CN103539998B - 多孔印章材料及其制造方法和印章 - Google Patents
多孔印章材料及其制造方法和印章 Download PDFInfo
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Abstract
本发明的目的在于提供多孔印章材料,其在激光雕刻中只是照射激光束的部分的树脂燃烧蒸发,能够防止不必要的部分的熔融,得到清晰的边缘,得到鲜明的印影。具有连续气泡的多孔印章材料,其包含:从低密度聚乙烯、直链状低密度聚乙烯、高密度聚乙烯、乙烯‑α‑烯烃共聚物、乙烯‑醋酸乙烯酯共聚物、乙烯‑丙烯酸系共聚物中选择的至少一种热塑性树脂,从氢化苯乙烯系热塑性弹性体中选择的至少1种热塑性弹性体,从无机化合物中选择的至少1种填充剂;使上述热塑性树脂和上述热塑性弹性体交联而成。
Description
技术领域
本发明涉及在内藏印章用墨的类型的所谓浸透印中使用的多孔印章材料,特别涉及最适合激光雕刻的具有连续气泡的多孔印章材料。
背景技术
具有连续气泡的多孔印章材料,已在特公昭47-1173号和特公昭47-39212号、特开昭51-74057号等中公开。此外,作为用激光雕刻机雕刻多孔印章材料的方法,特开平10-337943号、特开2001-150780号等已公知。此外,作为用激光雕刻机雕刻的印章的刻印形状,特开平6-234262号已公知。
但是,如果对以往的多孔印章材料实施激光雕刻,不仅照射了激光束的部分的树脂燃烧蒸发,而且其周边的树脂也同时熔融,因此,成为图1的a那样的印章,未能得到具有清晰的边缘的印章。
因此,使该印章内藏墨的印章的印影成为模糊的轮廓,并且发生了洇渗。
此外,如果实施激光雕刻,热塑性树脂过剩地熔融,压印时具有不稳的缺点。
现有技术文献
专利文献
专利文献1:特公昭47-1173号公报
专利文献2:特公昭47-39212号公报
专利文献3:特开昭51-74057号公报
专利文献4:特开平6-234262号公报
专利文献5:特开平10-337943号公报
专利文献6:特开2001-150780号公报
发明内容
发明要解决的课题
因此,本发明的目的在于提供在印章制作时的激光雕刻中只有照射了激光束的部分的树脂燃烧蒸发,防止不必要的部分的熔融,得到清晰的边缘,能够得到鲜明的印影的多孔印章材料。此外,目的在于同时提供其为以一般不耐高热或有机溶剂的热塑性树脂为主成分的印章材料,但兼具耐热性、耐溶剂性的多孔印章材料。
用于解决课题的手段
具有连续气泡的多孔印章材料,其包含:
从低密度聚乙烯、直链状低密度聚乙烯、高密度聚乙烯、乙烯-α-烯烃共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸系共聚物中选择的至少一种热塑性树脂,
从氢化苯乙烯系热塑性弹性体中选择的至少1种热塑性弹性体,
从无机化合物中选择的至少1种填充剂;
其是使上述热塑性树脂和/或上述热塑性弹性体交联而成的具有连续气泡的多孔印章材料。
具有连续气泡的多孔印章材料,其中,以上述热塑性弹性体的2倍~30倍的比例混合上述热塑性树脂。
具有连续气泡的多孔印章材料,其中,上述热塑性树脂的玻璃化转变温度为摄氏0℃以下。
具有连续气泡的多孔印章材料,其中,上述填充剂为从硅酸盐中选择的至少1种的填充剂。
具有连续气泡的多孔印章材料,其中,上述多孔印章材料的O型硬度计硬度为75以下(按照美国标准ASTM D2240,O型)。
具有连续气泡的多孔印章材料的制造方法,具有:
混合工序,其中,在从低密度聚乙烯、直链状低密度聚乙烯、高密度聚乙烯、乙烯-α-烯烃共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸系共聚物中选择的至少一种热塑性树脂、从氢化苯乙烯系热塑性弹性体中选择的至少1种热塑性弹性体、和从无机化合物中选择的至少1种填充剂的混合物中混合从水溶性化合物中选择的至少1种气泡形成剂、从多元醇中选择的至少1种气泡形成助剂和从有机过氧化物中选择的至少1种交联剂,得到成型材料,
交联成型工序,其中,加热上述成型材料,使用上述交联剂使上述热塑性树脂和/或上述热塑性弹性体交联而得到成型物,和
提取工序,其中,从上述交联成型工序中得到的成型物将上述气泡形成剂和上述气泡形成助剂提取,得到具有连续的气泡的多孔成型体。
印章,其通过对具有连续气泡的多孔印章材料施以激光雕刻,制成印章,使该印章内藏印章用墨而成。
发明的效果
根据本发明的多孔印章材料,激光雕刻时照射了激光束的部分以外的周边树脂完全没有熔融,因此能够得到具有清晰的边缘的印章。
因此,如果含浸墨,能够提供墨吸藏量也充分,能够进行无洇渗、飞白的鲜明的盖章的印章。此外,由于照射了激光束的部分的树脂完全燃烧蒸发,因此即使进行深度深的雕刻,也不会成为不稳的印章,也不产生雕刻渣,因此不需要加工后的洗净工序。
此外,根据本发明的多孔印章材料,激光雕刻时完全没有产生煤烟,相对于类似的其他的印章材料在激光雕刻后必须将加工面洗净,不需要洗净工序,此外,还具有不需要用于将向大气中排放的煤烟除去的抽吸装置的优点。
此外,由于激光雕刻时完全不产生恶臭,因此不需要恶臭条例等法令中规定的气味吸附装置,能够大幅度地削减印章制造成本。
此外,能够得到兼具耐热性和耐溶剂性的优异的多孔印章材料。
附图说明
图1a:现有例(比较例)、b:本发明(实施例)
图2硬度测定参考图
具体实施方式
以下对本发明的多孔印章材料进行说明。
本发明是包含热塑性树脂、热塑性弹性体和填充剂,使上述热塑性树脂和上述热塑性弹性体交联,并且具有连续气泡的多孔印章材料。
本发明中使用的热塑性树脂,是成为本发明多孔印章材料的主成分的材料,能够从低密度聚乙烯(LDPE)(玻璃化转变温度:约-125℃)、直链状低密度聚乙烯(LLDPE)(玻璃化转变温度:约-100℃)、高密度聚乙烯(HDPE)(玻璃化转变温度:约-120℃)、乙烯-α-烯烃共聚物(玻璃化转变温度:约-51℃)、乙烯-醋酸乙烯酯共聚物(EVA)(玻璃化转变温度:约-42℃)、乙烯-丙烯酸系共聚物(玻璃化转变温度:0℃~-80℃)这样的乙烯系树脂中选择至少1种使用。即使将这些树脂的2种以上混合也能够完全没有问题地使用,能够以任意的配合比率混合。这些乙烯系树脂在聚烯烃树脂中特别是玻璃化转变温度或熔点低,具有适度的弹力性,与后述的热塑性弹性体的相容性好,因此最适合浸透印用多孔印章材料,可选择使用。这些乙烯系树脂,为了促进完全燃烧,因此优选使用玻璃化转变温度为摄氏0℃以下的乙烯系树脂。
本发明中使用的热塑性弹性体,是成为本发明多孔印章材料的辅助成分的材料,可使用氢化苯乙烯系热塑性弹性体。具体地,为将苯乙烯和共轭二烯的共聚物氢化的热塑性弹性体,能够从聚苯乙烯-聚丁二烯共聚物、聚苯乙烯-聚丁二烯二嵌段共聚物、聚苯乙烯-聚丁二烯三嵌段共聚物、聚苯乙烯-乙烯基聚丁二烯三嵌段共聚物、聚苯乙烯-聚异戊二烯共聚物、聚苯乙烯-聚异戊二烯二嵌段共聚物(玻璃化转变温度:约-125℃)、聚苯乙烯-聚异戊二烯三嵌段共聚物、聚苯乙烯-乙烯基聚异戊二烯三嵌段共聚物(玻璃化转变温度:约-32℃)中选择至少1种使用。即使将这些树脂的2种以上混合也能够完全没有问题地使用,能够以任意的配合比率混合。这些热塑性弹性体的玻璃化转变温度或熔点低,与上述的乙烯系树脂的相容性好,能够赋予乙烯系树脂适度的弹力性,因此最适合作为辅助材料。这些热塑性弹性体,为了促进完全燃烧,特别优选使用玻璃化转变温度为摄氏0℃以下的热塑性弹性体。
上述主成分的热塑性树脂和上述辅助成分的热塑性弹性体,优选以上述热塑性树脂成为上述热塑性弹性体的2倍~30倍(热塑性树脂∶热塑性弹性体=2~30∶1)的比例的方式混合。如果超过比例,大量配合热塑性弹性体,激光雕刻时的本发明多孔印章材料的熔融变得显著,无法得到清晰轮廓的印章。如果配合与比例相比少量的热塑性弹性体,多孔印章材料变硬,无法得到适当的印章材料。
本发明中使填充剂作为必要成分。填充剂是对本发明多孔印章材料的强度进行补强,带来印章加工时的加工性提高的材料,能够从粘土、滑石、白云母、硅灰石、蛇纹石、叶蜡石、高岭石、埃洛石、绢云母、蒙脱石等无机化合物中选择至少1种使用。即使将这些填充剂的2种以上混合也能够完全无问题地使用,能够以任意的配合比率混合。
本发明中,如果使用如粘土、滑石、白云母、硅灰石、蛇纹石、叶蜡石、高岭石、埃洛石、绢云母、蒙脱石等的硅酸盐,能够获得最优选的结果。其理由尚不清楚,在激光雕刻时的轮廓的清晰程度、印章用墨的排出情况上,作为浸透印用多孔印章材料,具有最适合的性能。
硅酸盐以外的如碳酸钙、硫酸钡、氧化钛、碳酸镁、白云石、氧化铝等的填充剂也能够使用,但未能获得硅酸盐那样的性能。
本发明的多孔印章材料,以将上述热塑性树脂和上述热塑性弹性体交联为必要的。通过进行交联,成为热固化性的多孔印章材料,与上述填充剂的效果协同,在通常的聚乙烯的熔点下,不会容易地熔融,在激光雕刻温度下不熔融,而完全燃烧,因此认为轮廓变得极其清晰。
对于交联,使用交联剂,特别是使用有机过氧化物。作为有机过氧化物,能够使用过氧化二烷基、过氧缩酮、氢过氧化物、过氧酯、过氧化二烷基等,由于在混炼加工的阶段加热到100℃左右,因此优选分解温度(为140~170℃)高的的有机过氧化物。
本发明多孔印章材料优选设定为O型硬度计硬度75以下(按照美国标准ASTMD2240,O型)。因为作为浸透印用的具有连续气泡的多孔印章材料,对于墨的保持性、墨的排出性是最佳值。
为了制成这样的硬度的多孔印章材料,上述热塑性树脂和热塑性弹性体的混合物在后述的交联中间片材中成为5~50重量%,上述填充剂在后述的交联中间片材中成为5~50重量%,上述交联剂在后述的交联中间片材中成为0.1~5重量%的配合比率是适当的,在气泡直径10~300μm的气泡之间彼此连接的多孔印章材料中,制成气泡率为30~80%的多孔印章材料是适当的。
其次,对本发明的多孔印章材料的制造方法进行说明。
制造本发明这样的具有连续气泡的多孔化的印章材料,一般已知发泡法、烧结法、溶出法等。
其中,本发明中,为了作成气泡直径无波动、均一的气泡,选择作为气泡直径一定,气泡能够均一地分散,气泡之间的连接路的设计能够比较容易地进行的方法的溶出法。
作为本发明中能够使用的气泡形成剂,可列举盐和糖等水溶性化合物,使用微粉末的水溶性化合物。对于盐,优选容易微粉末化,在热塑性树脂的加工温度(40℃~180℃)下不分解,并且加热后用水能够容易地提取的化合物,具体地,优选使用氯化钠、硫酸钠、硝酸钠等金属盐。使用粒径为1~500μm的盐。对于糖,戊糖和己糖等单糖类、蔗糖和麦芽糖等二糖类、淀粉和糖原等多糖类、季戊四醇均能够使用,使用粒径为1~500μm的糖。对于气泡形成剂,可各自单独地使用盐和糖,也可并用,可根据用途适当选择。
作为本发明中能够使用的气泡形成助剂,能够使用聚乙二醇、聚丙二醇、聚乙二醇-聚丙二醇共聚物、聚乙二醇烷基醚、聚丙二醇烷基醚、聚乙烯醇、甘油等多元醇。具体地,优选将2元和3元的醇并用。
作为2元醇,可列举聚乙二醇,其中容易使用平均分子量为1,000以上的聚乙二醇。聚乙二醇不仅具有作为提取助剂的效果,而且也作为气泡形成剂的分散剂发挥功能。作为3元醇,可列举甘油。甘油还具有作为提取助剂的效果,使多孔印章材料的撕裂强度增强的作用大。只用聚乙二醇提取的多孔印章材料的撕裂强度弱,或者溶胀而尺寸稳定性变差,因此优选使用甘油。这样通过将2元和3元的醇并用获得均衡,从而能够得到提取、物性、墨吸收性优异的成型物。
制造本发明时,首先,作为混合工序,将气泡形成剂、气泡形成助剂投入双辊或捏合机中,边加热边搅拌。其次,投入填充剂和热塑性树脂切片和热塑性弹性体切片,边成为热塑性树脂和热塑性弹性体的熔点以上的温度边进一步混炼。最后,边保持交联剂的分解温度以下的温度,边投入交联剂,进一步混炼。这样,得到气泡形成剂、气泡形成助剂、填充剂、热塑性树脂切片、热塑性弹性体切片、交联剂混合的母料。
其次,将上述母料用压延辊机压延成型为片状,首先,作成中间片材。
其次,作为交联成型工序,将该中间片材用热压机等在交联剂的分解温度以上加热。这样,得到热塑性树脂和热塑性树脂、或、热塑性弹性体和热塑性弹性体、或、热塑性树脂和热塑性弹性体的全部或一部分交联了的交联中间片材。此外,边将上述母料用片材挤出机在交联剂的分解温度以上加热,边挤出成片状,也能够作成交联中间片材。
交联、成型的温度和时间,为热塑性树脂组合物熔融软化,多孔形成助剂熔融或软化的温度,并且交联剂分解,形成交联物的120~170℃的范围。时间包括预热、脱空气、脱气,为3~15分钟左右。如果交联-成型温度超过180℃,交联速度变快,因此在预热阶段交联反应过度进行,无法得到良好的成型物。此外,如果交联-成型温度不到100℃,交联反应不充分地进行,因此产生不从成型模脱模的部分,或者无法得到良好的成型物。对于交联-成型时间,如果太短,有时交联反应未完成,有时无法得到良好的成型物。此外,如果交联-成型时间长,则生产率降低,成本升高。
其次,作为提取工序,使用水等提取溶剂,从上述交联中间片材将气泡形成剂和气泡形成助剂完全提取,然后,使其脱水干燥,则能够得到本发明的具有连续气泡的多孔印章材料。本发明由于交联,因此热稳定性优异。因此,即使用70~100℃的温度的热水提取,也不损伤气泡。如果将如本发明那样交联的成型物与相同组成的未交联的成型物用气泡形成剂的提取时间进行比较,则由于加热效果,能够用快数倍的时间完成提取。因此,能够缩短提取工序所需的时间,特别对短交货期的商品有利地发挥作用。
用以上的工序得到的多孔印章材料,具有与成型材料中配合的气孔形成剂的量对应的气孔率,而且成为均质的连续气泡体。此外,由于成为基材的热塑性树脂交联,因此耐热性、耐磨性、拉伸强度等物理特性被作为原料的热塑性树脂组合物增强。因此,对于以往应用困难的需要耐热、耐磨性的用途特别有用。
其中,制作上述母料时,根据需要也能够适当地加入添加物等。例如,能够添加有效量的聚烯丙胺、石蜡、蜡、高级脂肪酸、氟系表面活性剂、有机硅系表面活性剂、非离子表面活性剂等润滑剂、胺系的防老剂、凡士林、增塑剂等软化剂等。
此外,本发明中,也能够任意地添加炭黑、苯胺黑、氧化铁红、群青、氧化钛、碳酸钙等着色剂。通过使上述着色剂混入,能够得到更鲜艳的颜色的多孔印章材料。
其次,对使用本发明的多孔印章材料制作印章的方法进行说明。
对于上述多孔印章材料,使用二氧化碳激光雕刻机或YAG激光雕刻机,将非印面部分雕刻到0.1~10mm左右的深度,形成图1的b那样的印面。然后,使其吸收印章用墨,能够得到内藏墨的印章。
激光雕刻时,认为填充剂作为激光束吸收物质发挥作用,认为防止上述多孔印章材料的不必要的部分的燃烧、熔融,有助于清晰边缘和适当的雕刻深度的形成,实现优异的加工精度。此外,通过交联,能够提高印章材料整体的强度,能够防止印面的凸版部分的倾倒。
实施例
以下通过实施例对本发明更详细地说明。但是,本发明不受这些实施例的任何限定。
(实施例1)
·混合工序:
将作为气泡形成剂的5~60μm的氯化钠61.4重量%投入捏合机,边加热到90℃边搅拌。
其次,边将热保持在90℃,边每次少量地加入作为气泡形成助剂的分子量为10,000的固体的聚乙二醇(熔点:62℃、分解温度:100℃)4.4重量%和甘油3.5重量%,进行混合。这样,聚乙二醇和甘油利用氯化钠的热而熔融,成为液体,与氯化钠浑然一体。
其次,加入作为填充剂的粘土12.3重量%,进一步进行混炼。
其次,加入作为热塑性树脂的聚乙烯切片(熔点:80℃)14.0重量%和作为热塑性弹性体的聚苯乙烯-乙烯基聚异戊二烯三嵌段共聚物切片(玻璃化转变温度:-32℃)3.5重量%,边将热保持在90℃,边进行混炼。
最后,边将热保持在90℃,边加入作为交联剂的有机过氧化物的过氧化二烷基0.9重量%,进一步进行混炼。
这样,得到氯化钠、聚乙二醇、甘油、粘土、聚乙烯、聚苯乙烯-乙烯基聚异戊二烯三嵌段共聚物、过氧化二烷基均一混合的母料。
其次,用压延辊将该母料压延为片状、成型、空冷,作成中间的中间片材。
·交联成型工序:
其次,用热压机将该中间片材夹持于模具,在过氧化二烷基的分解温度以上(100℃)加压加热5分钟,于是得到聚乙烯和聚苯乙烯-乙烯基聚异戊二烯三嵌段共聚物交联的交联中间片材。
该交联中间片材成为了氯化钠、聚乙二醇、甘油、粘土、聚乙烯、聚苯乙烯-乙烯基聚异戊二烯三嵌段共聚物、过氧化二烷基均一分散的状态,而且在熔点以下冷却,全部物质凝固,因此成为即使用手指按压也完全不变形的硬质体。
·提取工序:
其次,将该交联中间片材切断为所需的尺寸,将其在作为提取溶剂的70℃的温水中浸渍3小时,将氯化钠、聚乙二醇、甘油完全提取。
然后,将其用温风干燥机干燥2小时,则能够得到片状的具有30μm平均气泡直径、60%气孔率的连续气泡的多孔印章材料。
·雕刻工序
其次,使用YAG激光雕刻机(加工条件:功率5W、加工速度300mm/秒),对上述多孔印章材料照射激光束,以形成印面部(印面花纹保持部分)0.2mm、肩部(印面梯形部分)的最大深度0.8mm的印面部形状。这样,只是照射了激光束的部分的树脂燃烧蒸发,没有照射激光束的部分的树脂完全没有任何变化。因此,能够形成具有极清晰的边缘的印面。如果将其切割为所需的尺寸,能够得到印章。使该印章吸藏以丙二醇单烷基醚为主成分的印章用油性染料墨(シヤチハタTAT墨),制成印章,结果墨吸藏量也充分,能够长期进行无洇渗或飞白的鲜明的盖章,而且得到不会溶胀、气泡也不溃塌的印章。
以下,将实施例和比较例的配合表示于表1。各工序在与实施例1相同的条件下作成。不过,为了易与实施例比较,比较例的配合量不是重量%,用与各自的配合合计量的比率表示。
比较例1中,从实施例1中去除热塑性弹性体和交联剂,改变填充剂。
比较例2中,从实施例2中去除热塑性弹性体和交联剂,改变填充剂。
比较例3中,从实施例3中去除热塑性弹性体和交联剂,改变填充剂。
比较例4中,从实施例4中去除热塑性弹性体,改变填充剂。
比较例5中,从实施例5中去除热塑性弹性体,改变填充剂。
比较例6中,从实施例6中去除热塑性弹性体,改变填充剂。
(配合例)
使用O型硬度计(按照美国标准ASTM D2240,O型)测定。参考测定方法示于图2。
(耐热性试验)
为了评价多孔印章材料的耐热性,作成厚3mm、10mm见方的多孔印章材料,将其在沸水(100℃)中浸渍30分钟后,使其干燥,制成样品。
其次,测定各个样品的收缩率。如果因沸水而使气泡破坏,则推测收缩而变小,因此认为收缩率大的样品不耐热,收缩率小的样品耐热。
(激光雕刻性试验)
将实施例和比较例中作成的多孔印章材料,使用YAG激光雕刻机(加工条件:功率5W、加工速度300mm/秒),对上述多孔印章材料照射激光束,以形成0.2mm印面部(印面花纹保持部分)、肩部(印面梯形部分)的最大深度0.8mm的印面部形状。
○:激光束未照射部分完全未熔融,形成了清晰边缘的印面部。
△:激光束未照射部分少量熔融,形成了不稳的印面部。
×:激光束未照射部分大量熔融,形成了垂挂的印面部。
实施例中得到了图1的b那样的印面部。比较例中得到图1的a那样的印面部。
(缓冲性试验)
使切割为所需尺寸的多孔印章材料吸藏以丙二醇单烷基醚为主成分的印章用油性染料墨(シヤチハタTAT墨),作成印章,确认压印于非吸收性的铁板时的缓冲性。
Claims (7)
1.具有连续气泡的多孔印章材料,其包含:
从低密度聚乙烯、直链状低密度聚乙烯、高密度聚乙烯、乙烯-α-烯烃共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸系共聚物中选择的至少一种热塑性树脂,
从氢化苯乙烯系热塑性弹性体中选择的至少1种热塑性弹性体,
从无机化合物中选择的至少1种填充剂,上述填充剂为从硅酸盐中选择的至少1种的填充剂;
所述多孔印章材料是使上述热塑性树脂和上述热塑性弹性体交联而成的。
2.权利要求1所述的具有连续气泡的多孔印章材料,其中,以上述热塑性弹性体的2倍~30倍的比例混合上述热塑性树脂。
3.权利要求1~2任意一项所述的具有连续气泡的多孔印章材料,其中,上述热塑性树脂的玻璃化转变温度为摄氏0℃以下。
4.权利要求1~2任意一项所述的具有连续气泡的多孔印章材料,其中,按照美国标准ASTM D 2240 O型,上述多孔印章材料的O型硬度计硬度为75以下。
5.权利要求3所述的具有连续气泡的多孔印章材料,其中,按照美国标准ASTM D 2240O型,上述多孔印章材料的O型硬度计硬度为75以下。
6.权利要求1~5任意一项所述的具有连续气泡的多孔印章材料的制造方法,具有:
混合工序,其中,在从低密度聚乙烯、直链状低密度聚乙烯、高密度聚乙烯、乙烯-α-烯烃共聚物、乙烯-醋酸乙烯酯共聚物、乙烯-丙烯酸系共聚物中选择的至少一种热塑性树脂,从氢化苯乙烯系热塑性弹性体中选择的至少1种热塑性弹性体,和从无机化合物中选择的至少1种填充剂的混合物中混合从水溶性化合物中选择的至少1种气泡形成剂、从多元醇中选择的至少1种气泡形成助剂和从有机过氧化物中选择的至少1种交联剂,得到成型材料,
交联成型工序,其中,加热上述成型材料,使用上述交联剂使上述热塑性树脂和上述热塑性弹性体交联而得到成型物,和
提取工序,其中,从上述交联成型工序中得到的成型物将上述气泡形成剂和上述气泡形成助剂提取,得到具有连续的气泡的多孔成型体。
7.印章,其通过对权利要求1~5任意一项所述的具有连续气泡的多孔印章材料或者用权利要求6所述的制造方法制造的具有连续气泡的多孔印章材料施以激光雕刻,制成印章,使该印章内藏印章用墨而成。
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