CN1119988A - 印刷性极好的具有多层结构的合成纸 - Google Patents
印刷性极好的具有多层结构的合成纸 Download PDFInfo
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Abstract
一种具有多层结构的合成纸,它包括含5-40%(重量)平均粒径为0.01-10μm的无机细粉末、熔点(DSC曲线峰顶温度)为130-210℃的烯烃聚合物的双轴拉伸薄膜作为基材层(A),在其至少一个表面上粘有表面粗糙度为0.3-1.5μm的单轴拉伸层(B),该单轴拉伸层(B)包括熔点(DSC曲线峰顶温度)为120℃-160℃(较之基材层(A)的烯烃聚合物的熔点至少低5℃)的丙烯系列聚合物或高密度聚乙烯,并包含8-65%(重量)平均粒径为0.01-5μm的无机细粉末,其中单轴拉伸层(B)中所含的无机细粉末的表面被丙烯烃系列共聚物或高密度聚乙烯覆盖。
Description
本发明涉及一种具有多层结构的合成纸,它具有极好的印刷性,能使胶印油墨快速干燥,并且较少地产生纸粉(paper powder)问题。
该合成纸可用作广告纸、包装纸、标签纸等的材料。
有人提出并已实际使用了由双轴拉伸聚丙烯薄膜和单轴拉伸聚丙烯薄膜构成的合成纸,所述双轴拉伸聚丙烯薄膜含有5-40%(重量)无机细粉末,作为基材层来代替天然纸浆制成的纸;所述单轴拉伸聚丙烯薄膜含有8-65%(重量)无机细粉末,它迭压在基材层的两个表面上作为纸状层(参见,美国专利4,318,950,JP-B-46-40794,JP-B-60-36173,JP-B-62-35412等,术语“JP-B”此处意指“已审定公告的日本专利申请”)。
由于层压结构的合成纸在作为核心的无机细粉末周期有许多微孔并在表面上有长长的裂缝,有一部分成为微孔核心的无机细粉末和裂缝从表面上凸出(见图3),因此无机细粉末易于从表面层脱落下来(所谓“纸粉问题”),脱落下来的无机细粉末会污染毛毡滚筒并在胶板印刷时与印刷油墨混合,从而降低连续印刷性;而且这也是计算机房和使用CAD的绘图室中灰尘的原因,因而是不利的。
而且,当将胶粘带粘到合成纸的印刷表面上,然后再揭去时,如果纸张的表面强度较纸,则印刷油墨亦被揭去。因此,这样的合成纸不适合用作无需剥离纸的情况下的不干胶标签(热敏压敏粘合型标签)。
而且,当使用合成纸时,在胶板印刷中油墨干燥不完全,需要进一步迅速干燥。
为了避免纸粉问题的出现,美国专利4,663,216描述了一种高度玻璃态的合成纸,它由含有无机细粉末的纸状层和(如果有的话)位于纸状层表面上的不含无机细粉末或含有很少量(不超过3%(重量))无机细粉末的树脂薄膜层构成;JP-B-3-44909描述了一种合成纸,它由含10-40%(重量)无机细粉末的拉伸聚烯烃薄膜(a)和层压在一个表面上的不含无机细粉末的拉伸聚烯烃薄膜(b)构成,该面为印刷面(层(a)的厚度与层(b)的厚度之比至少为4)。
它些合成纸在避免纸粉问题和表面强度方面极好,但缺点是铅写性差并且胶印油墨干燥时间长。
而且,美国专利4,705,719提出了一个具有多层树脂结构的合成纸,它由作为基材层(1a)的双轴拉伸热塑性树脂薄膜和作为表面层(1c)的厚度为0.15-2μm的单轴拉伸苯乙烯/丙烯共聚物薄膜构成。在所述基材层(1a)的至少一个表面上迭压一层由含8-65%(重量)无机细粉末的单轴拉伸热塑性树脂薄膜构成的迭压层作为纸状层(1b)(此外,纸状层含有至少2%(重量)比表面至少为100m2/g的无机细粉末)。其中表面层(1c)的厚度(t)满足下述方程(1):
R≥t≥1/10×R (1)其中R定义为纸状层(1b)中无机细粉末的平均粒径。
然而,上述合成纸在表面强度、铅写性、避免出现纸粉问题和凸印性方面很好,但是胶印油墨的干燥性不够。
本发明的目的是提供一种表面强度、印刷性和铅写性极好,并且表现出胶印刷油墨干燥快,较少出现纸粉问题和进纸问题的合成纸。
也就是说,现在已经发现,上述目的可通过下文所述的本发明而得到实现。
根据本发明,提供了一种具有多层结构的合成纸,它包括含5-40%(重量)平均粒径为0.01-10μm的无机细粉末、熔点(DSC曲线峰顶温度)为130-210℃的烯烃聚合物的双轴拉伸薄膜作为基材层(A),在其至少一个表面上粘有表面粗糙度为0.3-1.5μm的单轴拉伸层(B),该单轴拉伸层(B)包括熔点(DSC曲线峰顶温度)为120℃-160℃(较之基材层(A)的烯烃聚合物的熔点至少低5℃)的丙烯系列聚合物或高密度聚乙烯,并包含8-65%(重量)平均粒径为0.01-5μm的无机细粉末,其中单轴拉伸层(B)中所含的无机细粉末的表面被丙烯烃系列共聚物或高密度聚乙烯覆盖。
在本发明中,形成合成纸表面的单轴拉伸层(B)中的无机细粉末表面被覆以树脂,避免了纸粉问题的出现,由于表面粗糙,胶印油墨干燥快,并由于单轴拉伸层(B)的粗糙,有可能用铅笔书写。
图1是本发明合成纸的一个实施方案的放大的剖面示意图。
图2是本发明合成纸的一个实施方案的表面状态的电子显微图。
图3是常规合成纸的放大的局部剖面图。
图4是美国专利4,318,950所述常规合成纸的表面状态的电子显微图。
在图1和图3中,A代表基材层,B代表表面层,1和2各代表无机细粉末,1′代表巨大颗粒,1″代表聚集的大颗粒。
现在我们详述本发明。
本发明的多层结构合成纸的基材层(A)是烯烃聚合物薄膜的双轴拉伸层,所述烯烃聚合物的熔点(DSC)曲线峰顶温度)最好是130℃至210℃,它含有5-40%(重量)、优选10-35%(重量)的平均粒径为0.01-10μm、优选0.05-8μm的无机细粉末。因为该薄层是含有由双轴拉伸而形成的、下式(2)所示的空洞率高达5-55%的微孔的烯烃聚合物的双轴拉伸膜,所以该薄膜层对合成纸重量的减轻作出了贡献。
空洞率(%)=(βo-β)/βo×100 (2)
βo:拉伸前薄膜的密度
β:拉伸后薄膜的密度
作为待与基材层混合物的无机细粉末,可以使用碳酸钙、氧化钛、煅烧粘土、硅藻土、滑石、硫酸钡、碳酸铝、二氧化硅等的细粉末。
作为用作基材层的烯烃聚合物,可以使用丙烯均聚物、聚(4-甲基戊烯-1)、丙烯/乙烯共聚物、丙烯/(4-甲基戊烯-1)共聚物等。其中优选熔点(DSC曲线峰顶温度)为160-174℃、熔融指数(JIS K7210)为0.5-10g/10分钟且结晶度为35-70%的丙烯均聚物。
基材层的厚度为20-200μm,优选30-150μm。
表面层是丙烯共聚物或高密度聚乙烯(密度:0.945-0.970g/cm3)的单轴拉伸薄膜。聚合物熔点(DSC曲线峰顶温度)为120-160℃并且比构成基材层的烯烃聚合物的熔点至少低5℃,聚合物中含有8-65%(重量)、优选15-55%(重量)平均粒径为0.01-5μm、优选0.05-3μm的无机细粉末、无机细粉末的表面被形成基体的丙烯系列共聚物或高密度聚乙烯所覆盖,并且该薄层的表面粗糙度Rα(JISB0602)为0.3-1.5μm。
如果表面粗糙度小于;0.3μm,则表面的光洁度增大,这将导致引起油墨的干燥性能降低的问题,并且当合成低被堆起来时会出现蹭背现象。同样,如果表面粗糙度超过1.5μm,则表面的不平度太大,这将导致印刷后产生的气体聚集在不平整表面的凹陷处,使得当表面被印刷(背印)时,易于产生所谓“鬼影”(纸正面印刷内容可从纸背面显出)。
单轴拉伸层(B)表面的光洁度(Bekk指数)(JIS P8119)最好低于500秒,其光泽度(JIS P8142;角度60°)最好低于20%。
作为无机细粉末,可以使用平均粒径为0.01-10μm的碳酸钙、氧化钛、煅烧粘土、硅藻土、滑石、硫酸钡、硫酸铝、二氧化硅等。同样,作为丙烯系列共聚物,可以使用丙烯作为主要成分与至少一种选自乙烯、丁烯-1,己烯-1、戊烯-1、4-甲基戊烯-1和3-甲基戊烯-1的α-烯烃的共聚物。该共聚物可以是无规型或嵌段型的。
单轴拉伸层的厚度以2-60μm最为适宜,特别优选2-5μm。
为了赋予作为表面层的单轴拉伸层以纸状感觉,可在上述单轴拉伸层(B)和基材层(A)之间加上一个含8-55%(重量)无机细粉末的丙烯系列树脂的单轴拉伸层。
作为位于单轴拉伸层(B)和基材层(A)之间并赋予单轴拉伸层(B)以纸状感觉的单轴拉伸层所用的丙烯系列树脂,可以使用丙烯均聚物、丙烯/乙烯共聚物、丙烯/(4-甲基戊烯-1)共聚物等。
作为与位于单轴拉伸层(B)和基材料(A)之间并赋予单轴拉伸层(B)以纸状感觉的与单轴拉伸层相混合的无机细粉末,可以使用碳酸钙、氧化钛、煅烧粘土、硅藻土、滑石、碳酸钡、硫酸铝、二氧化硅等。
而且,基材层(A)还可包含少于30%(重量)的低熔点树脂,如丙烯系列共聚物、高密度聚乙烯、聚苯乙烯、乙烯/醋酸乙烯酯共聚物等,以提高拉伸性能。
本发明合成纸可用下述方法获得:预先熔融捏合基材层(A)的树脂组合物,将经捏合的组合物挤塑成片状、利用辊子组圆周速率的差异将挤出片材在纵向拉伸至初始长度的4-12倍,然后将表面层(B)的树脂组合物熔融捏合,将其层压到拉伸片材的至少一个表面上成为片状,然后,用干毡机在比基材层的烯烃聚合物或高密度聚乙烯的熔点至少高3℃的温度下,将层压物在横向拉伸至初始宽度的4-12倍,然后进行热处理和冷却。
拉伸后,基材层被结晶取向,表面层被熔融取向,并且在表面层中不生成空洞。
本发明合成纸的厚度通常为35-300μm。
为改善本发明合成纸的胶印性能,可对表面层(B)的单轴拉伸层的表面进行电晕放电处理,或者用选自诸如聚乙烯亚胺、聚(乙烯亚胺-脲)、聚胺聚酰胺等的乙烯亚胺加成产物;聚胺聚酰胺的表氯醇加成产物;和含有三价或四价氮的丙烯酸树脂的水溶性涂底剂涂覆单轴拉伸层(B)的表面。
下述实施例是为了更具体地说明本发明,但决不对其构成限制。
实施例1
(1)将80%(重量)熔融指数(MI)为0.8g/10分钟(熔融峰顶温度:164℃;熔融结束温度:174℃)的聚丙烯均聚物和8%(重量)高密度聚乙烯的混合物与12%(重量)平均粒径为1.5μm的碳酸钙混合得组合物(A),将其在270℃的挤出机中熔融捏合,从口模中挤出成片状,通过冷却辊筒而使之冷却,得末拉伸片。将该未拉伸片加热至140℃,利用辊筒组的圆周速率的差异将其纵向拉伸至初始长度的5倍。
(2)将53%(重量)MI为10.0g/10分钟(熔融峰顶温度:140℃;熔融结束温度:151℃)的乙烯/丙烯无规共聚物(乙烯含量:2.0%(重量)、2%含有0.5%(重量)马来酸的马来酸改性丙烯均聚物和44.5%(重量)平均粒径为1.5μm的碳酸钙混合,得到组合物(B),将其在270℃的挤出机中熔融捏合。另外,将50%(重量)MI为4.0g/10分钟(熔融峰顶温度:164℃,熔融结束温度:178℃)的丙烯均聚物和50%(重量)平均粒径为1.5μm的碳酸钙混合,得组合物(C),将其在270℃的挤出机中熔融捏合。将经过熔融捏合的组合物(B)和经过熔融捏合的组合物(C)送入共挤出口模中。在将经过熔融捏合的组合物(B)和经过熔融捏合的组合物(C)在口模中层压之后,将层压组合物从口模中共挤出,将如此获得的共挤出片层压到上述步骤(1)得到的拉伸5倍的片材(A)的一个面上,使是含有乙烯/丙烯无规共聚物的薄层(B)成为外面。
然后,将类似方法挤出的组合物(B)与(C)在另一共挤出口模中层压并共挤出到片材(A)的另一面上,在这之前,片材(A)已被拉伸了5倍并被层压以含有乙烯/丙烯无规共聚物的外层薄层(B)。
将该5层层压膜进行电晕放电进行,得到(B)/(C)/(A)/(C)/(B)这样的5层结构的合成纸,其中各层薄膜的厚度分别为5/25/70/25/5μm。
实施例2
按照与实施例1相同的方法,只是要用由53%(重量)高密度聚乙烯(熔融峰顶温度129℃,熔融结束温度:136℃)、2%(重量)马来酸改性的乙烯/醋酸乙烯酯共聚物和45%(重量)平均粒径为1.5μm的碳酸钙组成的组合物来代替单轴拉伸层的树脂组合物(B),得到5层结构的合成纸。
实施例3
按照与实施例1相同的方法,只是要用由35%(重量)乙烯/丙烯无规共聚物(熔融峰顶温度:140℃;熔融结束温度:510℃;乙烯含量:2.0%(重量))、18%(重量)丙烯均聚物(熔融峰顶温度:164℃,熔融结束温度:174℃)、2%(重量)马来酸改性丙烯均聚物和45%(重量)平均粒径为1.5μm的碳酸钙组成的组合物来代替单轴拉伸层的树脂组合物(B),得到5层结构的合成纸。
实施例4
按照与实施例1相同的方法,只是要用平均粒径为0.8μm的碳酸钙来代替单轴拉伸层的组合物(B)中平均粒径为1.2μm的碳酸钙,得到5层结构的合成纸。
实施例5
按照与实施例1相同的方法,只是要用由53%(重量)MI为4g/10分钟(熔融峰顶温度:147℃)的乙烯/丙烯无规共聚物(乙烯含量:1.5%(重量))、2%(重量)马来酸含量为0.5%(重量)的马来酸改性丙烯均聚物和45%(重量)平均粒径为1.5μm的碳酸钙组成的组合物来代替双轴拉伸层的树脂组合物(A)作为基材层,得到5层结构的合成纸。
比较例1
按照与实施例1相同的方法,只是要用MI为4.0g/10分钟(熔融峰顶温度:164℃;熔融结束温度:174℃)的丙烯均聚物来代替单轴拉伸层的组合物(B)的乙烯/丙烯无规共聚物,得到5层结构的合成纸。
比较例2
按照与实施例1相同的方法,只是要用平均粒径为6μm的碳酸钙来代替单轴拉伸层的组合物(B)中平均粒径为1.2μm的碳酸钙,得到5层结构的合成纸。
比较例3
按照与实施例1相现的方法,只是要用由26.5%(重量)乙烯/丙烯无规共聚物(熔融峰顶温度:147℃;乙烯含量:2.0%(重量))、26.5%(重量)丙烯均聚物(熔融峰顶温度:164℃)、2%(重量)马来酸改性丙烯均聚物和45%(重量)平均粒径为1.5μm的碳酸钙组成的组合物来代替单轴拉伸层的树脂组合物(B),得到5层结构的合成纸。评定(1)对无机细粉末上的树脂覆盖的观察
用电子显微镜(2,000倍)观察各实施例和比较例获得的合成纸的表面,若合成纸中无机细粉末的整个表面均覆盖,(参见图1和图2)则评定为“覆盖”,若合成纸中仅有部分无机细粉末被覆盖(参见图3和图4),则评定为“未覆盖”。在图1和图3中,A代表基材层,B代表表面层,1和2各自代表无机细粉末,1′代表巨大颗粒,1″代表聚集的大颗粒。(2)光洁度:用JIS P8119的方法评定。(3)表面粗糙度:用JIS B0602的方法评定。(4)光泽度:用JIS P8142(角度:60°)的方法评定。(5)印刷性能的评定:
用612CD型印刷机(Hamade Printing Press Co.,Ltd.制造)并用胶印油墨、Best SP(商品名,T&K TOKA Co.,Ltd.制造)和深蓝(或靛蓝)印刷各合成纸,评定了下列项目。(5-1)纸粉问题的评定
在1,000个试样片上连续印刷,用肉眼评定毛毡辊筒的白度。
评定级别:
5.未白化。
4.极少白化。
3.少许白化,但白度不足以引起问题。
2.白化,其程度可以引起纸粉问题。
1.大量白化,引起纸粉问题。(5-2)胶印油墨的干燥性能:
用612CD型印刷机(Hamade Printing Press Co.,Ltd.制造)并用胶印油墨、Best SP(商品名,T&K TOKA CO.,Ltd.制造)和深蓝连续印刷1,000张合成纸,让印刷品处于堆集的状态,定时取样,评定干燥状态。
评定级别:
5.很快
4.快
3.不快,但其程度不引起问题
2.较慢,其程度可引起问题
1.很慢(5-3)油墨粘附
将压敏胶粘带(Cello-Tape,商品名,Nichiban Co.,Ltd.制造)粘在各印刷品上,以进行剥离试验,评定油墨的粘附程度。
评定级别:
5.很强。无剥离现象。
4.强。剥离少于5/100。
3.一般。其程度不引起问题(剥离5/100-15/100)。
2.弱。剥离超过20/100。
1.很弱。出现印刷表面的剥离。(6)铅写性能:
以200g的工具力(tool force)用铅笔(HB(即硬黑),#9800,Mitsubishi Pencil Co.,Ltd.制造)在合成纸上画两条交叉(即在纵向和横向)的直线,评定铅定性能的程度。
评定级别:
能写:能画出足够密度的线条。
不能写:不能画出足够密度的线条,即使增加工具力也是如此。
所得结果示于下表1。
表 1
在上表中(A):无机细粉末的覆盖状态。(B):光洁度(JIS P8119)。(C):表面粗糙度(JIS B0602)。(D):光泽度(JIS P9142;角度:60°)。(E):纸粉问题。(F):胶印油墨的干燥性能。(G):胶印油墨的粘附。(H):铅写性能1-5号试样:本发明试样
试样 | (A) | (B)(秒.) | (C)(μm) | (D)(%) | (E) | (F) | (G) | (H) |
12345 | 覆盖″″″″ | 320285370390305 | 0.901.101.000.860.95 | 1410131913 | 55455 | 44444 | 55455 | 能写.″″″″ |
C-1C-2C-3 | 未覆盖″″ | 420155330 | 0.681.651.05 | 171013 | 132 | 343 | 244 | ″″″ |
C-1至C-3号试样:比较用试样
如上表所示,可以看出在本发明的合成纸中,合成纸所含的无机细粉末的表面被丙烯系列共聚物或高密度聚乙烯很好地覆盖,胶印时较少出现纸粉问题。而且,由于在各合成纸的表面形成了适当的不平度,通过氧化性聚合来干燥油墨的过程被加速,并且避免了印刷的合成纸堆集状态下蹭背现象的出现。
尽管参照了具体实施例详述了本发明,但对于本领域技术人员来说,显然可在不背离本发明精神和范围的情况下对其作出多种变化和改进。
Claims (11)
1.一种具有多层结构的合成纸,它包括含5-40%(重量)平均粒径为0.01-10μm的无机细粉末、熔点(DSC曲线峰顶温度)为130-210℃的烯烃聚合物的双轴拉伸薄膜作为基材层(A),在其至少一个表面上粘有表面粗糙度为0.3-1.5μm的单轴拉伸层(B),该单轴拉伸层(B)包括熔点(DSC曲线峰顶温度)为120℃-160℃(较之基材层(A)的烯烃聚合物的熔点至少低5℃)的丙烯系列聚合物或高密度聚乙烯,并包含8-65%(重量)平均粒径为0.01-5μm的无机细粉末,其中单轴拉伸层(B)中所含的无机细粉末的表面被丙烯烃系列共聚物或高密度聚乙烯覆盖。
2.权利要求1所述的合成纸,其中薄层(A)的烯烃聚合物是熔点为160-174℃、熔融指数为0.5-10g/10分钟并且结晶度为35-70%的丙烯均聚物。
3.权利要求1所述的合成纸,其中薄层(B)的丙烯系列共聚物是乙烯/丙烯共聚物。
4.权利要求1所述的合成纸,其中单轴拉伸层(B)的厚度为2-60μm,基材层(A)的厚度为20-200μm。
5.权利要求1所述的合成纸,其中基材层(A)具有空洞率为5-55%的微孔。
6.权利要求1所述的合成纸,其中基材层(A)中的无机细粉末的含量为10-35%(重量),平均粒径为0.05-8μm。
7.权利要求1所述的合成纸,其中表面层(B)中无机细粉末的含量为15-55%(重量),平均粒径为0.05-3μm。
8.权利要求1所述的合成纸,还包括含有8-55%(重量)无机细粉末的丙烯系列树脂的单轴拉伸层(C),其中薄层(C)位于薄层(A)与薄层(B)之间。
9.权利要求1所述的合成纸,其中薄层(A)还包括丙烯系列共聚物、高密度聚乙烯、聚苯乙烯或乙烯/醋酸乙烯酯共聚物。
10.权利要求1所述的合成纸,其中单轴拉伸层(B)表面的光泽度小于20%。
11.权利要求1所述的合成纸,其中单轴拉伸层(B)表面的光洁度小于500秒。
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DE9300963U1 (zh) † | 1993-01-25 | 1993-06-17 | Hoechst Ag, 6230 Frankfurt, De |
-
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- 1994-05-30 JP JP13781794A patent/JP3773273B2/ja not_active Expired - Lifetime
-
1995
- 1995-02-16 TW TW084101407A patent/TW310350B/zh active
- 1995-02-22 DE DE69507538T patent/DE69507538T3/de not_active Expired - Lifetime
- 1995-02-22 EP EP95102507A patent/EP0685331B2/en not_active Expired - Lifetime
- 1995-02-28 KR KR1019950004126A patent/KR100304330B1/ko not_active IP Right Cessation
- 1995-02-28 CN CN95100485A patent/CN1057729C/zh not_active Expired - Lifetime
- 1995-02-28 US US08/395,835 patent/US5667872A/en not_active Expired - Lifetime
Cited By (4)
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CN102971144A (zh) * | 2010-06-30 | 2013-03-13 | 优泊公司 | 易剥离性薄膜、模内成型用标签、带标签的树脂成型品、壁纸、不干胶标签以及带标签的容器 |
CN102971144B (zh) * | 2010-06-30 | 2015-04-08 | 优泊公司 | 易剥离性薄膜、模内成型用标签、带标签的树脂成型品、壁纸、不干胶标签以及带标签的容器 |
CN113165327A (zh) * | 2018-12-28 | 2021-07-23 | 陶氏环球技术有限责任公司 | 层压结构和并有其的柔性包装材料 |
CN113165327B (zh) * | 2018-12-28 | 2023-10-03 | 陶氏环球技术有限责任公司 | 层压结构和并有其的柔性包装材料 |
Also Published As
Publication number | Publication date |
---|---|
US5667872A (en) | 1997-09-16 |
JPH07314622A (ja) | 1995-12-05 |
DE69507538T2 (de) | 1999-06-17 |
CN1057729C (zh) | 2000-10-25 |
DE69507538D1 (de) | 1999-03-11 |
DE69507538T3 (de) | 2006-07-06 |
EP0685331B1 (en) | 1999-01-27 |
EP0685331B2 (en) | 2005-11-23 |
JP3773273B2 (ja) | 2006-05-10 |
KR950032894A (ko) | 1995-12-22 |
EP0685331A1 (en) | 1995-12-06 |
TW310350B (zh) | 1997-07-11 |
KR100304330B1 (ko) | 2001-12-28 |
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