CN1767024A - 光信息记录介质 - Google Patents

光信息记录介质 Download PDF

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CN1767024A
CN1767024A CNA200510102872XA CN200510102872A CN1767024A CN 1767024 A CN1767024 A CN 1767024A CN A200510102872X A CNA200510102872X A CN A200510102872XA CN 200510102872 A CN200510102872 A CN 200510102872A CN 1767024 A CN1767024 A CN 1767024A
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optical information
light
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石桥佐知子
原风美
藤井彻
新井雄治
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Taiyo Yuden Co Ltd
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Abstract

本发明提供一种改善了光盘的耐湿可靠性、抖晃特性的贴合型光信息记录介质，其特征为，用于贴合的粘合剂层的玻璃化温度为100℃或100℃以上、200℃或200℃以下，25～80℃的弹性模量为1000MPa或1000MPa以上，粘合强度为4N或4N以上，反射层的硬度以纳米压痕硬度表示为60mgf/μm2或60mgf/μm2以上，色素层的色素对水的溶解性用吸光度表示为0.2或0.2以下。

Description

光信息记录介质
技术领域
本发明涉及一种具有良好记录特性的可记录型光信息记录介质。
背景技术
目前已知有下述贴合型光盘等可记录型光信息记录介质，即，在透光性基板上具有包括色素层、反射层、以及根据需要的保护层等各层的结构，将至少具有色素层的其它同样结构或者不同结构的光盘的各层侧对置并用粘合剂进行贴合，或者直接使透光性基板本身对置并用粘合剂贴合，从另一主表面侧入射例如波长为400～670nm的DVD半导体激光、或者入射波长更长的CD-R半导体激光，从而可对信息进行信息记录、再现。
专利文献1：特开平9-69239号公报
发明内容
该公报中记载的粘合剂层使用阳离子聚合类树脂为主体材料，由于玻璃化温度(Tg)太低，因此可能使两基板间发生剥离，而且Tg太低时，光盘的初期抖晃值(jitter)恶化、或者粘合剂层在空气中吸湿发生变质而导致其强度降低，即存在所谓耐湿可靠性恶化的倾向，因而不能满足作为光信息记录介质的光学特性及机械特性。
对于具有贴合结构的光盘的两基板间的剥离问题，目前还没有不仅从粘合剂层强度的角度，而且兼顾与其它结构部分之间的关系，从各种物性值着眼进行讨论的先例。
本发明的第1目的为提供一种适应高速化、初期抖晃及耐湿可靠性不发生恶化的光信息记录介质。
本发明的第2个目的为提供一种从贮存用盒中取出时也不发生剥离的、具有贴合结构的光信息记录介质。
本发明为了解决上述问题而提供一种光信息记录介质，是将一对透光性基板对置，在对置的至少一方的主表面侧具有包括用于记录或已记录的色素层的各层，将对置的表面用粘合剂层贴合，并且在各个透光性基板的反面侧的主表面侧至少可以入射记录光及再现光中的再现光，该光信息记录介质的特征为，粘合剂层具有下述弹性模量的温度特性，即，弹性模量相对于温度的变化中玻璃化温度为100℃或100℃以上、200℃或200℃以下。
并且，前述粘合剂层在25～80℃时的弹性模量优选为1000MPa或1000MPa以上。
另外，前述粘合剂层优选具有下述粘合强度特性，即前述一对透光性基板为圆板(直径240mm、厚0.6mm)时，将在其上形成前述各层后的圆板对置，用该粘合剂层贴合，在所述一对透光性基板的内周间隙插入薄膜状的刚性金属片，将上方固定，仅在下方施加荷重，两基板间即将剥离时的荷重值为4N或4N以上。
另外，前述各层包括反射层，所述反射层优选具有以下硬度特性：硬度以纳米压痕(Nanoindentation)硬度表示为60mgf/μm2或60mgf/μm2以上。
另外，优选使前述色素层的色素相对于水具有以下溶解特性：在2.5cm四方形聚碳酸酯基板上涂布该色素层的色素后，将其在5ml、75℃的热水中浸渍60分钟之后，前述热水的吸光度在最大吸收波长处为0.2或0.2以下。
本发明可以提供一种适应高速化、初期抖晃及耐湿可靠性不发生恶化的光信息记录介质，同时，提供一种从保管用贮存盒中取出时也不发生剥离的具有贴合结构的光信息记录介质。
具体实施方式
本发明中的光信息记录介质包括仅利用光学激光实现记录、再现方式、或者使用光磁性记录再现方式等任一种贴合型光信息记录介质。
例如，作为光信息记录介质具体可以举出下述贴合型光盘，即，将在透光性基板的一侧主表面上设置色素层、在色素层上设置金属反射层、根据需要进一步在反射层上设置保护层，并在另一侧主表面上根据需要设置可剥离的保护膜而得到的光盘与下述两种光盘的设置有各层的主表面侧对置并用粘合剂层接合形成的贴合型光盘，所述两种光盘为，与上述同样地全部设置所述色素层、反射层、根据需要的保护层(例如紫外线固化型树脂)及保护膜的光盘，或者不设置所述色素层、反射层、保护层及保护膜中的某部分、除此之外同样地设置的光盘；还可以举出将上述各光盘与除了预先在透光性基板上设置跟踪(dracking)用导向槽后再在其上设置色素层以外，与前述同样地构成的光盘的设置有各色素层的主表面侧对置，或者将上述各光盘与其它透光性基板对置，分别用粘合剂层接合形成的贴合型光盘。在上述光盘中进行记录、再现时，可以在剥离了保护膜的面侧、或者当未设置保护膜时直接在该面侧入射记录光、再现光。使用激光作为记录光、再现光时，在DVD±R的情况下通常采用波长为400～670nm的半导体激光、在CD-R的情况下通常采用波长为770～830nm的半导体激光，也可以使用除此之外的激光。
上述为含有色素层作为记录层的情况，也有不具备上述色素层、直接在透光性基板上进行记录，在其上依次叠层反射层及保护层的CD等读取专用光盘，其也是在透光性基板记录侧的反面侧入射再现光，利用透光性基板上形成的记录用凹坑(pit)和覆盖其的反射层可以再现信息，该光盘也可以作为贴合型光盘的一个光盘与前述同样地使用。
除了前述色素层、反射层，还可以具有其它层，例如、提高上述各层和其它相邻层的粘合性的层、用于记录信息之外的提高可靠性的例如SiO2等氧不透过性层、以及在光反射层和保护层之间防止光反射层氧化的耐氧化层。
设置在反射层上的保护层是用于保护信息记录部分免受外界物理性或者机械性损伤的层，其厚度优选在5～10微米的范围内。特别优选由紫外线固化型树脂形成的保护层，其可以避免形成上述保护层时加热对基板或记录层的不良影响、可以快速形成。
前述用于贴合的粘合剂层在干燥后或固化后必须至少具有下述(a)的特性，优选进一步具有下述(b)的特性。(a)弹性模量的温度特性为，弹性模量相对于温度的变化中玻璃化温度为100℃或100℃以上、200℃或200℃以下。(b)弹性模量特性为，在25～80℃时的弹性模量为1000MPa或1000MPa以上(至少为1000MPa，下文中，数值涉及“以上”时指“至少”，也可以强调下限)。
前述(b)的上限为5000MPa，高于此则产生两基板间的剥离问题，不能获得希望的粘合强度，即，前述(c)的粘合强度可能变为不足4N。另外，低于1000MPa则耐湿可靠性或初期抖晃恶化。从上述各方面考虑更优选1400MPa或1400MPa以上，由此可以赋予确实的耐湿可靠性，初期抖晃变良好。
此处，相对于温度的弹性模量(拉伸单位长度的应力)在从玻璃态向橡胶态转化的过程中，其变化率较大，由于其变化率较大而能够与该变化率较小的玻璃态或橡胶态相区别，变化曲线中对应于上述变化率较大范围的温度范围中存在玻璃化温度，以Tg表示。
就动态粘弹性的观点而言，表示聚合物弹性要素大小的动态贮能模量(G’)随温度的升高而降低，热塑性树脂在橡胶区域中G’也持续下降，然而，交联型聚合物在橡胶区域中G’不发生持续下降，而是成平坦状或上升。另一方面，表示聚合物粘性要素的大小的动态损失弹性模量(G”)与温度的关系用具有极大值的曲线表示，另外，力学损失(损失正切)tanδ(δ为相角(应力与变形矢量的相位差))可以从应力和变形的简谐振动的相位差进行测定，成为表示赋予系统的力学能量因发热而损失的程度的标尺，表示曲线G”、tanδ的峰值的温度成为动态测定的Tg(玻璃化温度)，也可以作为前述的玻璃化温度Tg。为了增大该Tg，可以增大交联密度，设计苯基核等核结构浓度高的聚合物；为了减低Tg，可以降低交联密度，例如可以在聚合物中导入脂肪酸的烷基链、或混合增塑剂。应予说明，详细情况可参考“最新颜料分散技术”(1993年、技术信息协会发行、第53～54页、2.1项)。
所述(b)更优选为下述(b)’。
(b)’可使弹性模量在25℃时为2500MPa或2500MPa以上(特别是3000MPa或3000MPa以上)、5000MPa或5000MPa以下，在80℃时为1000MPa或1000MPa以上(特别是2000MPa或2000MPa以上)、5000MPa或5000MPa以下。低于所述下限时，耐湿可靠性或抖晃方面可能出现问题，高于5000MPa时可能出现粘合强度不充分的问题。
此处，由于使25℃、80℃的弹性模量分别均衡化，因此其均衡化的协同效果赋予了确实的耐湿可靠性，初期抖晃也良好。特别是在色素水溶性较高的情况下也较为可靠，能够较好地适应高速化的要求。
从前述(a)、(b)的特性方面考虑，目前作为前述用于贴合的粘合剂使用的紫外线固化型树脂组合物的固化物，其Tg并不高于100℃、25～85℃的弹性模量也不高于1000MPa，(b)’中各温度的弹性模量也不大于上述各值，但本发明的粘合剂层通过选择使用具备前述(a)、(b)(特别是(b)’)的特性的粘合剂，不易受到湿度的影响，也可以抑制变形，因此不会损失光盘的初期抖晃或耐湿可靠性。
前述粘合剂层除了具备前述(a)、(b)的特性之外，更优选具有下述(c)、(d)的特性。
(c)粘合剂层的粘合强度特性为，当前述一对透光性基板为直径240mm、厚0.6mm的圆板时，将在其上形成有各层的基板对置并通过粘合剂层贴合，在所述一对透光性基板的内周间隙插入薄膜状的金属片，仅在其中一方的下方施加荷重，两块基板间即将剥离时的荷重值为4N或4N以上。
(d)各层中含有反射层，所述反射层具有以下硬度特性：硬度以纳米压痕硬度表示为60mgf/μm2或60mgf/μm2以上。
前述(c)的粘合强度为4N或4N以上，特别优选为7N或7N以上，小于4N则粘合强度不足，将贴合型光盘从贮存盒中取出时两基板间即可发生剥离。另外所述反射层的硬度也特别优选为130mgf/μm2或130mgf/μm2以上。
当粘合强度不足4N、或反射层的硬度不足60mgf/μm2时，不能够提高可靠性(抑制起因于色素溶解性的记录特性恶化)。
另外，也优选具有下述(e)的特性。
(e)色素层的色素相对于水的溶解特性为，在2.5cm四方形的聚碳酸酯基板上涂布该色素层的色素后，将其在5ml、75℃的热水中浸渍60分钟之后，该热水的吸光度在最大吸收波长处为0.2或0.2以下。
该(e)表示色素相对于水的溶解特性，如果前述吸光度为0.2或0.2以下、优选为0.15或0.15以下、更优选为0.1或0.1以下，则在涂布上述溶液形成色素层时，容易形成均匀的高密度连续薄膜，可以对该色素膜进行高精细的记录，也能够适应于高速记录。
如上所述，前述(a)～(e)中可以具有包括所述(a)的多种特性，具备多种特性，特别是具备全部特性时，可以利用使玻璃化温度、弹性模量、反射膜硬度、色素水溶性均衡化而得到的协同效果来提高光盘的初期抖晃或耐湿可靠性。
作为具备前述(a)～(c)特性的粘合剂，可以是非固化型粘合剂，也可以是固化型粘合剂，作为固化型粘合剂，可以是热固化型(包括常温固化)粘合剂，也可以举出紫外线固化型树脂组合物，均能够举出例如(甲基)丙烯酸类树脂组合物。作为紫外线固化型树脂组合物，由感光性预聚物(例如在聚酯树脂等高分子中设置双键得到的物质)、光聚合引发剂、反应性稀释剂(例如多官能丙烯酸酯单体等不饱和单体)等形成(用热聚合催化剂代替光聚合引发剂也可以形成热固化型)，可以举出例如SD-694(大日本INK化学工业社制)。在感光性预聚物中导入芳香环，或者提高双键密度，选择反应性稀释剂的种类或使用量，由此可以调整所述组合物固化物的玻璃化温度、各温度的弹性模量，另外，通过在感光性预聚物中导入官能基、选择反应性稀释剂的种类或使用量，由此可以提高对基板的粘合性，从而具备前述(a)～(c)的特性。形成粘合剂层时，在一方光盘的设置有各层的侧面利用旋涂法等涂布粘合剂，叠合另一光盘的设置有各层的侧面，或者叠合基板，从反面侧入射紫外线使其固化。
作为反射层，可以举出下述高反射率材料膜，即，利用蒸镀、溅镀等形成的Au、Al、Ag、Cu、Pt及它们彼此间形成的合金、以及添加了上述金属之外的微量成分的合金等的金属膜等。然而，作为具备前述(d)特性的反射层，例如可以由合金组合得到，可以举出例如AgPdIn、AgZnCu、AgBi、AgCuPd、AgPd、AgCuCa、AgNdCu、AgCuNi、AgZn、AgCuBi等的Ag和从Pd、In、Cu、Bi、Ca、Nd、Ni、Zn组成的组中选出的1种或者多种合金。
作为能够具备前述(e)特性的色素，可以优选使用三次甲基菁(trimethine cyanine)等，作为具体产品可以举出NK-5134、NK-5907、NK-4741、NK-4413。
本发明中，作为前述透光性基板可以使用由相对于激光的折射率在1.4～1.6范围内的透明度较高的材料形成的耐冲击性优良的树脂。具体而言，可以用聚碳酸酯、聚烯烃、丙烯酸酯等树脂以注塑成形等方法形成，此时，也可以设计前述导向槽为螺旋状或其它形状的跟踪导向单元。所述跟踪导向单元通常采用压模以公知的方法形成。
作为保护膜例如可以举出聚酯、尼龙、乙酸酯或者聚乙烯等聚烯烃等的膜，其优选的厚度为例如100μm左右。也可考虑使用其它环氧类材料、丙烯酸酯类材料等各种材料，其中优选丙烯酸酯类材料。
实施例
下面说明本发明的实施例。
实施例1
准备外径120mm、内径15mm、厚1.2mm的聚碳酸酯基板(Iupilon：三菱GAS化学社制)，在所述基板上用压模形成宽0.8μm、深0.08μm、轨道间距1.6μm的螺旋状导向槽，所述导向槽形成在直径为46～117mm的范围中用于跟踪导向。该基板的硬度为铅笔硬度(使用三菱铅笔)HB，热膨胀系数在20～120℃下为6×10.5/℃。
将0.65g色素(日本感光色素研究所制NK-4624)溶解在10ml双丙酮醇中，采用旋涂法，在前述聚碳酸酯基板的设置有导向槽的一侧边适当改变转速边涂布上述溶液，使平均膜厚在70～80nm的范围内，干燥形成色素层。
该色素在预先测定表示色素溶解特性的前述(e)的吸光度时，吸光度为0.1。所述测定是在2.5cm见方的聚碳酸酯基板(厚1mm)上采用旋涂法涂布前述色素溶液，形成膜厚100nm的色素膜，以此作为实验片。在50cc的烧杯中装入75℃的热水5ml，保温于该温度下并浸渍所述实验片，保持60分钟。然后取出试验片，将着色的热水冷却至常温，用分光光度计(日立制作所社制)测定吸光度。
在该色素层形成有由AgCuZn的合金膜构成的厚100nm的反射层。对该反射膜测定前述(d)的纳米压痕硬度，结果为130mgf/μm2。所述测定采用超微压痕硬度试验仪(ELIONIX社制)进行测定。
然后除去前述色素层和反射层的不必要部分，在直径42～118mm的范围内同心圆状地形成色素层和反射层的双层。
由此可以制成光盘，制作两个上述光盘，在一个光盘的形成了色素层等各层的侧面用旋涂法涂布由(甲基)丙烯酸类紫外线固化型树脂组合物构成的粘合剂(大日本INK化学社制SD-694)，将另一光盘的形成了色素层等各层的侧面对向重叠，用高压水银灯入射230mi/cm2的紫外线，使粘合剂固化，从而形成厚40μm的粘合剂层。由此得到贴合型光盘。
检查该贴合型光盘的前述(c)的特性时，粘合强度(剥离强度)为7N，直接剥离光盘。所述测定将厚0.1mm的刚性铁片插入两基板间的内周间隙，把持上侧基板的圆周侧将其固定后，对铁片施加荷重(每次10g)，读取两基板即将剥离时的荷重。
另外，使用前述SD-694，与前述同样地入射紫外线制作与前述粘合剂层同样的粘合剂层，由此得到试验片，利用动态粘弹性法测定弹性模量的温度分散行为从而求出前述(a)、(b)的物性值。应予说明，具体的测定基于JIS-K6251进行。结果如表1所示。
另外，在上述试验之前，对前述贴合型光盘利用搭载有半导体激光(NA(开口率)＝0.45)的PULSTEC工业社制光盘评价装置(DDU-1000)在线速1.2m/秒下对EMF信号进行了记录。记录后进行再现，测定反射率、调制度、PI误差时结果均良好，测定抖晃结果为7.7％。抖晃测定值在表1中示出。
另外，对于与检查前述(c)的特性时制作的光盘相同的贴合型光盘，其耐湿可靠性试验(在80℃、相对湿度80％的恒温槽中保持400小时后测定抖晃，以确认试验开始前后抖晃不变为良好(○)、以能够明显确认变化为不良(×)进行评价)结果良好。不良(×)的评价基准为抖晃在13％或13％以上、或者PI误差为280或280以上。
实施例2、比较例1～3
除了将实施例1中粘合剂的物性变化为表1中相应栏所记载的值之外，同样地制作贴合型光盘。将与实施例1同样测定的结果在表1中给出。需要说明的是，所述实施例2、比较例1～3中反射膜的硬度为130mgf/μm2、色素的水溶性测定中吸光度为0.1。
表1
  实施例   比较例
  1   2   1   2   3
玻璃化温度(Tg)(℃)   180   195   100   80   150
弹性模量(MPa)   25℃   3200   3500   1300   1500   2000
  80℃   2100   2000   460   1000   800
耐湿可靠性试验   ○   ○   ×   ×   ×
初期抖晃(％)   7.7   7.3   8.35   8.7   8.17
粘合强度(剥离强度)(N)   7   11.1   9.1   12.7   9.5

Claims (5)

1、一种光信息记录介质，是将一对透光性基板对置，在对置的至少一方的主表面侧具有包括用于记录或已记录的色素层的各层，将对置的表面用粘合剂层贴合，并且在各个透光性基板的反面侧的主表面侧至少可以入射记录光及再现光中的再现光，该光信息记录介质的特征为，粘合剂层具有下述弹性模量的温度特性，即，弹性模量相对于温度的变化中玻璃化温度为100℃或100℃以上、200℃或200℃以下。
2、如权利要求1所述的光信息记录介质，其特征为，所述粘合剂层在25～80℃的弹性模量为1000MPa或1000MPa以上。
3、如权利要求1所述的光信息记录介质，其特征为，前述粘合剂层具有下述粘合强度特性：所述一对透光性基板为圆板(直径240mm、厚0.6mm)时，将在其上形成了所述各层后的圆板对置并用粘合剂层贴合，在所述一对透光性基板的内周间隙插入薄膜状的刚性金属片，固定上方，仅在下方施加荷重，两基板间即将剥离时的荷重值为4N或4N以上。
4、如权利要求1或3所述的光信息记录介质，其特征为，所述各层包括反射层，该反射层具有以纳米压痕硬度表示为60mgf/μm2或60mgf/μm2以上的硬度特性。
5、如权利要求1或3所述的光信息记录介质，其特征为，所述色素层的色素相对于水的溶解特性为，在2.5cm见方的正方形聚碳酸酯基板上涂布该色素层的色素后，将其在5ml、75℃的热水中浸渍60分钟，此时所述热水的吸光度在最大吸收波长处为0.2或0.2以下。
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