CN110892013B - 介电加热可发泡组合物 - Google Patents
介电加热可发泡组合物 Download PDFInfo
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- CN110892013B CN110892013B CN201880047716.3A CN201880047716A CN110892013B CN 110892013 B CN110892013 B CN 110892013B CN 201880047716 A CN201880047716 A CN 201880047716A CN 110892013 B CN110892013 B CN 110892013B
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Abstract
描述了一种介电加热可发泡组合物以使所述组合物发泡和固化的方法。具体地,使用射频(RF)加热来加热所述可发泡组合物以在制备制品时提供隔热。
Description
技术领域
本发明涉及介电加热可发泡组合物。具体地,使用射频(RF)加热来加热可发泡组合物以在制备制品时提供隔热。
背景技术
寻求比传统的闭孔挤塑聚苯乙烯泡沫包装更对环境无害的一次性食品包装和容器。完全由塑料制成的包装通常在少于400年内不会生物降解,或者如果有的话,一些法规也禁止使用此类包装和容器。
需要可回收、可生物降解和/或可堆肥的替代包装。一种这样的包装包括基于纤维素的基材,其来源于可回收和/或可堆肥的可再生材料。所述包装是通过将两个纤维素基材连接在一起并在两者之间留有空气间隙而制成的。这些替代包装的一些缺点包括隔热性低和在塑料包装上的结构完整性差。当包装被处理和弯曲时,两个基材之间的空气间隙被压缩,在那些压缩区域中的隔热性降低。可以通过增加纤维素基材层之间的空气间隙、增加纤维素基材的厚度或在两层之间插入纤维素介质来改善隔热。
上面提到的一些改善的包装描述于US 9,580,629、US 8,747,603、US 9,273,230、US 9,657,200、US 20140087109、US 20170130399、US 20170130058和US 20160263876。形成的包装在夹在两个基材之间的涂层/粘合剂中具有提供隔热的空气间隙。常规加热需要很长时间和大的空间,用于使水蒸发和使聚合物固化/聚结。此外,由于包装尺寸不同,隔热间隙并不总是均匀的。尽管微波加热提供了对水分含量和均匀空气间隙的严格控制,但穿透深度仅限于约1.5英寸。因此,任何厚度大于约1.5英寸的基材都可能导致包装不均匀。
本领域中需要为所有尺寸的包装提供均匀隔热的方法。本发明提供了生产对环境无害和对经济有利的包装的方法,其为各种尺寸的包装提供了均匀的隔热。
发明内容
本发明涉及使微球填充的水性组合物(waterborne composition)发泡和聚结的方法。
一个实施方案涉及一种使组合物发泡和聚结的方法,该方法包括:
(a)制备包含以下组分的组合物:(i)水基聚合物(water-based polymer),(ii)多个可膨胀微球,多个可膨胀微球的初始可膨胀温度范围为约80℃至约110℃,最大可膨胀温度范围为约50℃至约150℃,和(iii)任选存在的添加剂;以及
(b)将所述组合物暴露于介电加热;
由此,所述组合物中的多个可膨胀微球膨胀并且所述组合物聚结。
另一个实施方案涉及一种形成制品的方法,该方法包括以下步骤:
(a)制备包含以下组分的组合物:(i)水基聚合物,(ii)多个可膨胀微球,所述可膨胀微球的初始可膨胀温度范围为约80℃至约110℃,最大可膨胀温度范围为约50℃至约150℃,和(iii)任选存在的添加剂;
(b)将所述组合物施加到第一基材上;
(c)将第二基材施加到所述组合物上,从而形成其中所述组合物被夹在所述两个基材之间的制品;
(d)对所述制品施加介电加热;
由此,所述组合物中的多个可膨胀微球膨胀并且所述组合物聚结。
介电加热在整个组合物中提供均匀的加热,并且在整个组合物和制品中形成基本上均匀的空气间隙厚度。
附图说明
图1A示出了在微球膨胀后立即通过RF介电加热活化的微球填充的组合物的照片。
图1B示出了在组合物完全干燥之后通过RF介电加热活化的微球填充的组合物的照片。
图2A示出了在微球膨胀后立即通过对流加热活化的微球填充的组合物的照片。
图2B示出了在组合物完全干燥之后通过对流加热活化的微球填充的组合物的照片。
图3A示出了在微球膨胀后立即通过微波加热活化的微球填充的组合物的照片。
图3B示出了在组合物完全干燥之后通过微波加热活化的微球填充的组合物的照片。
图4A示出了在环境温度下干燥小于1分钟后通过RF活化的包装的照片。
图4B示出了在环境温度下干燥小于1分钟后通过RF活化的基材上的粘合剂的照片。
图5A示出了在环境温度下干燥2分钟后通过RF活化的包装的照片。
图5B示出了在环境温度下干燥2分钟后通过RF活化的基材上的粘合剂的照片。
图6A示出了在环境温度下干燥5分钟后通过RF活化的包装的照片。
图6B示出了在环境温度下干燥5分钟后通过RF活化的基材上的粘合剂的照片。
具体实施方式
本发明提供了一种使多个微球发泡并使水性组合物中的发泡的微球聚结以及原位锁定的方法。所述水性组合物包含聚合物和多个微球,并被施加到一个或多个纤维素基材上以形成包装。一旦膨胀并原位(in place)锁定,发泡的微球中的空气间隙将为包装提供隔热和结构完整性。该包装比传统的挤塑聚苯乙烯泡沫包装更对环境无害。
常规加热需要具有长带子的烘箱,这需要大的空间和大量的热量输出。传统加热器通常使用约212°F(100℃)至约450°F(177℃)的温度范围。
微波加热是另一种方法。微波加热在干燥和水分控制方面提供均匀性,并且可以将水分控制在约1%。但是,微波能量会耗散并且不能穿透大于约1.5英寸(4厘米)的深度。此外,微波是已知的辐射危害,因此应使工作人员在此类有害辐射下的暴露最小化。为了使健康风险最小化,工业微波机器通常具有小的开口,因此,将大而且形状奇怪的容器装配到小孔中是具有挑战性的。
在本文中可互换使用的介电加热、电子加热、射频(RF)加热和高频加热是高频交变电场或无线电波加热介电材料的过程。RF加热有别于微波加热。工业无线电频率在大约2MHz至300MHz之间运行,其典型波长为约141至约24英尺(43至7.3米)。工业微波系统使用的频率超过300MHz,其典型波长为约13至约5英寸(33至12cm)。RF发生器中的功率利用效率远低于微波单元,因此,微波单元通常是优选的加热源。
本发明提供对可发泡水性组合物的介电加热(特别是RF加热)。RF在介电材料(在本发明中为极性水分子)之间产生交变电场。制品在电极之间传送,使组合物中的水分子连续地重新取向以面对相对的电极。这种分子运动产生的摩擦导致快速加热。RF以远低于微波加热的频率运行,并且与微波相比,具有更低的健康风险。由于RF较高的穿透深度,因此它也适用于加热体积较大和形状奇怪的容器。
另外,本发明的方法可以包括介电加热和直接加热应用的组合。例如,微球的膨胀可以通过介电加热来实现,而膨胀之后去除多余的水分可以通过直接加热来实现。
RF加热包含水基聚合物和多个可膨胀微球的组合物提供了水和膨胀的微球的均匀加热和干燥。
本发明还基于以下发现:RF加热施加到制品上的包含水基聚合物和多个可膨胀微球的组合物,为制品提供了改善的均匀隔热。
一个实施方案涉及使组合物发泡和聚结的方法,该方法包括:
(a)制备包含以下组分的组合物:(i)水基聚合物,(ii)多个可膨胀微球,所述可膨胀微球的初始可膨胀温度范围为约80℃至约110℃,最大可膨胀温度范围为约50℃至约150℃,和(iii)任选存在的添加剂;以及
(b)将所述组合物暴露于介电加热;
由此,所述组合物中的多个可膨胀微球膨胀并且所述组合物聚结。
RF加热驱使水离开组合物以使水基聚合物聚结,同时,当温度达到微球的活化状态时使微球膨胀。特别优选在约14、27和41MHz的RF频率加热。RF设备可以设计有运算放大器,以使加热最佳。
本文所述的组合物可用于多层基材,特别是用于纤维素基材。使用所述组合物,可以在两个基材之间提供更大的隔热空间,该隔热空间在粘附点处连接。用于本发明的隔热产品包括供消费者使用的纸产品,例如用于以下用途的纸产品:热饮杯和盖、冷饮杯和盖、热食容器和盖、冷食容器和盖、冷冻纸箱(freezer cartons)和盒子、信封、袋子等。
所述组合物可以形成为粘合剂或涂层,粘合剂或涂层在本文中可互换使用。通过形成水基聚合物、多个可膨胀微球和任选存在的添加剂的混合物来制备组合物。
水基聚合物通过乳液聚合来制备,并且可以是单级的(single grade)、或者合成乳液聚合物或天然来源的聚合物的混合物。通过乳液聚合制备的水基聚合物可包括任何期望的聚合物组分,包括淀粉、乙酸乙烯酯乙烯分散体、聚乙酸乙烯酯、聚乙酸乙烯酯聚乙烯醇、糊精稳定的聚乙酸乙烯酯、聚乙酸乙烯酯共聚物、乙酸乙烯酯乙烯共聚物、乙烯基丙烯酸类、苯乙烯丙烯酸类、丙烯酸类、苯乙烯丁基橡胶、聚氨酯、淀粉及它们的混合物。特别优选的乳液聚合物组分是乙酸乙烯酯乙烯分散体、聚乙酸乙烯酯和淀粉。优选地,乳液聚合物被亲水性保护胶体稳定。
水基聚合物可以以任何量存在于所述组合物中,并且在组合物固化之前,理想地以组合物的约60重量%至约99.5重量%的量存在,优选约65重量%至约95重量%。取决于乳液聚合物,基于乳液聚合物,固体含量为约40重量%至约65重量%。
用于本发明的可膨胀微球可以在存在热和/或RF辐射的情况下发生尺寸膨胀。可用于本发明的微球包括,例如,可热膨胀聚合物微球,包括具有烃核和聚丙烯腈壳的那些(例如以商品名出售的那些)和其他类似的微球(例如以商标名出售的那些)。可膨胀微球可具有任何未膨胀的尺寸,包括直径约5微米至约30微米。在存在热或辐射的情况下,本发明的可膨胀微球的直径的增加量可为原始尺寸的约3倍至约10倍。当组合物中的微球膨胀时,组合物变成泡沫状材料,其具有改善的隔热性能。微球通常由塑料或聚合物壳制成,发泡剂位于壳内,设计成在达到特定温度时活化。
可膨胀微球具有使它们开始膨胀的具体温度和它们已经达到最大膨胀的第二温度。微球等级通常以特定膨胀温度(Texp)和最大膨胀温度(Tmax)出售。初始膨胀温度(Texp)是微球开始膨胀的典型温度(Texp),最大膨胀温度(Tmax)是约80%的微球已膨胀的温度。如果微球暴露于远高于Tmax的温度,则微球开始爆炸和收缩(deflate)。
一种特别有用的微球的Texp为约80℃至约105℃。微球已经达到最大膨胀的温度(Tmax)理想地为约90℃至约140℃。
具体微球及其相应的Texp和Tmax的选择对本发明至关重要。尽管在本发明中可以使用任何具体等级的微球,但是在RF条件下配制和活化时应考虑微球的Texp和Tmax。RF辐射从组合物中蒸发出水,但组合物的温度限制在约小于约100℃。如果组合物中存在添加剂和/或盐,则在RF加热期间可能会发生超临界加热,从而将温度推高至高于100℃。但是,可膨胀微球的优选Texp和Tmax分别为小于约100℃和小于约140℃。具有更高温度的微球在RF加热期间不会活化。一旦组合物聚结,微球就基本上被原位锁定,即便不是不可能膨胀,也会使其难以膨胀。令人惊讶的是,RF加热允许微球更稳健地膨胀。与传统的对流加热相比,RF活化的使用允许微球膨胀的自限制,并减少爆炸和收缩。
在优选的实施方案中,理想的是在组合物固化之前,可膨胀微球在组合物中以组合物的约0.1重量%至约70重量%的量存在,更期望的是在组合物固化之前,以组合物的约0.5重量%至约60重量%的量存在,最理想的是在组合物固化之前,以组合物的约1重量%至约50重量%的量存在。可膨胀微球的膨胀率和微球的装载水平彼此相关。
取决于微球的量和聚合物的类型,聚结的组合物可以具有粘合性能。高含量的微球会导致粘合性能较低或没有粘合性能,而低含量(基于组合物的总重量约低于约30重量%)会导致组合物的粘合性能。
取决于微球的完全膨胀的尺寸,可以调节组合物中可膨胀微球的量。取决于组合物中使用的具体的可膨胀微球,可以改变组合物中微球的期望量。
微球在膨胀后进一步增加了聚结的组合物的结构完整性。尽管在基质中引入空隙通常降低机械完整性,但聚合物基质中的微球在施加到基材上时会提供刚性。这对于包装易碎物品特别有用。
在另一个实施方案中,微球可以被预膨胀。如果在组合物中加入预膨胀的微球,则应选择预膨胀的微球,以使RF加热不会使微球开始分解。在又一个实施方案中,微球可以是预膨胀微球和可膨胀微球的混合物。
组合物任选地还包含任何增塑剂;增粘剂;湿润剂;促进剂;填料;颜料;染料;稳定剂;流变改性剂;聚乙烯醇;防腐剂,如抗氧化剂,杀生物剂;及它们的混合物。这些组分的含量可以为组合物的约0.05重量%至约15重量%。
促进剂是来自水溶性盐的多价阳离子,包括常见的硝酸铝(Al(NO3)3)、乙酸锆、碳酸氧锆铵(ammonium zirconyl carbonate)(从Zirconium Chemicals以Bacote 20可得)。多价水溶性盐的添加缩短了组合物膨胀期间所需的辐射时间。当添加时,基于组合物的总重量,可以使用约0.05重量%至约1重量%,优选约0.1重量%至0.3重量%的促进剂。
示例性的防腐剂包括1,2-苯并异噻唑啉-3-酮、5-氯-2-甲基-4-异噻唑啉-3-酮和2-甲基-4-异噻唑啉-3-酮。通常,在组合物固化之前,可以以组合物的约0.05重量%至约0.5重量%的量使用防腐剂。
示例性的填料包括珍珠淀粉、物理改性淀粉和化学改性淀粉。
可以根据需要使用不会不利地影响组合物和组合物的隔热性能的其他材料。期望组合物中可以包括其他添加剂和/或盐以增加组合物的聚结。
尽管组合物可以在室温开始聚结,但是高水分含量会使组合物基本上是流体,直到水分含量为基于总重量的约20重量%、19重量%、18重量%、17重量%、16重量%、15重量%、14重量%、13重量%、12重量%、11重量%、10重量%、9重量%、8重量%、7重量%、6重量%、5重量%、4重量%、3重量%、2重量%或1重量%。优选地,水分含量应保持在大于约20重量%的水平,以防止过早聚结。过早聚结会导致干燥不均匀,从而导致基材上干燥组合物的厚度不均匀。
RF加热还允许以快速通量(throughput)制造制品。必须将组合物设计为适应这种快速通量方法,以使组合物中的固体含量最大化。优选水分子被有效地驱除而不会在基材上留下难看的皱纹或不平整。
令人惊讶地,RF加热以更快的通量提供了微球的均匀且平整的活化以及使水从组合物中更快排出。聚结涂层的均匀和平整为制品提供了均匀的隔热,并将基材上难看的皱纹降至最少,同时提高了产量。
另一个实施方案涉及形成制品的方法,该方法包括以下步骤:
(a)制备包含以下组分的组合物:(i)水基聚合物,(ii)多个可膨胀微球,所述可膨胀微球的初始可膨胀温度范围为约80℃至约110℃,最大可膨胀温度范围为约50℃至约150℃,和(iii)任选存在的添加剂;
(b)将所述组合物施加到第一基材上;
(c)将第二基材施加到所述组合物上,从而形成其中所述组合物夹在所述两个基材之间的制品;
(d)对所述制品施加介电加热;
由此,所述组合物中的多个可膨胀微球膨胀并且所述组合物聚结。
制品适合作为保护性包装、运输包装、耐冲击包装和隔热包装。包装包括杯子、食物容器、盒子、纸箱、袋子、盖、箱子、信封、运输袋(shipping bags)、包裹物(wraps)、翻盖(clamshells)等。
基材包括纤维板、刨花板(chipboards)、瓦楞纸板(corrugated boards)、瓦楞芯纸(corrugated mediums)、固体漂白板(solid bleached boards,SBB)、固体漂白亚硫酸盐板(SBS)、固体未漂白板(solid unbleached board,SLB)、白浆衬里的粗纸板(white linedchipboards,WLC)、牛皮纸、牛皮纸板、铜版纸(coated papers)和书皮纸板(binderboards)。
可以以任何期望的构型将组合物施加到第一基材上,包括一系列的点、条纹、波浪、棋盘图案、具有基本平坦基底的任何一般的多面体形状、以及它们的组合。此外,可以将组合物以一系列圆柱的形式施加到第一表面上。另外,如果需要,可以将组合物作为基本上平坦的片材施加到第一表面上,覆盖整个第一表面(完全层合)或覆盖第一表面的一部分。将第二基材施加到组合物的顶表面,形成以下夹心构型:第一基材–具有可膨胀微球的组合物–第二基材。
在又一个实施方案中,隔热制品包含基本上平坦的基材和不平坦的圆形基材。将组合物施加到基本上平坦的基材上、不平坦的基材上或施加到这两种基材上,以形成隔热制品。可施加组合物以完全涂覆(一种或多种)基材的表面或选择性地涂覆(一种或多种)基材表面的一部分。图案可以是随机的,也可以是各种有序设计。因此,所得制品在衬里表面之间具有隔热空间。具有图案化组合物的制品模仿插在两个基材之间的分隔物。两个基材之间的空间由膨胀的微球产生并保持。
任选地,可以在两个基材之间施加不同的粘合剂。如果组合物具有低的粘合性能或没有粘合性能,这对于将两个基材粘合在一起特别有用。可以在将组合物施加到第一基材上之前、同时或之后施加不同的粘合剂。在另一个实施方案中,可以将不同的粘合剂施加在第二基材上,用组合物将两个基材连接在一起,并且将不同的粘合剂夹在两个基材之间。示例性的不同的粘合剂包括热熔粘合剂、压敏粘合剂、水性粘合剂和溶剂基粘合剂。
将湿组合物施加在两个基材之间以形成制品,然后暴露于介电加热以使组合物聚结并使微球膨胀。因此,加热将包括多个膨胀的微球的组分锁定在基材表面。介电加热在极性水分子之间产生交变电场,并导致快速加热。在水的存在下,温度上升到100℃,水被蒸发掉,同时微球膨胀。具有约80℃至约100℃的Texp和约90℃至约140℃的Tmax的微球等级随着介电加热而膨胀。
使用介电加热,特别是RF加热,允许快速加工。因此,RF方法允许快速通量,并且与对流加热方法相比,可确保更小的面积。而且,由于穿透深度更高,并且烘箱的开口(aperture)比微波炉更灵活,因此可以通过RF处理来制造体积更大且形状奇怪的包装。
用包含微球的组合物形成的多层基材包装改善了包装在升高和/或降低的温度和恒定应力下承受应变的能力。本领域技术人员预期,通过添加微球,组合物在温度升高时的应变增加。
通过分析以下实施例可以更好地理解本发明,这些实施例是非限制性的,并且仅旨在帮助解释本发明。
实施例
实施例1:水基聚合物
表1
树脂乳液 | 水基聚合物名称 | 乳液聚合物 | 固体含量 | pH |
1 | Dur-O-Set C-325 | PVAc | 54-58% | 4.5-6.0 |
2 | Resyn 1072 | PVAc | 62-67% | 3.5-5.5 |
3 | Dur-O-Set E-200 | EVA | 53-59% | 4.0-5.0 |
实施例2:组合物
用以下组分制备组合物。每种树脂乳液用于制备以下组合物。
表2
组合物 | A(%) | 1(%) | 2(%) | 3(%) | 4(%) | 5(%) |
树脂乳液 | 91.4 | 87.4 | 89.4 | 86.4 | 85.4 | 83.4 |
可膨胀微球* | 0 | 4.0 | 4.0 | 6.0 | 8.0 | 8.0 |
Benzoflex K88,Eastman | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 |
NaCl,Aldrich | 2.0 | 2.0 | 0 | 1.0 | 0 | 2.0 |
甘油,Aldrich | 2.4 | 2.4 | 2.4 | 2.4 | 2.4 | 2.4 |
Methocel K4M,Colorcon | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
Kathon,Dow Chemical | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
*Texp 80℃,Tmax 135℃,中值粒径15.2μm,发泡剂异丁烷(浓度为10-20%),密度≤10kg/m3
各组合物是通过在容器中混合组分而制备的。
实施例3:活化
将处于湿润状态的组合物4和树脂乳液3组合物以一系列的点状图案施加到纸基材(20磅和24磅纸,Golden Kraft)上。通过常规加热、微波或RF介电加热(40MHz和55-62Amps)来活化每种基材。涂层的初始高度和活化后的最终高度记录在表3中。通过计算涂层的非膨胀区段(segments)的量,目测活化后即刻的湿度百分比。
表3
用RF活化在微球膨胀和平整度方面比另外两种加热方法具有优越的增加百分比。而且,RF加热提供了快得多的干燥,因为湿度百分比显著低于对流和微波加热。
活化的组合物在纸上的照片如图1-3所示。RF加热,如图1A和图1B所示,提供一致的和平整的膨胀,而对流加热(图2A和2B)和微波加热(图3A和3B)没有提供组合物的一致的膨胀。
实施例4:固体含量
为了理解速度通量,通过在第一基材上涂覆组合物4(树脂乳液3)并将第二基材放置在第一基材的顶部来形成包装。然后,在用40MHz和55-62Amps的RF活化之前,将包装在环境温度(约72oF至约90oF)中放置少于1分钟、2分钟或5分钟。
在图4A、5A和6A中示出了涂覆的基材的背面的包装外观。将两个基材拉开并拍照,示于图4B、5B和6B。
表4
尽管高固体含量允许更快的制造通量,但是高固体含量组合物的表面可以在组合物的表面上形成表皮,从而防止水分逸出。为了使皱纹和不均匀发泡最小化,应在小于1分钟内用RF活化组合物。包括涂覆和在小于1分钟内活化涂层的快速通量方法允许最大收益。
Claims (7)
1.用于制备制品的方法,其包括以下步骤:
(a)制备包含以下组分的可发泡组合物:(i)水中的水基聚合物,(ii)多个可膨胀微球,所述可膨胀微球的初始可膨胀温度范围为80℃至110℃,最大可膨胀温度范围为90℃至150℃,和(iii)任选存在的添加剂;
(b)将所述可发泡组合物施加到第一基材上;
(c)将第二基材施加到所述可发泡组合物上;
(d)将所述制品暴露于介电加热以进行射频加热,所述射频加热在小于300MHz的频率下进行,由此在所述第一基材和第二基材之间形成发泡的组合物;
其中,步骤(b)和(c)在小于1分钟内完成,
其中,所述发泡的组合物的厚度为0.125至0.135英寸,并且在形成所述发泡的组合物后少于10%的所述第一基材和第二基材包含皱纹。
2.根据权利要求1所述的方法,其中所述基材是纤维板、瓦楞纸板、固体漂白板、牛皮纸或铜版纸。
3.根据权利要求1所述的方法,其中以图案形式施加所述组合物,所述图案是一系列的点、条纹、波浪、棋盘、或具有基本平坦基底的多面体形状。
4.根据权利要求1所述的方法,其进一步包括以下步骤:在所述第一基材与第二基材之间施加粘合剂,所述粘合剂是热熔粘合剂。
5.根据权利要求1所述的方法,其中所述射频加热在13、27或40MHz的范围进行。
6.根据权利要求1所述的方法,其中所述制品是杯子、食物容器、盒子、袋子、箱子、盖、信封或包裹物。
7.根据权利要求1所述的方法,其中所述制品是纸箱或翻盖。
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CN116496545A (zh) | 2023-07-28 |
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US20210214581A1 (en) | 2021-07-15 |
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