CN100350481C - 光信息记录介质 - Google Patents

光信息记录介质 Download PDF

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Publication number
CN100350481C
CN100350481C CNB2004100053202A CN200410005320A CN100350481C CN 100350481 C CN100350481 C CN 100350481C CN B2004100053202 A CNB2004100053202 A CN B2004100053202A CN 200410005320 A CN200410005320 A CN 200410005320A CN 100350481 C CN100350481 C CN 100350481C
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China
Prior art keywords
recording medium
optical information
information recording
sticker
storage module
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Expired - Fee Related
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CN1534645A (zh
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角田毅
石田寿男
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Fujifilm Corp
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Fujifilm Corp
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    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
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Abstract

提供一种不受使用环境中温度变化的影响，具有经常稳定的记录再生特性的光信息记录介质。本发明的光信息记录介质，是在基板上形成记录层，并在该记录层上通过粘接层设有透明片材的光信息记录介质，其特征在于上述粘接层的损失弹性模数峰值温度为0℃以下，上述粘接层的25℃下的储藏弹性模数(E1’)和80℃下储藏弹性模数(E2’)之比(E1’/E2’)为2.0以下。

Description

光信息记录介质
技术领域
本发明涉及光信息记录介质，特别涉及加热型的光信息记录介质。
背景技术
为了大量记录和再生文字信息、图像信息、声音信息，不断要求光信息记录介质(例如DVD等)的记录密度进一步提高。特别是由于要与数字高清晰度电视画面的播送相对应，对光信息记录介质的更高记录密度进行了研究。
其中，自从蓝紫色激光器被开发以来，人们研究了使用这种蓝紫色激光器和高NA拾音的光盘系统。而且由《ISO2000》发表了索尼公司使用蓝紫色激光的本身属于相变记录介质的DVR-蓝色系统。作为DVR-蓝色系统中相变记录介质的层结构特征，可以举出在激光光线的入射侧设有被称为表层的厚度0.1毫米的透明层。
作为厚度0.1毫米透明层的形成方法，有人提出例如通过采用紫外线固化树脂或压敏性粘着剂等的粘接层将透明片粘合的方法(例如参见专利文献1～3)。
上述光信息记录介质，可以在TV录像、个人电脑的数据存储器等用途中使用。使用环境多为室温。
但是实际使用的驱动器内部，因其装置自身产生的热量而往往为高温下。特别在长时间连续使用的情况下，驱动器内部温度有时能达到40℃以上。当然，光盘感受其温度变化才得以记录再生，但是特性变化受温度变化的影响必须小。
记录材料一般使用的相变材料或有机色素，在室温至100℃左右的性能变化不太稳定。与此相比，为粘合表层而使用的紫外线固化树脂或压敏性粘着剂，其所具有的玻璃转变点(Tg)大多处在该温度范围内，粘接层的性能(硬度)大多随着温度的上升而发生变化。在使用环境的温度范围内一旦产生性能变化，其温度范围内的记录特性就会发生变化，因而不能获得稳定的记录再生特性。特别是记录材料使用有机色素的追记型光信息记录介质，有时利用由记录部分粘接层的变形而得到的记录部分与未记录部分反射率之差(调制度)来获得高调制度，硬度一旦不同变形的容易度也会不同，导致灵敏度不同。
专利文献1：特开2000-285520号公报
专利文献2：特开2002-8265号公报
专利文献3：特开2000-67468号公报
发明内容
综上，本发明目的在于提供一种不受使用环境中温度变化的影响、具有经常稳定的记录再生特性的光信息记录介质。
为了达成上述目的，本发明人等通过对粘着剂的种类、物质性质等进行深入研究，发明了能在通常使用的温度范围内获得稳定记录再生特性的光信息记录介质。
也就是说，本发明涉及一种光信息记录介质，是在基板上形成记录层，并通过由丙稀系粘接剂或紫外固化树脂构成的粘接层在该记录层上设有透明片材的光信息记录介质，其特征在于上述粘接层的损失弹性模数峰值温度为0℃以下，上述粘接层在25℃下的储藏弹性模数(E1’)和80℃下储藏弹性模数(E2’)之比(E1’/E2’)小于2.0。
而且上述记录层优选是含有有机色素(dye)的层。
另外，在上述基板和记录层之间优选还包括反射层。
另外，在上述记录层和粘接层之间优选还包括中间层。
并且，上述粘接层的损失弹性模数峰值温度优选为-50℃～-15℃。
另外，上述粘接层的损失弹性模数峰值温度优选为-40℃～-25℃。
另外，上述粘接层25℃下的储藏弹性模数(E1’)和80℃下储藏弹性模数(E2’)之比(E1’/E2’)优选为1.5以下。
另外，上述粘接层25℃下的储藏弹性模数(E1’)和80℃下储藏弹性模数(E2’)之比(E1’/E2’)优选为1.0以下。
发明的实施方式
本发明的光信息记录介质，其结构为在基板上形成记录层，通过粘接层在该记录层上设置透明片。
具体讲，可以举出在基板上依次形成反射层、记录层、中间层和粘接层，在该粘接层上设置透明片。
以下举例说明本发明的光信息记录介质的上述结构。
(基板)
作为基板可以任意选择使用过去作为光信息记录介质基板材料使用的各种材料。
具体讲，可以举出玻璃，聚碳酸酯、聚甲基丙烯酸甲酯等丙烯树脂，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，聚酯，铝等金属等，而且还可以根据需要并用这些物质。
在上述材料中，从耐湿性、尺寸稳定性和价格低廉等观点来看，优选聚碳酸酯和无定形聚烯烃，特别优选聚碳酸酯。而且基板厚度优选为0.5～1.4mm。
基板上形成随纹用引导槽或表示地址等信息的凹凸(叫作预制纹道(pregroove)或纹道(groove))。为了获得更高记录密度，优选使用能形成比CD-R或DVD-R更狭窄纹道间距的预制纹道的基板。
具体讲，预制纹道的磁道间距优选为300～600nm范围内。而且预制纹道深度(沟槽深度)优选为20～150nm范围内。
其中为了改善平面性和提高粘着力，优选在设有后述光反射层一侧的基板表面上形成底涂层。
作为底涂层材料，例如可以举出聚甲基丙烯酸甲酯、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、氯磺酰化聚乙烯、硝基纤维素、聚氯乙烯、氯代聚烯烃、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，以及硅烷偶合剂等表面改性剂。
将上述材料溶解或者分散在适当溶剂中制成涂布液后，可以用旋涂法、浸涂法、挤压涂布法等涂布方法在基板表面上涂布这种涂布液的方式形成。底涂层的厚度，一般为0.005～20微米范围内，优选为0.01～10微米范围内。
(光反射层)
光反射层可以使用对激光光线反射率高的光反射性物质。其反射率优选为70％以上。
作为反射率高的光反射性物质，可以举出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等金属和准金属或不锈钢。这些光反射性物质可以单独使用或者两种以上组合使用，或者以合金形式使用。
作为其中优选的可以举出Cr、Ni、Pt、Cu、Ag、Au、Al和不锈钢。而且更优选Au、Ag、Al或其合金，最优选Au、Ag或其合金。
反射层可以采用蒸镀、溅射或离子镀上述的光反射性物质的方法，在基板(纹道形成面)上形成。反射层的厚度优选为10～300纳米，更优选为50～200纳米范围内。
其中当下述的记录层反射率足够大的情况下无需该反射层。
(记录层)
记录层可以在基板的形成纹道的面(形成反射层的情况下，是该反射层)上形成。
记录层既可以是含有有机色素的层，也可以是含有相变记录材料的层(相变记录层)，但是从容易形成明显纹坑(pit)的观点来看，优选含有有机色素的层。
作为上述有机色素，优选三唑系化合物、酞菁化合物、聚非丽苷(ポリフイリン)系化合物、氨基丁二烯系化合物、部花青化合物和花青系化合物等之中的至少一种化合物。作为酞青化合物，优选烷氧基取代物、磺酰胺取代物、氨磺酰基取代物、磺酸取代物中的至少一种物质。
而且可以并用在特开平4-74690、特开平8-127174、特开平11-53758、特开平11-334204、特开平11-334205、特开平11-334206、特开平11-334207等号公报、和特开2000-43423、特开2000-108513和特开2000-158818等号公报中记载的色素。
记录层可以采用将上述色素(有机物等)等记录物质与结合剂等一起溶解在适当溶剂中制成涂布液后，在基板或基板上形成的反射层上涂布此涂布液形成涂膜，然后干燥的方法形成。记录层涂布液中记录物质的浓度，优选为0.01～15重量％范围内，更优选为0.1～10重量％范围内，更优选为0.5～5重量％范围内，最好为0.5～3重量％范围内。
而且作为溶解处理记录物质等的方法，可以采用超声波处理法、均质处理法、加热等方法。
制备涂布液时使用的溶剂，可以举出乙酸丁酯、乳酸甲酯、乳酸乙酯、乙酸溶纤剂等酯类，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、氯仿等氯代烃类，二甲基甲酰胺等酰胺类，甲基环己烷等烃类，四氢呋喃、乙醚、二烷等醚类，乙醇、正丙醇、异丙醇、正丁醇、二丙酮醇等醇类，2，2，3，3-四氟丙醇等含氟溶剂，乙二醇单甲醚、乙二醇单乙醚、丙二醇单甲醚等二醇醚类等。
考虑到使用记录物质的溶解性能，上述溶剂可以单独使用或者两种以上组合使用。必要时还可以在涂布液中添加抗氧化剂、UV吸收剂、增塑剂、润滑剂等各种添加剂。
使用结合剂的情况下，结合剂的实例例如可以举出明胶、纤维素衍生物、糊精、松香、橡胶等天然有机高分子物质，以及聚乙烯、聚丙烯、聚苯乙烯、聚异丁烯等烃系树脂，聚氯乙烯、聚偏氯乙烯、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系树脂，聚乙烯醇、氯代聚乙烯、环氧树脂、丁醛树脂、橡胶衍生物、酚醛树脂等热固性树脂的初期缩合物等合成有机高分子等。作为记录层的材料并用结合剂时，结合剂的用量相对于记录物质而言一般为0.01倍～50倍量(重量比)范围内，优选为0.1倍～5倍量(重量比)范围内。这样调制的涂布液中的记录物质的浓度，一般为0.01～10重量％范围内，更优选为0.1～5重量％范围内。
涂布方法可以举出喷涂法、旋涂法、浸涂法、辊涂法、刮涂法、刀涂法、丝网印刷法等。记录层可以是单层或多层。记录层的厚度一般为20～500nm范围内，优选为30～300nm范围内，更优选为50～100nm范围内。
而且涂布温度若为23～50℃虽然没有特别问题，但是优选24～40℃，更优选25～37℃。
为提高该记录层的耐光性，可以使其含有各种褪色防止剂。
作为褪色防止剂，一般可以采用单态氧猝灭剂。而作为单态氧猝灭剂可以利用在公知的专利说明书等出版物上述载的那些。
其具体实例，例如可以举出特开昭58-175693、同59-81194、同60-18387、同60-19586、同60-19587、同60-35054、同60-36190、同60-36191、同60-44554、同60-44555、同60-44389、同60-44390、同60-54892、同60-47069、同63-229995号公报、特开平4-25492、特公平1-38680和同6-26028等各号公报，和德国专利350399号说明书以及日本化学会志1992年10月号第1141页等上述载的物质。
上述单态氧猝灭剂等褪色防止剂的用量，相对于记录用化合物重量，通常为0.1～50重量％范围内，优选为0.5～45重量％范围内，更优选为3～40重量％范围内，特别优选为5～25重量％范围内。
另一方面，记录层也可以使用相变记录层。相变记录层是由经过激光光线照射能在晶相与非晶相之间反复相变的材料组成的层。
例如可以举出利用以下方法在晶相与非晶相之间反复变化。也就是说，信息记录时，短时间照射聚光的激光光线脉冲，使相变记录层部分熔融。熔融的部分经热扩散而被骤冷、固化，形成非晶状态的记录标记。而且消去时，对记录部分照射激光光线，将记录层加热至熔点以下结晶温度以上温度下，而且通过除冷使非晶状态记录标记结晶，返回到原始的未记录状态。
构成相变记录层材料的具体实例，可以举出Sb-Te合金、Ge-Sb-Te合金、Pd-Ge-Sb-Te合金、Nb-Ge-Sb-Te合金、Pd-Nb-Ge-Sb-Te合金、Pt-Ge-Sb-Te合金、Co-Ge-Sb-Te合金、In-Sb-Te合金、Ag-In-Sb-Te合金、Ag-V-In-Sb-Te合金、Ag-Ge-In-Sb-Te合金等。其中从能够多次重写来看，优选Ge-Sb-Te合金和Ag-In-Sb-Te合金。
相变记录层的厚度，优选10～50纳米，更优选15～30纳米。
以上相变记录层可以用溅射法、真空蒸镀法等，气相薄膜沉积法等形成。
(中间层)
中间层是在上述记录层与后述的粘接层之间形成的任意层。一旦在记录层上形成粘接层，粘接层的粘接剂或者粘着剂就会溶解记录层的有机物。这种情况下，通过设置中间层能使粘着剂等与记录层不直接接触，所以能够防止记录层被粘接剂或粘着剂溶解。
上述中间层的厚度优选1～300纳米，更优选3～110纳米。
构成中间层的材料，只要是能透过光线的材料就无特别限制，但是优选电介质，更具体讲可以举出ZnS、TiO2、SiO2、ZnS-SiO2、GeO2、Si3N4、Ge3N4、Mg F2等无机氧化物、氮化物、硫化物等，其中优选ZnS-SiO2或SiO2。
(粘接层和透明片)
透明片是为保护光信息记录介质内部使之免遭化学变化或物理变化而设置的。
该透明片借助于粘接剂或粘着剂组成的粘接层而被设置在记录层或中间层上。
其中使透明片固着用的粘接层，其损失弹性模数的峰值温度(以下有时叫作“峰值温度”)定为0℃以下。一旦超过0℃，记录时粘接层的变形减小，调制度也减小。为了获得高调制度，该峰值温度优选为-50～-15℃，更优选为-40～-25℃。
而且粘接层在25℃下的储藏弹性模数(E1’)与80℃下的储藏弹性模数(E2’)之比(以下将E1'/E2'称为“储藏弹性模数比”)定为2.0以下。该储藏弹性模数比一旦超过2.0，25℃下与80℃下储藏弹性模数之差就会增大，记录时粘接层的变形量不同，使记录适应性变差。考虑到使记录适应性变化小，储藏弹性模数比优选为1.5以下，更优选为1.0以下。
如上所述，当峰值温度和储藏弹性模数比为上述所定范围内时，能够得到不受使用环境温度变化影响，具有经常稳定的记录再生特性的光信息记录介质。
为了使峰值温度和储藏弹性模数比为上述所定范围内，优选在粘接层中使用具有这些物质性质的粘接剂或粘着剂，考虑到生产率和耐久性，优选实用粘着剂。
作为粘接剂优选使用紫外线固化树脂。
作为粘着剂可以举出丙烯系、橡胶系、硅酮系的等，考虑耐久性和与透明片的粘接性等，优选使用丙烯系的。
丙烯系粘着剂，以赋予粘着性的主要单体、赋予内部凝聚性的共聚性单体(共聚单体)、和因形成交联点而赋予粘着性的官能性单体作为主要成分，其中适当添加提高凝聚力用的交联剂。
作为主要单体，可以举出丙烯酸乙酯、丙烯酸丁酯、2-乙基己基丙烯酸酯、丙烯酸异辛酯、丙烯酸异壬基酯等。
共聚单体可以举出醋酸乙烯酯、丙烯腈、丙烯酰胺、苯乙烯、甲基丙烯酸甲酯、丙烯酸甲酯等。
官能性单体可以举出甲基丙烯酸、丙烯酸等不饱和一元酸，衣康酸等不饱和二元酸，甲基丙烯酸羟基乙酯、甲基丙烯酸羟基丙酯、甲基丙烯酸二甲基氨基乙酯、丙烯酰胺、羟甲基丙烯酰胺、甲基丙烯酸缩水甘油酯、马来酸酐等。
有时也可以不含共聚单体和官能性单体，由多种主要单体构成。
交联剂可以适当使用环氧系、异氰酸酯系等，优选相对于100重量份丙烯系共聚物添加0.1～10重量份。
由这些单体得到的共聚物，优选含有30～90重量％主要单体成分、30～90重量％共聚单体成分、0.1～10重量％官能性单体成分，优选向其中例如添加异氰酸酯系交联剂等，得到丙烯系粘着剂。上述丙烯系共聚物交联前的平均分子量，优选为10000～150000之间。
当丙烯系共聚物的组成和平均分子量为上述范围内时，可以制成能够形成具有已说明所需储藏弹性模数比和峰值温度的粘接层的粘着剂。
根据以下说明的方式能够确定该粘看剂和粘接剂是否具有已说明所需储藏弹性模数比和峰值温度。
首先在测定温度范围内(例如-50～100℃左右)不具有玻璃转变点(Tg)的透明片(例如厚度7微米的聚对苯二甲酸乙二醇酯膜)上，流延粘接剂涂布液或粘着剂涂布液(或UV固化剂)，使厚度达到50～80微米左右。
经过50～60℃数小时干燥后，在设定为40℃的干燥机中放置三天，进行交联。其中使用UV固化剂的情况下，覆盖透明片材之前经过50～60℃数小时干燥后，覆盖上述透明片材，照射紫外线。
将与上述相同的透明片材覆盖在经交联的粘着剂上，制成将粘着剂或粘接剂夹在其间的三层结构膜。
将该膜剪切成所定大小(例如长度5厘米X宽度3毫米)，读出自动动态粘弹性测定器(例如RHEOVIBRON DDV-II-EA，东洋ボ-ルドウイン制造)上25℃的储藏弹性模数(E1’)和80℃的储藏弹性模数(E2’)，求出储藏弹性模数比(E1’/E2’)。而且用该测定器求出损失弹性模数的峰值时的温度。
使用粘接剂形成粘接层的情况下，可以适当采用以下方法等，即首先在记录层上等的透明片材粘合面上涂布粘接剂，然后旋涂覆盖透明片材，使透明片材固着在粘合面上。
另一方面，使用粘着剂形成粘接层的情况下，可以适当采用使赋予了上述粘接剂的透明片材与透明片材粘合面粘合的方法。
粘接层的厚度优选5～50微米，更优选10～30微米。
透明片材只要是透明材料的就无特别限制，但是优选聚碳酸酯、三乙酸纤维素等，更优选23℃50％RH下吸水率5％以下的材料。
而且透明片材的厚度优选为50～95微米范围内，更优选为70～90微米范围内。透明片材厚度小于50微米时，粘接层的厚度增厚，难于均一涂布，不能满足厚度不均为±3微米的规格。而且一旦超过95微米，往往难于满足表层厚度的规格(100微米)。
其中所谓“透明”是指在透过(透过率90％以上)记录用激光光线和再生激光光线的程度上是透明的。
以下说明在本发明光信息记录介质上的信息记录方法和记录信息的再生方法。
在光信息记录介质上述录信息，例如可以进行如下。
首先一边使光信息记录介质以一定线速度旋转，一边从透明片材侧照射记录用500nm以下激光光线。
当记录层含有色素层的情况下，通过这种激光光线的照射，记录层吸收该光线后局部温度上升，产生物理或化学变化(例如形成纹坑)，使其光学特性产生变化。利用这种光学特性的变化记录信息。
另一方面，当记录层含有相变材料层的情况下，通过这种激光光线的照射和骤冷，在照射之处产生结晶学变化(从晶态向非晶态变化)，以此方式记录信息。
作为具有500nm以下谐振波长激光光源，例如可以举出具有390～415nm范围谐振波长的蓝紫色半导体激光器和中心谐振波长约430nm的蓝紫色SHG激光器。
而且为了提高记录密度，拾音用的对物镜开口率(NA)优选为0.7以上，更优选为0.85以上。
另一方面被记录信息的再生，可以采用以下方式进行，即一边使光信息记录介质以与上述同一线速度旋转，一边从透明片材侧照射与信息记录用激光具有同一波长或者波长更短的激光光线，检出其反射光线。
实施例
以下利用实施例更详细说明本发明，但是本发明不受这些实施例的限制。
(实施例1)
(赋予粘着剂的透明片材的制作)
1)溶液制备
将丙烯系共聚物A(溶剂：乙酸乙酯/甲苯＝1/1，以下同)与异氰酸酯交联剂(溶剂：乙酸乙酯/甲苯＝1/1，以下同)混合，使丙烯系共聚物A与异氰酸酯交联剂之比为100∶1(重量比)，制成粘着剂涂布液A。
其中丙烯系共聚物A的组成如表1所示。而且与以下实施例和比较例用的丙烯系共聚物B～E一起记载在表1之中。
表1
     主要单体(重量％)    共聚单体(重量％)   官能性单体(重量％)
丙烯系共聚物A 丙烯酸正丁酯/丙烯酸2-乙基己酯  40/30 甲基丙烯酸酯     25 丙烯酸，甲基丙烯酸     5
丙烯系共聚物B 丙烯酸正丁酯/丙烯酸2-乙基己酯  30/30 甲基丙烯酸酯     35 丙烯酸，甲基丙烯酸     5
丙烯系共聚物C 丙烯酸正丁酯/丙烯酸2-乙基己酯  25/25 甲基丙烯酸酯     45 丙烯酸，甲基丙烯酸     5
丙烯系共聚物D 丙烯酸正丁酯/丙烯酸2-乙基己酯 50 醋酸乙烯酯     45 丙烯酸，甲基丙烯酸     5
丙烯系共聚物E 丙烯酸正丁酯/丙烯酸2-乙基己酯 50 醋酸乙烯酯     49 丙烯酸，甲基丙烯酸     1
2)涂布、干燥、卷曲
一边输送被缠绕成卷状的聚乙烯脱膜膜，一边连续在脱模膜上涂布粘着剂涂布液A，使干燥厚度达到20微米。使之在干燥区(100℃)中干燥后，立即与同样以绕成卷状被输送的聚碳酸酯膜(帝人制造的ピユアエ-ス，厚度80微米，一面设有脱模膜)一起卷成卷状，使聚碳酸酯面与脱模膜的粘着剂面粘合。在共卷状态下在23℃和50％RH条件下保持72小时。
3)冲切、水平保持
对粘合脱模膜的聚碳酸酯膜进行冲切，使之形成与制作的光信息记录介质具有同一形状，制成了光信息记录介质用透明片材。
(光信息记录介质的制作)
在具有厚度1.1毫米、外径120毫米螺旋状纹道(100纳米、宽度120纳米、纹道间距320纳米)的、注塑成形的聚碳酸酯(帝人化成株式会社制聚碳酸酯，商品名：パンライトAD5503)基板的纹道表面上，利用溅射Ag形成其膜厚100纳米的反射层。
然后将酞青系色素A(商品名：ォラゾ-ルブル-GN，Ciba SpecialtyChemicals K.K制造)添加在2，2，3，3-四氟丙醇中，进行2小时超声波处理使之溶解，制成色素涂布液。用旋涂法一边使转速在300～4000转/分钟范围内变化，一边在23℃和50％RH条件下将制成的色素涂布液涂布在反射层上，形成了记录层(厚度80纳米)。
在23℃和50％RH条件下保存1小时后，在记录层上溅射ZnS-SiO2，形成厚度5纳米的中间层。
中间层形成后，剥离上述制作的赋予粘着剂的透明片材，采用轧辊挤压方式使透明片材粘合在中间层上，制成了光信息记录介质。
(实施例2)
除了将丙烯系共聚物B(溶剂：乙酸乙酯/甲苯)和异氰酸酯系交联剂(溶剂：乙酸乙酯/甲苯)以100∶1(重量比)混合制成粘着剂涂布液B，使用粘着剂涂布液B代替粘着剂涂布液A以外，与实施例1同样制成透明片材，制成了光信息记录介质。
(实施例3)
除了将丙烯系共聚物C(溶剂：乙酸乙酯/甲苯)和异氰酸酯系交联剂(溶剂：乙酸乙酯/甲苯)以100∶1(重量比)混合制成粘着剂涂布液C，使用粘着剂涂布液C代替粘着剂涂布液A以外，与实施例1同样制成透明片材，制成了光信息记录介质。
(实施例4)
利用溅射法，在厚度1.1毫米、具有直径120毫米螺旋状纹道(纹间表面高度40纳米、宽度120纳米、磁道间距0.3微米)的、注塑成形的聚碳酸酯(帝人化成株式会社制聚碳酸酯，商品名：パンライトAD5503)基板的纹道表面上，依次形成由反射层(Ag：膜厚100纳米)、下部耐热保护层(ZnS-SiO2：厚度170纳米)、记录层(AgInSbTe：厚度215纳米)和上部耐热保护层(ZnS-SiO2：厚度35纳米)。
然后实用以辊压的方式将实施例1制作的赋予粘着剂的透明片材粘合在一起。
(比较例1)
除了将丙烯系共聚物D(溶剂：乙酸乙酯/甲苯)和异氰酸酯系交联剂(溶剂：乙酸乙酯/甲苯)以100∶1(重量比)混合制成粘着剂涂布液D，使用粘着剂涂布液D代替粘着剂涂布液A以外，与实施例1同样制成透明片材，制成了光信息记录介质。
(比较例2)
除了将丙烯系共聚物E(溶剂：乙酸乙酯/甲苯)和异氰酸酯系交联剂(溶剂：乙酸乙酯/甲苯)以100∶1(重量比)混合制成粘着剂涂布液E，使用粘着剂涂布液E代替粘着剂涂布液A以外，与实施例1同样制成透明片材，制成了光信息记录介质。
(比较例3)
除了将丙烯系共聚物E(溶剂：乙酸乙酯/甲苯)和异氰酸酯系交联剂(溶剂：乙酸乙酯/甲苯)以100∶1(重量比)混合制成粘着剂涂布液E，使用粘着剂涂布液E代替粘着剂涂布液A以外，与实施例1同样制成透明片材，制成了光信息记录介质。其中固化温度比比较例2高30℃左右。
(比较例4)
在厚度1.1毫米、直径120毫米、具有螺旋状纹道(深度100纳米、宽度120纳米、磁道间距320纳米)的注塑成形聚碳酸酯树脂(帝人株式会社制造，商品名：パンライトAD5503)基板的纹道的面上，溅射Ag形成100纳米膜厚的光反射层。
然后将将酞青系色素A(商品名：ォラゾ- ルブル-GN，Ciba SpecialtyChemicals K.K制造)添加在100毫升2，2，3，3-四氯丙醇中混合，进行2小时超声波处理，使之溶解制成色素涂布液。用旋涂法一边使转速在300～4000转/分钟范围内变化，一边在23℃和50％RH条件下将此色素涂布液涂布在光反射层上形成记录层。
在23℃和50％RH条件下保存1小时后，在记录层上溅射ZnS-SiO2，形成厚度5纳米的中间层。
利用旋涂法以100～300rpm转数在形成的中间层上涂布UV粘着剂(大日本油墨株式会社制造，SD-347，在色素中的溶解度为0.05重量％)，与聚碳酸酯片材(帝人制造的聚碳酸酯片材，商品名：ピユアエ-ス，厚度0.07毫米)重合，然后一边使转数从300rpm至4000rpm变化，一边使粘着剂在整个表面上扩展后，用UV灯照射紫外线使之固化，形成了由透明片材构成的表层。进而利用旋涂法以100～300rpm转数在表层上涂布UV粘着剂(大日本油墨株式会社制造，ダイキユリアSD-661)，然后一边使转数从300rpm至4000rpm变化，一边使粘着剂在整个表面上扩展后，用UV灯照射紫外线使之固化，制成了光信息记录介质。其中，记录再生在纹道部分(从表层侧看凹凸)进行。
就实施例1～4和比较例1～4制作的光信息记录介质，测定了粘接层的储藏弹性模数和损失弹性模数，而且对光信息记录介质的特性进行了评价。
结果示于表2之中。
其中储藏弹性模数和损失弹性模数的测定，及特性的评价如下。
1)粘接层储藏弹性模数的测定方法
·测定装置：自动动态粘弹性测定器，RHEOVIBRON DDV-II-EA，(东洋ボ-ルドウイン制造)
·测定频率：110Hz
·测定温度范围：-100℃～100℃
·升温温度：2℃/分钟
·测定样品的制备方法
①使粘着剂涂布液A～E(比较例4的情况下是UV固化粘着剂)在测定温度范围内不具有玻璃转变点(Tg)的薄膜(例如厚度7微米的聚对苯二甲酸乙二醇酯膜)上流延至厚度达到50微米左右。
②50℃下干燥2小时后，40℃的干燥中放置3日进行交联。其中在UV粘着剂(比较例4)的情况下，50℃下干燥2小时后覆盖相同的膜，用紫外灯进行紫外线照射。
③将与上述①相同的薄膜覆盖在交联后的粘着剂(比较例4的情况下是UV粘着剂)上，制成将粘着剂或固化性粘着剂夹在中间的三层结构的膜。
④将上述③的膜剪切成所定大小(长5厘米、宽3毫米)后，用上述测定装置进行测定，读取25℃下的储藏弹性模数(E1’)和80℃下储藏弹性模数(E2’)，求出(E1’/E2’)。而且同时求出损失弹性模数的峰值温度。
2)光盘特性评价
作为光盘的特性评价分为25℃50％RH室温条件下和48℃50％RH高温条件下两种，根据以下方式测定了载波噪声比C/N。
也就是说，在积存有405nm激光器和NA0.85拾音器的记录再生仪(パルステツク株式会社制造，DDU1000型)上，就制作的光信息记录介质，用时钟频率66MHz、线速度5.6米/秒导电性单一频率信号(2T＝0.13微米)记录再生光谱分析仪测定了C/N。
表2
 E”峰值温度(℃)  E1’/E2’(-)   25℃50％RH下的C/N(dB)   25℃50％RH下的C/N(dB)
实施例1     -30     1.2     52  ○     51  ○
实施例2     -5     1.3     51  ○     50  ○
实施例3     -5     1.9     51  ○     49  △
实施例4     -30     1.2     51  ○     50  ○
比较例1     5     1.3     40  ×     39  ×
比较例2     -5     2.2     51  ○     39  ×
比较例3     5     2.2     41  ×     39  ×
比较例4     10     2.1     39  ×     39  ×
上述结果说明，实施例1～4的光信息记录介质，粘接层的损失弹性模数的峰值温度和储藏弹性模数比(E1’/E2’)为所定范围内，与使用温度无关，可以发挥良好的光盘特性。
综上所述，本发明可以提供一种不受使用环境中温度变化的影响，具有经常稳定的记录再生特性的光信息记录介质。

Claims (8)

1.一种光信息记录介质，是在基板上形成记录层，并通过由丙稀系粘接剂或紫外固化树脂构成的粘接层在该记录层上设有透明片材的光信息记录介质，其特征在于上述粘接层的损失弹性模数峰值温度为0℃以下，上述粘接层25℃下的储藏弹性模数(E1’)和80℃下储藏弹性模数(E2’)之比(E1’/E2’)小于2.0。
2.根据权利要求1所述的光信息记录介质，其特征在于：
上述记录层包含有机色素。
3.根据权利要求1所述的光信息记录介质，其特征在于：
在上述基板和记录层之间还包括反射层。
4.根据权利要求1所述的光信息记录介质，其特征在于：
在上述记录层和粘接层之间还包括中间层。
5.根据权利要求1所述的光信息记录介质，其特征在于：
上述粘接层的损失弹性模数峰值温度为-50℃～-15℃。
6.根据权利要求1所述的光信息记录介质，其特征在于：
上述粘接层的损失弹性模数峰值温度为-40℃～-25℃。
7.根据权利要求1所述的光信息记录介质，其特征在于：
上述粘接层25℃下的储藏弹性模数(E1’)和80℃下储藏弹性模数(E2’)之比(E1’/E2’)为1.5以下。
8.根据权利要求1所述的光信息记录介质，其特征在于：
上述粘接层25℃下的储藏弹性模数(E1’)和80℃下储藏弹性模数(E2’)之比(E1’/E2’)为1.0以下。
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EP1447799B1 (en) 2006-07-19
TW200425132A (en) 2004-11-16
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US20040168182A1 (en) 2004-08-26
US7103897B2 (en) 2006-09-05

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