.65),Pulstech工业有限公司制造;
8倍速记录/ODU-1000T5(波长658.5nm,NA=0.65),Pulstech工业有限公司制造;
记录速度:2.4倍DVD速度(线速度9.22m/s:表示为2.4×;注意,正常速率时线速度是3.84m/s是正常速度)和8倍速(线速度30.72m/s:表示为8×);
记录脉冲方案:根据DVD+R规范2.1版执行;
抖动测量:在1倍速下读取。
注意记录功率在2.4×记录下为21.6mW,在8×记录下P0=50mW,Pm=29.5mW。其结果与下面对照例1和2的结果一起显示在表2中。
(对照例1和2)
在与实施例8类似的条件下制备双层光记录介质(对照例1和2的两个试样),所不同的是反射层(1)的膜厚分别设定为100nm(对照例1)和120nm(对照例2)。以与实施例8相同的方式在2.4×和8×的速度下进行记录。结果见表2。
注意在对照例1中,2.4×记录下的记录功率为21.6mW,在8×记录下P0=50mW,P0=29.5mW。在对照例2中,2.4×记录下的记录功率为22.2mW,在8×记录下P0=52mW,P0=30.5mW。
表2
反射层膜厚(μm)   MT(%)-ST(%)   @2.4×   @8×
  @2.4×   @8×   MT(%)   ST(%)   MT(%)   ST(%)
 实施例8  80   -0.7   0.8   7.3   8   7.5   6.7
 对照例1  100   0.5   1.1   7.9   7.4   7.9   6.8
 对照例2  120   0.6   1.2   7.6   7   8.2   7
图6显示的是根据表2的结果绘制的(MT(%)-ST(%))值对反射层(1)厚度的关系图。如图6所示,随着反射层(1)厚度的增加,(MT(%)-ST(%))值增加,串扰随之减小。当膜厚达100nm或以上时,(MT(%)-ST(%))值达到饱和;但串扰比膜厚为80nm时的低。
由图6所示结果看出,通过将反射层(1)的膜厚设定得比常规反射层的(通常在100nm以上)更低,有可能改进串扰和(MT(%)-ST(%))。
注意,正如用图5(b)所解释的那样,当反射层的膜厚为40nm或更小时,反射率会减小,此外,当膜厚为30nm或更小时,反射率会在很大程度上减小。因此,反射层(1)的膜厚不宜小于30nm。
在本实施方式中,描述了通过粘合两个盘基制造双层光记录介质的方法;但是,也可使用透明压模机采用2P方法形成双层光记录介质。
在2P法中,表面具有导槽和预制凹坑的透明树脂层通过下述步骤形成:使用旋涂法在常规层叠结构的反射层(2)上施涂可UV固化树脂层,在所形成的树脂层上放置透明树脂压模,使用例如紫外线照射透明树脂压模使可UV固化树脂层固化,当树脂层完全固化后移除树脂压模。在所形成的透明树脂层上,使用旋涂法形成含有有机色素的记录层(1),并进行干燥以形成反射层(1)。在记录层(1)上,形成由金属组成的反射层(1)。此外,在反射层(1)上形成粘合层。使用粘合剂粘合如此制备的基层(1)以制成双层光记录介质。
如上述所述,在本实施方式的光记录介质100中,当形成有透明树脂层105且记录标记是形成在倒置层叠结构11的基层(1)100的槽间部(岸台部)中时,有可能抑制因记录标记突出到靠近槽间部的槽中的厚色素膜部分中而引起的串扰的增加。
此外,本发明人在研究中发现,通过将反射层(1)102的膜厚降低到某一范围内以产生不同的导热性参数,来降低串扰。
本发明是基于申请日为2004年7月6日的日本专利申请(专利申请No.2004-199770),其整个文件引入在此作为参考。

Claims (14)

1.一种光记录介质,其特征在于,包含
顺序层叠有基层、反射层和记录层的倒置层叠结构,以及
设置在所述倒置层叠结构的所述记录层一侧上的透明树脂层,
其中,所述透明树脂层的厚度(t)和25±5℃下的弹性模量(E)的乘积(E×t)为2.0×104MPa·μm或以上。
2.如权利要求1所述的光记录介质,其特征在于,所述透明树脂层的厚度(t)和25±5℃下的弹性模量(E)的乘积(E×t)为30.0×104 MPa·μm或以下。
3.如权利要求1所述的光记录介质,其特征在于,形成所述透明树脂层的树脂在25±5℃下的弹性模量(E)不小于3.0×103MPa且不大于6.0×103MPa。
4.如权利要求1所述的光记录介质,其特征在于,所述透明树脂层的膜厚(h)不小于20μm且不大于200μm。
5.如权利要求1所述的光记录介质,其特征在于,所述记录层是含有有机色素的记录层。
6.如权利要求1所述的光记录介质,其特征在于,在所述记录层和所述透明树脂层之间进一步包含中间层。
7.如权利要求1所述的光记录介质,其特征在于,在所述透明树脂层的与设置有倒置层叠结构一侧相对的的一侧上进一步顺序设置有第二反射层、第二记录层和透明基层。
8.一种光记录介质,其特征在于,包含:
记录层,通过光照射在其上来记录和/或读取信息;
设置在所述记录层的光入射表面上的透明树脂层;以及
设置在所述记录层上与所述光入射表面相对一侧上的反射层,
其中所述透明树脂层的厚度(t)和25±5℃下的弹性模量(E)的乘积(E×t)为2.0×104MPa·μm或以上。
9.如权利要求8所述的光记录介质,其特征在于,所述透明树脂层是由玻璃化转变温度为150℃或以上的透明树脂组成。
10.如权利要求8所述的光记录介质,其特征在于,在所述透明树脂层的光入射表面上进一步包含以直接方式或以中间插入有另一层的方式顺序层叠的第二反射层和第二记录层,其中,所述记录层和所述第二记录层之间的间隔为40μm~70μm。
11.一种光记录介质,其特征在于,顺序层叠有基层、反射层、记录层和透明树脂层,其中,所述反射层含有以Ag为主要组分的金属,其膜厚不小于30nm且不大于80nm。
12.如权利要求11所述的光记录介质,其特征在于,所述反射层的Ag含量在50%或以上。
13.如权利要求11所述的光记录介质,其特征在于,所述记录层含有有机色素。
14.如权利要求11所述的光记录介质,其特征的于,形成所述透明树脂层的树脂在25±5℃下的弹性模量E不小于3.0×103MPa且不大于6.0×103MPa。
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CN107767887A (zh) * 2017-12-06 2018-03-06 苏州盤谷信息光学有限公司 一种基于分色反射层的全息存储装置
CN110632331A (zh) * 2019-10-31 2019-12-31 无锡锦帛诚医疗器械科技有限公司 一种用于总胆固醇定量检测的干片试剂

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