CN1099180A - 光情报媒体及其制造方法 - Google Patents
光情报媒体及其制造方法 Download PDFInfo
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- CN1099180A CN1099180A CN94103974A CN94103974A CN1099180A CN 1099180 A CN1099180 A CN 1099180A CN 94103974 A CN94103974 A CN 94103974A CN 94103974 A CN94103974 A CN 94103974A CN 1099180 A CN1099180 A CN 1099180A
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- Prior art keywords
- optical information
- hydrophilic resin
- information medium
- adipose membrane
- protective seam
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Abstract
有保护透光基板上的记录部分的保护层的光情
报媒体,可记录能够用激光进行光学读取的情报。在
透光基板的再生光(读取光)入射面的反面形成水性
印刷墨水可附着的亲水性树脂膜,在该亲水性树脂膜
的表面容易印刷一定的文字和图案,而且印刷质量良
好。例如可用喷墨打印机印刷文字和图案。
Description
本发明是关于读取光入射面及其反面可用印刷油墨印刷的光情报媒体及其制造方法的发明。
现在,在音响及情报处理等领域广泛使用被称为“小型光盘”的光情报媒体(以下简称“CD”)。这种CD盘的构造是:在由聚碳酸酯等制成的园状基板上蒸镀上金或铝等反射层,然后在其上覆盖以紫外线硬化树脂构成的保护层。情报数据以在上述基板的表面形成螺旋状凹凸槽的方式记录下来,在基板成形时,以模压的方式形成该凹凸槽,在该槽上再覆盖反射层。所以,这种CD盘在制造时已记录下情报数据,是一种读取专用的光情报媒体。
这种CD盘是在保护层的表面用紫外线硬化树脂墨水或油性墨水印刷其记录内容的说明和各种图案设计等,可采用丝网印刷或胶印等方法印刷。这种印刷方式可大量印刷同一图案,是一种适用大量印刷的印刷方式。
但是,以卡拉OK为代表,随着业余自演活动的增加,很多业余演奏家自己少量制作CD盘的活动也很昌盛。这种自制CD多用于促销、试听考试或自费出版等。特别是采用激光可仅记录一次,而用CD唱机将录入内容反复播放,即,由于CD-WO等一次写入型光情报媒体的开发,可以很便捷地自己制作CD盘。而且在计算机领域,随着CD-ROM的广泛普及和一次写入型光情报媒体的普及,用户也可以利用CD-WO自己制作CD-ROM。
这种自制CD盘等光情报媒体的保护层上,或者什么也不印,或者采用紫外线硬化树脂墨水或油墨印上文字或图案,在将个人情报数据记录在光情报媒体之前或之后,在保护层表面或标签的印刷面上有时需要印上说明文字,需要的话还要印上图案设计。
但是上述印刷方法是在覆盖保护层后采用印刷工序,因为无论保护层还是印刷面都具有疏水性,所以在将个人情报数据记录后在保护层表面印刷时需要庞大的设备,个人将所需情报自由地进行印刷是很困难的。所以一般多采用使用油性毛毡笔在保护层表面书写的方法或在保护层表面贴标签等方法。但是在每张盘上手写说明文字很麻烦,而且手画的图案质量不好,有损精心制作的光情报媒体的外观,描画时还有可能损伤光盘。粘贴标签的话,贴了标签的地方厚,有可能在播放时或追记时光情报媒体的偏心。
本发明的目的之一是能够容易地在光情报媒体的保护层表面印刷或书写描述文字或图案,而且印刷或书写质量上乘,并确保光情报媒体的记录内容。本发明的目的之二是在光情报媒体的表面少量印刷文字或图案并保证质量。
本发明在光情报媒体的透光性基板的读取光入射面的反面形成水性印刷墨水可着色的亲水性树脂膜,在该亲水性树脂膜的表面可用水性墨水书写或印刷。
这样制成的光情报媒体,在板状的透光性基板上有另外一层,在其上再由树脂形成保护层,可用激光读取所记录的情报和/或记录情报。上述CD一次写入型光盘是这种光情报媒体的代表。
本发明的光情报媒体,在读取光入射面的反面可用水性笔或油性笔等任何书写工具书写任意文字或描画任意图案。当然也可用紫外线硬化墨水等其它方法。
在亲水性树脂膜表面印刷文字或图案时,向该亲水性树脂膜表面喷射水性墨水、使墨水付着在该表面上并固定在该表面上。采用这种印刷方法,对保护层和基板无任何损伤,将文字或图案印刷在光情报媒体的表面上。而且由于水性墨水固定在光情报媒体的亲水性树脂膜上,所以固定性好,印刷质量好。因为在光盘表面有一层亲水性树脂膜,所以指纹和灰尘的付着少,外观美丽且容易处理。为保证墨水的付着和固定,该亲水性树脂膜应有一定的厚度,这样可防止墨水的渗润而且质量好。在亲水性树脂膜的表面用墨水印刷时表面平坦,没有粘贴标签出现的表面凹凸的现象,可防止播放时或追记时光盘的偏心或表面污损的发生。在采用喷墨印刷在亲水性树脂膜的表面印刷时,预先用个人计算机制作需印刷的文字或图案,可以反复印刷。
为保证墨水的湿润性、亲水性等印刷性好,可选用至少含有下述之一的树脂膜作为亲水性树脂膜:
聚乙二醇、聚乙烯醇、聚乙烯基甲醚、聚乙烯醇缩甲醛、羧基乙烯聚合物、羟乙基纤维素、羟丙基纤维素、甲基纤维素、羧甲基纤维素钠盐、聚乙烯吡咯烷酮、吗啉。
这种亲水性树脂膜在进行耐水试验或暴露于其它环境中时,有水分付着时会发生膨润现象,一旦干燥后则恢复到原来的体积。这时,在中间层的边缘部有参差,该部的强度减弱,在亲水性树脂膨润、干燥时有破损之虞。因此,最好使亲水性树脂膜设置在上述中间层的内外周的周缘部的内侧。这样,在喷射印刷墨水而使亲水性树脂膜反复进行膨润和收缩时,即使在保护层上产生应力,该应力也难以达到中间层的边缘部,减少了在中间层缘部发生裂纹和剥离等现象。加速试验的结果表明这样作可以防止记录再生特性的劣化。
亲水性树脂膜与保护层之间的接合性最好比构成透光性基板的其它层之间的接合性好。这样,在亲水性树脂膜上付着墨水、干燥的过程中,该树脂膜即使膨胀和收缩,亲水性树脂膜也不会从保护层上脱落下来,而与保护层形成一体,起到保护中间层的作用,故而不会产生记录特性或再生特性劣化的现象。而且,在减少光情报媒体的翘曲、亲水性树脂的剥离和防止记录再生特性劣化的同时,可得到耐候性好、依赖性高的光情报媒体。
作为光情报媒体代表的CD的保护层,多数是用紫外线硬化树脂制成的,最好是在该保护层上形成亲水性紫外线硬化树脂膜。紫外线照射使保护层硬化后,在该保护层上再形成水性印刷墨水可着色的亲水性树脂膜,紫外线照射使其硬化,这样保护层与亲水性树脂膜之间的接合性较构成透光性基板的其它层之间的接合性要好。该亲水性紫外线硬化树脂膜可用已知的厚膜形成工艺和相同的工艺(例如丝网印刷)来形成。亲水性紫外线硬化树脂膜形成时,很少发生光情报媒体的翘曲或偏心现象,有效地防止了记录再生特性的劣化。
在形成亲水性树脂膜时,最好是在预先形成的保护层表面上紫外线硬化树脂中的游离分子未发生反应或未消失之前尚存在的状态下形成。这样,可进一步提高层间接合性。
上述保护层可在涂覆液态紫外线硬化树脂后,用紫外线照射使其固化成形。这种方法可在短时间内形成保护层膜。亲水性树脂膜可在涂覆液态亲水性紫外线硬化树脂后,用紫外线照射使其固化成形。因其与紫外线硬化树脂层的固化工序相同,所以可用同一生产线在短时间内形成。而且形成亲水性树脂膜时无光情报媒体的翘曲或偏心,可有效地防止记录再生特性的劣化。这种亲水性紫外线硬化树脂,可通过用丝网印刷在保护层上印刷的方法在需要的地方进行印刷。
亲水性树脂膜的硬化收缩率最好比下层的紫外线硬化树脂的硬化收缩率小。为形成该保护层和亲水性树脂膜而采用硬化时有收缩性的树脂时,最好是使亲水性树脂膜的材料的硬化收缩率比保护层材料的硬化收缩率小。这样可防止形成亲水性树脂膜时光情报媒体的翘曲。
亲水性树脂膜的厚度最好比保护层薄,而且其硬度也最好比保护层小,这样可防止用笔在表面书写时损伤光情报媒体。
最好是形成的亲水性树脂膜的表面有一定的粗糙度,这样树脂间的接触角较平面小,因而付着性好,可使印刷性提高。而且用手接触光情报媒体时也不会留下指纹。亲水性树脂膜表面细微的粗糙度,可通过使颜料在亲水性树脂中分散的方法形成,也可在亲水性树脂膜形成后进行表面粗糙加工的方法形成。
图1是光情报媒体的外观斜视图。
图2是图1A-A线断面图。
图3是本发明实施例的光情报媒体的要部纵断面图。
图4是本发明实施例的表示光情报媒体树脂固定状态的要部扩大模式纵断面图。
图5是在光情报媒体表用喷墨印刷方法印刷时使用的保持架和光情报媒体的分解斜视图。
图是本发明实施例中使用喷墨印刷机的要部断面图。
图1是从读取光入射面的反面来看的光情报媒体图,透光基板21在图的下方。如图所示,在紫外线硬化树脂层25的表面形成亲水性树脂膜26。在光情报媒体的中心部有固定孔4,用于将光情报媒体放在CD播放机上时轴的卡盘将其卡紧。
图2是图1的光情报媒体的A-A线断面图,作图时厚度进行了一定放大。图3是光情报媒体的一个例子,是一次写入型光情报媒体的断面放大图。在由聚碳酸酯构成的透光基板21上形成螺旋状导槽22,其上涂覆色素记录层23。在色素记录层23上形成由金、银、铝等金属膜构成的反射层24,24上形成保护层25,在保护层25上再形成下面要进行描述的亲水性树脂膜26。图4是进一步放大的光情报媒体的断面图,在保护层25上形成的亲水性树脂26上固定有水性墨水27。
图6是在一次写入型光情报媒体的上述亲水性树脂膜26上进行喷墨印刷时的印刷装置的要部构成图,图5是用该装置进行喷墨印刷时固定光情报媒体2的保持架31。保持架31为矩形,其中心有比光情报媒体2的外径稍大一点的园形孔33,在园孔的内侧有保护光情报媒体2的外缘部的凹槽32,该凹槽的深度比光情报媒体2的厚度略浅。如图5所示,使亲水性树脂膜26朝上,将光情报媒体2嵌入保持架31的孔33中,光情报媒体2的读取光入射面的外缘部嵌入凹槽32,光情报媒体2由保持架31保持,其亲水性树脂膜26的表面比保持架31的表面略高一点。
由保持架31保持的光情报媒体2,如图6所示,被送在印刷装置的传送带41上,滚轮42、43在保持架31的端部位置。当由计算机输入印刷指令时,滚轮42、43将保持架31向前运送,在光情报媒体2通过传送带41的位置的正上方设有打印头44,由该打印头44将印刷油墨喷到光情报媒体2的亲水性树脂膜26的表面上,在该26上印刷文字和图案。
如上所述,图6所示为进行喷墨印刷的喷墨印刷装置。这种印刷装置打印头44上有多个细喷嘴。这种喷嘴通过电信号操作的电热块使喷嘴中的印刷油墨发泡、再从喷嘴中喷出。这样,在传送带41上传送的光情报媒体2的亲水性树脂膜26的表面所需位置即可印上油墨。
光情报媒体2的板状透光基板21,可用对激光的折射率为1.4-1.6的透明度高的材料、耐冲击好的树脂制造,例如采用聚碳酸酯、聚烯烃、丙烯等制造,当然并不仅限于此。
透光基板21可使用上述材料用射出成形法制造。如图3所示,该透光基板21的表面有螺旋状或其它形状的导槽22,这种导槽22可用压纹成型等公知技术形成。
光情报媒体有记录通过激光照射可光学读取情报的部分或已记录情报的部分,就是说,有通过激光照射读取情报或记录情报的层、它可以是基板表面,也可以是另外的层。例如,图1-图3所示的一次写入型光情报媒体,在透光基板21上形成的色素记录层23和在其上形成的反射层24就是记录和读取情报的层。另外,在基板上的光反射层和保护层顺次叠层的CD盘等专用的光情报媒体,是通过在透光基板21上形成的槽和槽上的反射层来读取情报的。
读取情报的方式一般有仅用激光的方式和用光磁记录读取的方式等。这种方式的情报读取或记录一般只能在光情报媒体的单面进行,具体地说,是通过激光入射透光基板21的表面来进行的,另一面则不能进行情报的光记录和读取。
当用激光来作为记录光和读取光时,一般选用波长770-830mm的激光,也可使用其它波长的激光。
如图3所示,除色素记录层23和反射层24外,也可有其它层。例如,用于提高接合性的层、除记录情报外用于提高可靠性的层等。另外,在光反射层24和保护层25之间,还可有防止光反射层24氧化的耐氧化层。图3中,记录层23是直接覆盖在透光基板21上的,在它们之间也可以有其它层。
保护层25是保护透光基板21不受反面来的物理或机械损害从而保护情报记录部分的保护层,它覆盖在透光基板21的表面和背面。保护层25最好用耐冲击性好的树脂制作。保护层25的硬度最好有2H-7H铅笔硬度/玻璃,其热变形温度应高于80度,甚至100度。保护层25的厚度应为5-10μm,由不同材质的多层构成也可以。
保护层25一般通过涂覆可聚合的有机化合物单体和齐聚物,然后通过交联反应(架桥反应)来形成。通过交联反应来生成有机聚合物时,在分子中有一个以上的反应性丙烯基(-CH=CH2)的有机聚合物单体和齐聚物的混合物中加入少量反应开始剂和催化剂,根据情况可用甲基乙基甲酮、醇等溶剂稀释,使其成为液体,然后涂覆,用紫外线或电子照射,产生交联反应而形成。特别是,为防止在保护层25形成对基板和情报层产生坏影响,保护层25应在尽短时间内形成,所以最好使用紫外线硬化树脂。
公知的紫外线硬化树脂均可用作光情报媒体用的紫外线硬化树脂。例如:N-乙烯吡咯烷酮、三丙烯乙二醇二丙烯酸盐、三羟甲基丙烷三丙烯盐、己酸二醇二丙烯酸盐等。
交联的方法并不仅限于上述用紫外线照射的方法,环氧树脂、尿烷树脂等也可通过加热进行交联反应,二烷氧基硅烷偶合剂等也可通过空气中的水分进行聚合反应。
这样制得的聚合物的主链和侧链可为饱和或不饱和直链状碳氢化合物,含有蜜胺、双酚等环状化合物也无妨。交联物的主链或侧链中含有一个以上醚结合的聚醚、含有酯结合的聚酯、含有尿烷结合的聚氨脂、含有离子结合的离子键聚合物、含有酰胺结合的聚酰胺、含有砜结合的聚砜、含有硫结合的多硫化合物以及其它结合均可,含有两个以上述结合的共聚合化物也可以,也可以是块状聚合物。
为提高交联物的防湿性,可在侧链中含有碳氟化合物,为防止卤化氢的劣化也可以含有环氧树脂。
为提高保护层25与光反射层24和亲水性树脂膜26的接合性,上述交联物的侧链中可含有羟基、羧基、丙烯基、氨基、醋酸乙烯基等,主链或铡链中也可含碱性酸。
在形成保护层25时,除涂覆树脂和反应剂、反应开始剂之外,为提高涂覆性可加入溶剂和稀释剂。而且为使涂膜稳定,还可加入调平剂、可塑剂、防氧化剂、防止带电剂等。需要时还可加入颜料或染料。
树脂硬化因交联密度及反应性丙烯酰基浓度而变化,也因主链的齐聚物本身的分子回转的自由度而变化。保护层25硬化时如收缩率低,在硬化后,在进行热循环试验以消除树脂变形时保护层25也不易产生裂痕。考虑到机械强度,其收缩率最好在12%以下,10%以下更好。
另外,保护层25也可不用涂覆方法而采用铺在光反射层24上的方法。材质也不仅限于有机化合物,采用无机物用喷涂或真空镀膜法等已知方法形成也可以。
该光情报媒体的读取光入射面和背面有可固定印刷墨水的亲水性树脂膜26。当滴上水性墨水时,30分钟后手触摸不渗出墨水的程度使墨水固定,即树脂膜26是有充分亲水性的亲水性树脂膜。即,它不是仅靠墨水干燥而使墨水固定而是不容易去除的程度使墨水固定的膜。在亲水性树脂膜26上印刷的墨水,几乎无付着面积的缩小,印在亲水性树脂膜上,而且印刷后表面平坦,这里所说的平坦是指表示部分和非表示部分的表面粗糙度无实质差别。
亲水性树脂膜26可以全面覆盖保护层25,也可如图1及图2所示仅覆盖除保护层25内外周边缘外的部分。亲例如反射层24小,也就是说最好在其内外周的边缘部内侧。最好是如图2所示的那样,亲水性树脂膜26比反射层24的内外周的边缘部要小(向内)。但是例如,保护层25与透光基板21一样大小,即达到透光基板21的边缘部时,因为透光基板21与保护层25的外周缘部的接合性特别好,所以这种情况下,亲水性树脂膜26比反射层24的外周大也无妨。
亲水性树脂可举例如下:聚氧化乙烯、多元醇、聚乙烯基甲醚、聚乙烯醇缩甲醛、羧基乙烯聚合物、羟基乙基纤维素、羟基丙基纤维素、甲基纤维素、羧甲基纤维素钠盐、聚乙烯基吡咯烷酮、吗啉、甲醛酮、苯乙烯/无水马来酸共聚合物、虫胶、糊精、聚丙烯酸吡咯乙酯、聚丙烯酸及其金属盐、聚胺、聚丙烯酰胺、聚氧乙烯、聚二乙基氨基乙基(偏)丙烯酸盐、聚羟基苯乙烯、聚乙烯烷基醚、聚乙烯羟基苯基盐、聚酞酸、醋酸纤维素羟基二烯酞盐、主链为甲基偏丙烯酯,侧链为N-甲基丙烯酰胺构成的LH-40(日本综研化学社生产)这样的接枝聚合物类、水溶性醇酸树脂、水溶性聚酯、水溶性环氧树脂、聚酰胺、聚乙烯甲基醚、聚乙酸乙烯的皂化物、羧基甲基纤维素、羧甲基纤维素钠盐、阿拉伯胶、胍尔豆胶、藻酸苏打等等。至少准备一种以上上述亲水性树脂,配以下述光聚合单体或光开始剂、需要时再配以其它添加剂,然后进行涂覆。
考虑到光情报媒体的耐候性、耐水性、翘曲等性能及制造的方便,这些树脂的比例应进行调整。亲水性树脂的添加量应为液体总重量的5%以上,考虑到溶解限度(比如为重量的50%),最好应为总重量的5-20%。过多的话,耐水性不好,印刷作业性也差。过少的话,墨水不易扩散,印刷后也易生成飞白。
最好在上述亲水性树脂中加入光聚合单体。也可以不用树脂而代之以亲水性光聚合单体。亲水性光聚合单体举例如下:聚醚变性-(偏)丙烯酸盐、(偏)丙烯酰胺衍生物、有氨基的-(偏)丙烯酸盐、有羟基的-(偏)丙烯酸盐、有磷酸基的-(偏)丙烯酸盐、含氮环状乙烯单体中至少一种的单体。具体可选用:二乙基丙烯酰胺、二甲基丙烯酰胺(SN-SX-2883)、聚乙烯、有乙二醇结构的一(偏)丙烯酸盐、烷基置换(偏)丙烯酰胺、烷氧基变性(偏)丙烯酰胺、羟甲基变性(偏)丙烯酰胺、N,N-二甲胺乙基(偏)丙烯酸盐、N,N-二乙胺乙基(偏)丙烯酸盐、羟乙基(偏)丙烯酸盐、羟丙基(偏)丙烯酸盐、多价醇二甘油醚-(偏)丙烯酸盐、亚烃基氧化物变性磷酸-(偏)丙烯酸盐、己内酯变性磷酸-(偏)丙烯酸盐、丙烯酰吗啉、N-乙烯恶唑啉、N-乙烯吡咯烷酮、N-乙烯琥珀酰亚胺、N-乙烯己内酰胺中至少选择一种单体。为提高光硬化性,可使用多价醇及其亚烃基氧化物的(偏)丙烯酸酯类、多价醇二甘油醚二(偏)丙烯酸盐等。上述光聚合单体可适量加入重量的50-100%,也就是说,可以全部使用光聚合单体。
上述物质中加入光开始剂即成为紫外线硬化树脂。光开始剂举例如下:乙酰苯、苯酮、米蚩酮、苯甲基苯偶姻、二苯乙醇酮醚、苯甲酰苯甲酸盐、苯偶酰二甲基酮缩醇、1-羧基环己苯基酮、噻吨类、苯偶酰、2-乙基蒽醌、甲基苯甲酰甲酸盐、联乙酰等。加入这些光开始剂的量为重量的1-8%,最好为1-6%。如加入量过多则印刷作业性不好,但加入量过少的话,固化时间长,产量低,或者达不到紫外线硬化的效果。另外为调整粘度可在光聚合单体中加入上述树脂。
亲水性紫外线硬化树脂材料中还可加入其它添加剂。例如,可加入吸水性颜料、湿润剂、消泡剂、表面张力调整剂等。具体地说,可加入二氧化硅细粉、滑石、云母、碳酸钙、氧化钛、氧化锌、胶体二氧化硅、碳黑、氧化铁等无机颜料,羧甲基纤维素、糊精、甲基纤维素等微细粉末、采用特殊涂覆方法在酰胺丙烯酸盐上涂覆不溶性聚乙烯吡咯烷酮、丙烯酸乙烯醇共聚合物、骨胶原等有机颜料、已知的阴离子或非离子湿润剂、消泡剂、表面张力调整剂、聚乙烯亚胺等增粘剂。
作为添加剂加入的吸水性颜料具有调整墨水的印刷性以及形成亲水性膜时的作业性等作用。湿润剂可提高湿润性、调整流动性,有助于得到低起泡性的物质,在采用丝网印刷等光情报媒体的制造过程中可用制造其它层的设备来制造,所以可提高制造效率。消泡剂和表面张力调整剂有助于形成光滑的涂膜。
通过加入颜料可使亲水性树脂膜26作成不透明的和各种颜色。这样可以选择与墨水的颜色和印刷工序相应的光情报媒体,可使其外观更加漂亮。通过对保护层下面涂层的颜色的处理使其具有条纹状可以形成浮雕图案。
上述亲水性树脂中应不含有水、乙醇、异丁醇、乙二醇、乙基溶纤剂、二甲基甲酰胺等溶剂。溶剂有时会浸入保护层和紫外线硬化树脂从而降低产品性能。而且,含有溶剂的话在采用丝网印刷形成亲水性树脂膜时粘度会发生变化、产生制造上的困难。
关于亲水性树脂膜26的厚度,为防止影响对光情报的读取,亲水性树脂膜26的厚度应为5-30μm。通过适当配合上述材料并进行粘度调整可以得到这样的膜厚。亲水性树脂膜26的厚度比保护层25的厚度稍厚一些可以提高缓冲效果。
亲水性树脂膜应在紫外线硬化树脂形成的保护层25的上面,而且应在紫外线硬化树脂形成保护层25的膜后立即,即紫外线硬化树脂完全硬化前,在其上形成亲水性树脂膜26,这样可使其层界成为一体,提高接合性。
亲水性树脂膜26与保护层25之间的接合性应比构成透光基板的其它层之间的接合性好。可通过适当选择形成保护层25的树脂材料和在其表面的亲水性树脂材料的组合和成膜法来保证其接合性。例如,在图3所示的光情报媒体中,该媒体的基板上有色素记录层23和金属反射膜24,反射膜24上有环氧树脂、聚丙烯树脂等紫外线硬化树脂形成的保护层25,这样的光情报媒体的亲水性树脂膜26如果是含有酰胺类丙烯酸盐和聚乙烯吡咯烷酮的亲水性紫外线树脂膜,即可以得到上述接合性。保护层25和亲水性树脂膜之间的接合性好的话,即使亲水性树脂膜26仅在保护层25的表面的一部分形成也难剥离,可与保护层25一起发挥保护光情报媒体的作用。而且,光情报媒体的翘曲和剥离少,防止了记录或读取特性的劣化。
为防止光情报媒体的翘曲,亲水性树脂膜26形成时的收缩率应小于形成保护层25的紫外线硬化树脂干燥时的收缩率。从保护光情报媒体不受笔压、印字时压力的损害的角度,亲水性树脂膜26的硬度应比保护层25的硬度小。例如应比保护层25的硬度2H-7H铅笔硬度小。这种收缩率和硬度可以通过根据配合材料的性能,适当选择单官能基单体或官能基为2的单体来得到,因为收缩率和硬度取决于形成保护层25的紫外线硬化树脂及在其表面形成的亲水性树脂膜26中配入的单体的官能团的数目。这样作可以防止光情报媒体的翘曲、剥离等性能下降,可以稳定地记录和读取情报。
亲水性树脂膜26的表面最好呈细微粗糙,这种细微粗糙的表面,在印刷墨水付着在保护层25上时,墨水容易付着在细微凹部,即具有投锚效果。而且,亲水性树脂膜26的表面积也因粗糙面而增大,可促进墨水的吸收。
这里所说的粗糙面是指对墨水的接触角比非粗糙面的小,最好表面粗糙度(Ra)为用触针式表面粗糙度测量器测量2.0-0.1μm范围。表面粗糙度对墨水的效果因膜的性能不同而不同,一般地说,表面粗糙度小时,细线画得清晰而且折像度好,在充满墨水时有可能写出飞白;表面粗糙度太大时,细线和全面书写均易渗出。平均粗糙度(Ra)为1.0-0.5μm时,无论是细线印刷还是全面积印刷均可得到很好效果。
这种亲水性树脂膜26的细微粗糙表面,可以通过在保护层25的表面用凹板涂覆亲水性紫外线硬化树脂来形成,例如在保护层25的表面2上采用丝网印刷或旋转涂覆等方法涂覆混合了填充剂的树脂。在亲水性树脂中混入有机或无机颜料作为填充剂时容易形成粗糙面,其投锚效果好。颜料的粒度以1-10μm为好,其中尤以3-5μm为最好。
对亲水性树脂膜26的表面进行等离子处理可提高其墨水的付着性。具体作法是:在真空状态的稀薄惰性气体气氛中放入光情报媒体,使该气中发生等离子进行处理。进行这样的处理后,付着在被处理表面的墨水的表面强力变小,墨水的接触角小,提高了墨水的印刷性。表面印刷最好在进行等离子处理后尽快进行。
适用于本发明的光情报媒体的墨水最好是水性墨水,但也可以使用油性墨水或紫外线硬化墨水。
如上所述,在亲水性树脂膜26的表面2上印刷文字等时,可用笔写或丝网印刷,以喷墨印刷为最好。众所周知,喷墨印刷多用于个人计算机的打印机,所以可以将计算机作成的印刷文字或图案反复印刷在上述亲水性树脂膜26的表面。适用于在少量光情报媒体上印刷上一定文字或图案。而且由于印刷时无打击等撞击和使墨水付着的加热,所以对光情报媒体无损害。当然也可用在喷嘴处进行加热的加热喷墨方式或作成墨水粒来进行印刷的泡式喷墨方式。
下面对本发明的具体实施例进行说明。
准备外径120mmΦ、内径15mmΦ、厚度为1.2mm的聚碳酸酯基板,在直径为46-117mmΦ的范围内形成幅0.8μm、深0.08μm、轨距1.6μm的导槽,该导槽用压纹方法作成螺旋状,基板硬度为HB铅笔硬度,在20-120℃温度下热膨胀系数为6×10-5/℃。
将0.65克1.1-二丁基3、3、3、3、四甲基4、5、4、5-二苯偶姻二羰花青高氯酸盐(日本感光色素研究所制)溶解在10ml二丙酮醇中,将其旋转涂在基板上,涂的次数有所不同。达到平均膜厚130nm,干燥后形成色素记录层。在其表面溅射金以形成厚度为100nm的反射层。将不需涂覆部分的色素膜和金属膜去掉,就形成了在Φ42-118范围内的同心园状的色素膜和金属膜。
然后采用旋转涂覆法将以多官能丙烯酸盐单体为主要成分的紫外线硬化树脂(SD-17,日本大墨水会社制)涂覆在其表面,用高压水银灯进行照射,照度为230mj/cm2,使其固化,即可形成厚度为10μm的保护层。由这种紫外线硬化树脂制成的保护层的厚度在玻璃上为5H铅笔硬度(2H/在PC上)。
将含有光开始剂的单官能紫外线硬化酰胺基丙烯酸盐(SN5X-2883,三能浦克会社制)作为A成分混入C成分-二官能分子量为400的聚乙二醇二丙烯酸盐(SN5X-2911,三能浦克会社制),在混合而成的液体中,加入重量10%的粉末状聚乙烯吡咯烷酮(K90,东京化成工业制)作为B成分,使其充分溶解混合后按下述比例加入D成分-粒径约4μm的二氧化硅细粉(XR37B、德山遭达制)或D′成分-表面进行了不溶涂覆处理的粒径约4μm的紫外线硬化树脂粒子(KOL1DON CLM,BASF制),混合后使用21孔12球的球磨机搅拌24小时制成亲水性树脂溶液。
混合比例如下:
实施例1 成分A∶B∶C∶D=67∶15∶5∶1
实施例2 成分A∶B∶C∶D=65∶15∶5∶1
实施例3 成分A∶B∶C∶D=57∶15∶15∶13
实施例4 成分A∶B∶C∶D=50∶15∶20∶15
在保护层形成后,用300筛的丝网,将上述亲水性树脂溶液用丝网印刷的方法印刷在保护层的Φ44-117的部分成同心园状,与保护层用同样的条件下紫外线照射即形成厚度为15μm的亲水性树脂膜。
上述实施例1-4中,在实施例3和4中使用的亲水性树脂溶液的粘度随时间的变化情况示于表1。
为对收缩率进行比较,将形成保护层的紫外线硬化树脂和亲水性树脂分别涂在厚度为10μm的聚乙烯对苯二酸盐胶片上,涂厚为15μm,用紫外线照射使其固化,涂了紫外线树脂的比亲水性树脂的弯曲度大,即保护层用紫外线硬化树脂的收缩率比亲水性树脂膜大。
这样形成的亲水性树脂膜的表面是半透明的细微粗糙面,用触针式表面粗糙度测定器(DEKTAK 3030)测量其表面粗糙度(Ra)为0.9-0.6μm。树脂硬度为4H铅笔硬度/在玻璃上(2H/在PC上)。
在这样制得的光情报媒体上用EFM信号调制的波长为780nm的半导体激光以功率为7.8mW、线速度1.4m/秒沿导槽照射即可记录所要求的情报信息。
对所制得的光情报媒体在70℃、湿度为85%RH条件下进行加速劣化试验。从试验开始经100小时后检查亲水性树脂膜的表面,与初始状态相比较未发现任何变化。为进行比较,对喷墨印刷用的OHP板也进行相同的加速劣化试验,从试验开始经100小时后,表面有溶化的斑点。
对未进行加速劣化试验、经24小时时试验和经100小时试验的试验片,用喷墨印刷机分别印刷黑色墨水,检查其喷墨印刷性能(IJP性能)。用喷墨印刷机印刷●和■,检查其是否可不成网目状全面积印刷,印刷笔画多的汉字,检查其线间是否有不整齐的现象、汉字印刷性如何等。检查结果示于表2。
对实施例3和4,在70℃、湿度3%RH(干)的条件下进行加速劣化试验,检查其试验前后的IJP性能,检查结果示于表3。
对实施例3和4,在70℃、湿度3%RH(干)条件下进行加速劣化试验,测定其试验前后的反张角,测定结果示于表4。在23℃、湿度50%RH标准条件下放置98小时后测量的反张角也示于表4。反张角的测定按CD规格,测量自中心半径为55mm位置的径方向反张角,表中所示为平均值。与其相比较的是有厚度为25μm的保护层、但没有亲水性树脂膜的试片,均按CD规格规定的0.6°以下。
表4
反张角(°)
初期 100小时后 标准条件(98小时)
实施例3 0.05 0.18 0.13
实施例4 0.02 0.17 0.15
比较例 0.02 0.17 0.15
用喷墨机在光情报媒体表面印刷上述IJP试验用印字,印后将其放在温度70℃、温度为85%RH和温度70℃、8小时、湿度为3%RH(干)条件下放置100小时,进行加速劣化试验,检查有无字迹不清或渗润现象,检查结果均未发现字迹不清或墨水渗润现象。在亲水性树脂膜表面印字3分钟后,用手摩擦印刷面也无字迹脱落现象。
为比较保护层和亲水性树脂膜之间的接合性,进行了剥离试验(交错划线试验),试验结果是:保护层部分为97/100,而亲水性树脂膜部分为100/100。
Claims (27)
1、通过激光可光学记录或读取情报的光情报媒体,在板状透光基板上间隔有其它层、在其上有由树脂形成的保护层,其特征是在透光基板的读取光入射面的反面形成水性印刷墨水可付着的亲水性树脂膜。
2、权利要求1所述的光情报媒体,其特征是在透光基板的读取光入射面的反面形成水性印刷墨水可付着的亲水性树脂膜,在该亲水性树脂膜上印刷有水性墨水进行标记。
3、权利要求2所述的光情报媒体,其特征是付着有标记用水性墨水的亲水性树脂膜的表面是平坦的。
4、权利要求1所述的光情报媒体,其特征是亲水性树脂膜由放射能硬化树脂层形成。
5、权利要求4所述的光情报媒体,其特征是亲水性树脂膜是在透光基板上直接或间隔有其它层的由放射能硬化树脂层密接形成的保护层上形成的。
6、权利要求4所述的光情报媒体,其特征是亲水性树脂膜的厚度比保护层厚。
7、权利要求4所述的光情报媒体,其特征是亲水性树脂膜与保护层之间的接合性比其它层间的接合性好。
8、权利要求4所述的光情报媒体,其特征是亲水性树脂膜干燥时的收缩率比保护层干燥时的收缩率小。
9、权利要求4所述的光情报媒体,其特征是亲水性树脂膜的硬度比保护层小。
10、权利要求4所述的光情报媒体,其特征是亲水性树脂膜由含有光聚合单体的树脂形成膜。
11、权利要求4所述的光情报媒体,其特征是亲水性树脂膜由含有从聚醚变性-(偏)丙烯酸盐、(偏)丙烯酰胺衍生物、有羟基的-(偏)丙烯酸盐、有氨基的-(偏)丙烯酸盐、有磷酸基的-(偏)丙烯酸盐、含氮环状乙烯单体中选择至少一种光聚合单体的树脂来形成膜。
12、权利要求4所述的光情报媒体,其特征是亲水性树脂膜由含有从二乙基丙烯酰胺、二甲基丙烯酰胺、聚乙烯、有乙二醇结构的-(偏)丙烯酸盐、烷基置换(偏)丙烯酰胺、烷氧基变性(偏)丙烯酰胺、羟甲基变换(偏)丙烯酰胺、N,N-二甲胺乙基(偏)丙烯酸盐、N,N-二乙胺乙基(偏)丙烯酸盐、羟乙基(偏)丙烯酸盐、羟丙基(偏)丙烯酸盐、多价醇二甘油醚-(偏)丙烯酸盐、亚烃基氧化物变性磷酸-(偏)丙烯酸盐、己内酯变性磷酸-(偏)丙烯酸盐、丙烯酰吗啉、N-乙烯恶唑啉、N-乙烯吡咯烷酮、N-乙烯琥珀酰亚胺、N-乙烯己内酰胺中选择至少一种光聚合单体的树脂来形成膜。
13、权利要求1所述的光情报媒体,其特征是亲水性树脂膜由含有下述树脂中至少一种的树脂形成膜:聚氧化乙烯、多元醇、聚乙烯基甲醚、聚乙烯醇缩甲醛、羧基乙烯聚合物、羟乙基纤维素、羟丙基纤维素、甲基纤维素、羧甲基纤维素钠盐、聚乙烯吡咯烷酮、吗啉、甲醛酮、苯乙烯/无水马来酸共聚合物、虫胶、糊精、聚丙烯酸吡咯乙酯、聚丙烯酸及其金属盐、聚胺、聚丙烯酰胺、聚氧乙烯、聚二乙基氨基乙基(偏)丙烯酸盐、聚羟基苯乙烯、聚乙烯烷基醚、聚乙烯羟基苯基盐、聚酞酸、醋酸纤维素羟基二烯酞盐、主链为甲基偏丙烯酯、侧链为N-甲基丙烯酰胺构成的接枝聚合物类、水溶性醇酸树脂、水溶性聚酯、水溶性环氧树脂、聚酰胺、聚乙烯甲基醚、聚醋酸乙烯的皂化物、羧基甲基纤维素、羧甲基纤维素钠盐、阿拉伯胶、胍尔豆胶、藻酸苏打等。
14、权利要求1所述的光情报媒体,其特征是亲水性树脂膜形成于保护层与透光基板的中间层的内外周的周缘部的内侧。
15、权利要求1所述的光情报媒体,其特征是亲水性树脂膜的表面为细微的粗糙面。
16、权利要求15所述的光情报媒体,其特征是亲水性树脂膜的细微粗糙表面是由在亲水性树脂中分散粒状颜料来形成的。
17、权利要求15所述的光情报媒体,其特征是亲水性树脂膜的细微粗糙表面是在亲水性树脂膜成形后进行表面加工来形成的。
18、权利要求1所述的光情报媒体,其特征是亲水性树脂膜与保护层的接合性比保护层与透光基板上的其它层之间的接合性好。
19、在板状透光基板上直接或间隔有其它层上有树脂形成紧密接合的保护层,用激光可光学记录或读取情报的光情报媒体的制造方法,其特征是:在透光基板的读取光入射面的反面形成水性印刷墨水可付着的亲水性树脂膜,向该亲水性树脂膜喷水性墨水,使其付着在树脂膜的表面,且该水性墨水固定在树脂膜的表面。
20、权利要求19所述的光情报媒体的制造方法,其特征是水性墨水是通过喷墨打印机喷在亲水性树脂膜的表面。
21、在板状透光基板上直接或间隔有其它层上有树脂形成保护层,用激光可光学记录或读取情报的光情报媒体的制造方法,其特征是:在透光基板上直接或间隔有其它层上形成紧密接合的保护层后,在该保护层上形成水性印刷墨水可付着的亲水性树脂膜。
22、权利要求21所述的光情报媒体的制造方法,其特征是保护层是涂覆放射能硬化物后,通过放射能照射使其硬化来形成的。
23、权利要求21所述的光情报媒体的制造方法,其特征是:亲水性树脂膜是涂覆亲水性放射能硬化物后,通过放射能照射使其硬化来形成的。
24、权利要求21所述的光情报媒体的制造方法,其特征是:亲水性树脂膜是在保护层表面活性尚未失去时形成的。
25、权利要求21所述的光情报媒体的制造方法,其特征是:在亲水性树脂膜的表面活性尚未失去时,使水性墨水付着在其表面。
26、权利要求21所述的光情报媒体的制造方法,其特征是:形成保护层和亲水性树脂膜的物质在硬化时具有收缩硬化性,形成亲水性树脂膜用的物质硬化时的收缩率比形成保护层的物质的收缩率小。
27、权利要求21所述的光情报媒体的制造方法,其特征是:亲水性树脂膜用丝网印刷的方法形成。
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- 1994-04-01 KR KR1019940006893A patent/KR0185765B1/ko not_active IP Right Cessation
- 1994-04-05 US US08/223,465 patent/US5470691A/en not_active Expired - Lifetime
- 1994-04-06 EP EP94105334A patent/EP0628956B1/en not_active Expired - Lifetime
- 1994-04-06 DE DE69428305T patent/DE69428305T2/de not_active Expired - Lifetime
- 1994-04-07 CA CA002120791A patent/CA2120791C/en not_active Expired - Lifetime
- 1994-04-09 CN CN94103974A patent/CN1062082C/zh not_active Expired - Lifetime
-
1995
- 1995-05-09 US US08/437,394 patent/US5616450A/en not_active Expired - Lifetime
-
1996
- 1996-07-02 US US08/674,347 patent/US5705247A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1294581C (zh) * | 2001-10-03 | 2007-01-10 | 索尼公司 | 光信息媒体 |
CN102256769A (zh) * | 2008-12-19 | 2011-11-23 | 爱克发印艺公司 | 用于减少三维印刷中的图像质量伪影的方法 |
CN102317394A (zh) * | 2008-12-22 | 2012-01-11 | 3M创新有限公司 | 含聚乙烯醇缩丁醛的层状材料 |
CN102317394B (zh) * | 2008-12-22 | 2014-06-11 | 3M创新有限公司 | 含聚乙烯醇缩丁醛的层状材料 |
CN111942052A (zh) * | 2020-08-26 | 2020-11-17 | 东莞光群雷射科技有限公司 | 一种热转印定位花纸及其生产工艺和应用方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0628956B1 (en) | 2001-09-19 |
US5705247A (en) | 1998-01-06 |
EP0628956A1 (en) | 1994-12-14 |
DE69428305T2 (de) | 2002-04-18 |
CA2120791C (en) | 1999-02-02 |
KR0185765B1 (ko) | 1999-04-15 |
CA2120791A1 (en) | 1994-10-11 |
CN1062082C (zh) | 2001-02-14 |
US5616450A (en) | 1997-04-01 |
US5470691A (en) | 1995-11-28 |
KR940024717A (ko) | 1994-11-18 |
DE69428305D1 (de) | 2001-10-25 |
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