CN110049871A - 聚合物多层膜 - Google Patents
聚合物多层膜 Download PDFInfo
- Publication number
- CN110049871A CN110049871A CN201780076134.3A CN201780076134A CN110049871A CN 110049871 A CN110049871 A CN 110049871A CN 201780076134 A CN201780076134 A CN 201780076134A CN 110049871 A CN110049871 A CN 110049871A
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- multilayer film
- polymer multilayer
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- polymer
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Abstract
本发明提供了聚合物多层膜,该聚合物多层膜包括其余表现出股线和连接区域的无规网络的层,所述层是与其余聚合物多层膜可分离的。聚合物多层膜可用于例如带材和图形制品。
Description
相关申请的交叉引用
本申请要求2016年12月9日提交的美国临时专利申请62/432384的权益,该临时专利申请的公开内容全文以引用方式并入本文。
背景技术
期望使聚合物膜和膜复合物具有提供附加功能性的结构和/或纹理。此类功能性可包括光学效应、和/或由于纹理表面相对于平滑表面增大的表面积而增强的液体吸收程度或固体保持程度。
纹理或结构可例如通过将熔融聚合物浇铸到图案化的冷却辊上来添加到聚合物膜。这需要针对每个期望的纹理或结构化膜使用特定的图案化辊。另选地,非图案化聚合物膜可在膜制作过程之后通过重新加热膜表面的至少一部分并在高压辊隙(其中辊中的至少一个具有期望的图案的相反面)之间穿过来进行压花。此技术需要另外的工艺步骤,并且需要针对每个期望的最终纹理或结构制造和使用图案化辊。
纹理化膜还可通过将聚合物层涂覆或层压到非织造幅材上来生产。非织造层提供期望的纹理或结构,同时膜层提供其它功能性,诸如阻隔或装饰层。这个过程需要多个过程步骤来生产期望的最终产品—生产非织造幅材并且需要至少一个第二步骤来提供聚合物层到非织造材料上的层压或涂覆。
仍然需要生产可在不需要独特的图案化辊或不需要二次加工来产生纹理或结构的情况下生产的结构化和/或纹理化的聚合物膜或膜复合物。
发明内容
本公开描述了一种聚合物多层膜,该聚合物多层膜包括其余表现出股线(在一些实施方案中,长形股线)和连接区域的无规网络(该无规网络具有第一光密度并且该连接区域具有第二光密度,其中该第一光密度大于该第二光密度;在一些实施方案中,在这些连接区域中的至少一些区域中存在开孔,而在一些实施方案中,在层中不存在开孔(即,没有通孔))的聚合物层,该聚合物层是与其余聚合物多层膜可分离的。在一些实施方案中,聚合物多层膜还包括表现出股线和连接区域的无规网络的至少一个附加聚合物层(在一些实施方案中,包括各自表现出股线和连接区域的无规网络的至少2个、3个、4个、5个、6个或甚至至少7个附加聚合物层。在一些实施方案中,所有的层或这些层中的一些与表现出股线和连接区域的无规网络的另一个层相邻。在一些实施方案中,各自表现出股线和连接区域的无规网络的一个或多个附加聚合物层包含压敏粘合剂,其中的每一个都可以与第一压敏粘合剂相同或不同,或者彼此相同或不同。
本文所述的聚合物多层膜的实施方案可用于例如带材和图形制品。
附图说明
图1是股线和连接区域的一个示例性无规网络的顶部示意图。
图2是股线和连接区域的另一个示例性无规网络的顶部示意图。
图3是用于制作本文所述的聚合物多层膜的示例性设备。
图3A是图3所示的设备中使用的示例性环形模头。
图4和图4A是实施例1的聚合物多层膜的光学图像。
图5和图5A是实施例2的聚合物多层膜的光学图像。
具体实施方式
本公开描述了一种聚合物多层膜,该聚合物多层膜包括其余表现出股线(在一些实施方案中,长形股线)和连接区域的无规网络(该无规网络具有第一光密度并且该连接区域具有第二光密度,其中该第一光密度大于该第二光密度;在一些实施方案中,在这些连接区域中的至少一些区域中存在开孔,而在一些实施方案中,在层中不存在开孔(即,没有通孔))的聚合物层,该聚合物层是与其余聚合物多层膜可分离的。在一些实施方案中,聚合物多层膜还包括表现出股线和连接区域的无规网络的至少一个附加聚合物层(在一些实施方案中,包括各自表现出股线和连接区域的无规网络的至少2个、3个、4个、5个、6个或甚至至少7个附加聚合物层。在一些实施方案中,所有的层或这些层中的一些与表现出股线和连接区域的无规网络的另一个层相邻。在一些实施方案中,各自表现出股线和连接区域的无规网络的一个或多个附加聚合物层包含压敏粘合剂,其中的每一个都可以与第一压敏粘合剂相同或不同,或者彼此相同或不同。
参见图1,示出了股线103和连接区域104的无规网络的一个示例。
参见图2,示出了股线203和连接区域204的无规网络的另一个示例。
在一些实施方案中,表现出股线和连接区域的无规网络的层以及其它层独立地包含以下中的至少一种:聚烯烃材料(例如,聚丙烯和/或聚乙烯)、改性聚烯烃材料、聚氯乙烯、聚碳酸酯、聚苯乙烯、聚酯(包括共聚酯)、聚交酯、聚偏二氟乙烯、(甲基)丙烯酸(例如,聚甲基丙烯酸甲酯)、氨基甲酸酯、丙烯酸氨基甲酸酯、乙烯乙酸乙烯酯共聚物、丙烯酸酯改性乙烯乙酸乙烯酯聚合物、乙烯丙烯酸共聚物、尼龙、工程聚合物(聚酮和/或聚甲基戊烷)、或弹性体(例如,天然橡胶;合成橡胶;含有异戊二烯、丁二烯、或乙烯(丁烯)嵌段的苯乙烯嵌段共聚物;茂金属催化的聚烯烃、聚氨酯;或聚二有机硅氧烷)。
在一些实施方案中,表现出股线和连接区域的无规网络的层具有至少1%的开孔孔隙度(在一些实施方案中,为至少5%、10%、15%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、或甚至至少80%;在一些实施方案中,在1%至80%的范围内)。
一般来讲,包含(表现出本文所述的股线和连接区域的无规网络的)至少一个层的聚合物多层膜可通过在吹塑膜方法中对层进行过度发泡制成,该吹塑膜方法使用环形模头以形成熔融膜管,该熔融膜管通过“气泡”中的气压径向定向,并且还在膜熔融区域中纵向地拉动以使膜变薄至最终期望的厚度。例如,参见图3,用于制作包含(各自表现出本文所述的股线和连接区域的无规网络的)至少两个相邻层的聚合物多层膜的设备300包括:料斗304、挤出机306、环形模头308、气环310、塌缩框架314、形成辊隙317的辊316A、316B、裁切站323和惰辊318、319。参见图3A,示出了九层环形模头308的进一步细节,该九层环形模头308包括堆叠的模板,其中每个单独的模板堆叠层具有机加工的聚合物流动通道309A、309B、309C、309D、309E、309F、309G、309H、309I。在膜制作过程期间,熔融聚合物穿过流动通道309A、309B、309C、309D、309E、309F、309G、309H、309I并接触中心模筒310,并且然后向上流动以与其它层结合,并且离开环形模头开孔311以形成多层膜管312。聚合物多层膜中的层的数目可通过环形模头中的堆叠的模板的数目来调节。
在操作时,将树脂302(通常呈球剂的形式)和其它添加剂添加到料斗304中。熔融的或能够以其它方式流动的树脂离开挤出机306进入环形模头308中。气环310在熔融聚合物气泡上提供均匀的气流,其稳定聚合物气泡并有助于冷却聚合物气泡,从而借助于穿过通过接触压料辊316A和316B形成的辊隙317来将圆形膜泡312形成为塌缩膜管320。塌缩膜管横过惰辊318并且穿过裁切站323,从而导致在另外的惰辊319上经过的两个平膜320A和320B的形成。然后将膜320A和320B分别卷绕到单个辊321A和321B中。聚合物多层膜的层可例如通过将气体引入到挤出机内的熔融聚合物中来发泡或过度发泡。在挤出过程的热和压力下,气体容易地被吸收到聚合物中。当熔融聚合物离开挤出模头时,被吸收的加压气体快速地膨胀并形成空隙。可调节正确的工艺条件,使得当聚合物固化时,空隙结构被“锁定”,从而在聚合物膜中产生泡沫结构。
可例如通过在层的树脂中包括或注入起泡剂来促进该层的发泡。起泡剂是本领域已知的,并且包括将气体(例如,氮气或二氧化碳)注入到熔融聚合物中。起泡剂是本领域已知的,并且包括碱土金属碳酸盐和碱金属酸盐的共混物,上述内容在美国专利8,563,621(Lapierre)中有所描述,其公开内容以引用方式并入本文。示例性可商购获得的发泡剂包括以商品名“ECOCELL H”得自新泽西州罗卡韦的Polyfil公司(Polyfil Corp.,Rockaway,NJ)的那些。用于聚合物的其它示例性化学发泡剂是本领域熟知的,并且包括肼、酰肼和偶氮二碳酰胺材料(例如,4,4’-氧代双(苯磺酰肼))(OBSH)(例如以母料形式、以商品名“CELOGEN OT”购自华盛顿州贝尔维尤的ChemPoint公司(ChemPoint,Bellevue,WA))。另一个示例性化学发泡剂是吸热起泡剂,其以母料形式、以商品名“FCX111263”购自明尼苏达州威诺纳的RTP公司(RTP Company,Winona,MN)。
在一些实施方案中,将形成剂添加到馈送到挤出机中的树脂中。选择或调节起泡剂和其它加工条件以提供期望的或可接受的聚合物多层膜,该聚合物多层膜包括表现出股线和连接区域的无规网络的层。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含紫外线(UV)吸收剂。UV吸收层(例如,UV保护层)可通过吸收UV光(在一些实施方案中,任何UV光)而有助于保护其它层或基底免受随时间推移UV光导致的破坏/降解。
在一些实施方案中,UV吸收剂为红移UV吸收剂(RUVA),其吸收在180nm至400nm的波长区域中至少70%(在一些实施方案中,至少80%或甚至大于90%)的UV光。通常,期望RUVA应是高度可溶于聚合物的、高度吸收性的、光持久的并且至少在200℃至300℃的温度范围内是热稳定的以便于挤出过程形成保护层。在一些实施方案中,RUVA可通过自由基引发剂固化、UV固化、γ射线固化、电子束固化或热固化工艺中的至少一者与单体共聚,以形成保护性涂层。示例性UVA是如例如在PCT公布WO2014/10055A1(Olson等人)和WO2014/100580A1(Olson等人)、WO 2015/200655(Olson等人)、WO 2015/200669(Olson等人)和WO2015/200657(Olson等人)中描述的UVA低聚物,其公开内容以引用方式并入本文。
RUVA通常在长波UV区域(即300nm至400nm)中具有增大的光谱覆盖率,使得它们能够阻挡可在大多数聚合物中引起泛黄的高波长UV光。典型的UV保护层的厚度在约13微米至380微米的范围内并且RUVA装填量在约2重量%至10重量%的范围内。示例性RUVA包括苯并三唑化合物、5-三氟甲基-2-(2-羟基-3-α-枯基-5-叔辛基苯基)-2H-苯并三唑(可以商品名“CGL-0139”购自新泽西州弗洛勒姆帕克的巴斯夫公司)、苯并三唑(例如,2-(2-羟基-3,5-二-α-枯基苯基)-2H-苯并三唑、5-氯-2-(2-羟基-3-叔丁基-5-甲基苯基)-2H-苯并三唑、5-氯-2-(2-羟基-3,5-二叔丁基苯基)-2H-苯并三唑、2-(2-羟基-3,5-二叔戊基苯基)-2H-苯并三唑、2-(2-羟基-3-α-枯基-5-叔辛基苯基)-2H-苯并三唑、2-(3-叔丁基-2-羟基-5-甲基苯基)-5-氯-2H-苯并三唑)和2(-4,6-二苯基-1-3,5-三嗪-2-基)-5-己氧基-苯酚。另外的可商购获得的RUVA包括可以商品名“TINUVIN 1577”、“TINUVIN 1600”和“TINUVIN 777”购自巴斯夫公司(BASF Corporation)的那些。其它示例性UV吸收剂是可以商品名“TA11-10MB03”购自南卡罗来纳州邓肯的苏卡诺聚合物公司(Sukano Polymers Corporation,Duncan,SC)的聚甲基丙烯酸甲酯(PMMA)UVA母料。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含受阻胺光稳定剂(HALS)。示例性HALS包括可以商品名“CHIMASSORB 944”和“TINUVIN 123”购自巴斯夫公司(BASF Corporation)的那些。另一种示例性HALS可例如以商品名“TINUVIN 944”购自巴斯夫公司(BASF Corp.)。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含抗氧化剂。示例性抗氧化剂包括可以商品名“IRGANOX 1010”和“ULTRANOX 626”购自巴斯夫公司(BASFCorporation)的那些。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含抗氧化剂。抗氧化剂可减少或防止彩色显影以及聚合物多层膜的物理和机械性能的退化。示例性抗氧化剂材料包括可例如以商品名“CYANOX 1790”和“CYANOX 2777”商购自新泽西州伍德兰帕克的氰特索尔维集团(Cytec Solvay Group,Woodland Park,NJ)的那些。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含亲水性材料。亲水性添加剂可以增加对含水液体的吸收。这可用于例如清洁产品以吸收溢出物和含水清洁剂、以及用于医疗应用以吸收体液。示例性亲水性材料包括可例如以商品名“JDOSS 50P”购自宾夕法尼亚州库珀斯堡的JLK实业公司(JLK Industries,Coopersburg,PA)的阴离子表面活性剂、或可例如以商品名“HETOXAMIDE C4”购自新泽西州富兰克林的Global 7实业公司(Global 7Industries,Franklin,NJ)的非离子表面活性剂(PEG-5椰油酰胺)。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含至少一种防静电材料。防静电材料可例如减少成品吸尘和吸灰,减少通过放电产生的火花,减少易燃的液体和气体的点火,减少对电子电路的损坏,以及减少运输设备的干扰。示例性防静电材料包括可以商品名“CTASTAT 609”和“CYASTAT SN”购自新泽西州伍德兰帕克的氰特索尔维集团(Cytec Solvay Group,Woodland Park,NJ)的那些。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含防粘剂。示例性防粘剂包括烷基聚二甲基硅氧烷、聚乙烯十八烷基氨基甲酸酯、或亚乙基双硬脂酰胺中的至少一者。例如在美国专利9,187,678(Boardman等人)中描述的烷基聚二甲基硅氧烷。聚乙烯十八烷基氨基甲酸酯可例如以商品名“ESCOAT P-77”(线性、低密度载体树脂中的聚乙烯十八烷基氨基甲酸酯)商购自佐治亚州苏万尼的Mayzo公司(Mayzo,Inc.,Suwanee,GA)。亚乙基双硬脂酰胺可例如以商品名“AMPACET 100666”购自纽约州塔里敦的安帕西公司(Ampacet Corporation,Tarrytown,NY)。压敏粘合带或粘合带常常以卷形式提供,其中带构造包括背衬、背衬的一个主侧面上的粘合剂层、以及背衬的另一个主侧面上的防粘层。防粘层允许带以受控的水平从卷上退绕。在多种应用中采用了其它具有防粘特征的制品。从实用性上讲,任何粘合剂涂覆的制品(包括带材、模切粘合剂制品、标签)需要防粘涂层或单独的防粘衬件。防粘涂层或衬件提供了制品不能永久性地粘附的表面。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含滑爽添加剂或粘连剂中的至少一者。滑爽添加剂可改变膜的表面性能,减少膜层和其它表面之间的摩擦。为了有效,滑爽添加剂需要迁移出聚合物以到达表面,并且因此它需要与聚合物具有一定程度的不相容性。
示例性滑爽添加剂包括脂肪酸酰胺,诸如芥酸酰胺或油酰胺。在加工过程中,滑爽添加剂溶解在无定形熔体中,但随着聚合物冷却并结晶,脂肪酸酰胺被“挤压”出来,从而在聚合物表面处形成润滑层。滑爽添加剂的添加可减少或防止膜粘着和牵拉,从而有助于增加吞吐量。示例性滑爽添加剂可例如以商品名“AMPACET 100497”(低密度聚乙烯载体树脂中的包含1%的芥酸酰胺的母料);和“#10358”(聚乙烯载体中的具有5%油酰胺的母料)商购自纽约州塔里敦的安帕西公司(Ampacet Corporation,Tarrytown,NY)。
粘连剂可减少或防止层的粘连。聚烯烃和其它塑料膜具有粘附在一起的趋势,从而通常使得难以分离层。膜层之间的这种粘附性(称为粘连)是一些聚合物的固有性能。可将防粘连添加剂添加到膜,以使得这种粘附性最小化,并减少层之间的粘连力。一旦配混成塑料,这些添加剂就形成微粗糙表面,这降低了膜层之间的粘附性并降低了粘连趋势。示例性防粘连剂通常是无机材料,诸如硅藻土、滑石、碳酸钙、粘土、云母和陶瓷球体。示例性防粘连剂可例如以商品名“ABC5000”商购自新泽西州罗卡韦的Polyfil公司(PolyfilCorporation,Rockaway,NJ);并且以商品名“AMPACET 102077”商购自安帕西公司(AmpacetCorp.)。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含耐磨材料。可添加耐磨材料以减少成品的刮痕、划痕和磨蚀。示例性耐磨添加剂可例如以商品名“MB25-381”(包含硅氧烷聚合物的母料)商购自密歇根州奥本的道康宁公司(Dow Corning,Auburn,MI)。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含染料或颜料(例如,赋予颜色,诸如白色、黄色、绿色、蓝色、红色、橙色、棕色、黑色等)中的至少一者。示例性染料包括可例如以商品名“CLARIANT REMAFIN PE63421213-ZN”(绿色染料母料)商购自瑞士穆滕茨的克莱恩国际有限公司(Clariant International AG,Muttenz,Switzerland)的那些。示例性颜料包括二氧化钛、氧化锌和二氧化锆。一种示例性颜料,可以商品名“#11937”(聚烯烃载体中的二氧化钛颜料的母料)商购自佐治亚州索舍尔瑟克尔的斯坦德瑞琪色彩公司(Standridge Color Corporation,Social Circle,GA)。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含油墨吸收材料或油漆吸收材料中的至少一种。油墨吸收材料可能期望向膜添加信息或装饰性元素以改善膜的功能性或美观性。示例性吸收材料包括(例如)如例如在美国专利6,316,120(Emslander)中描述的乙烯/乙酸乙烯酯/一氧化碳三元共聚物,其公开内容以引用方式并入本文。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层包含金属(例如,铝、青铜、不锈钢、锌、铁、锡、银、金和/或钛)颗粒。金属颗粒可提供独特的装饰性方面,诸如膜的闪光或珠光。示例性金属颗粒添加剂可例如以商品名“PELLEX A240-50”(金属闪光剂母料)商购自伊利诺伊州艾迪生的Cary公司(The Cary Company,Addison,IL)。
在一些实施方案中,本文所述的聚合物多层膜中的至少一个层(包括表现出股线和连接区域的无规网络的层)包含粘合剂(包括压敏粘合剂)。
在一些实施方案中,本文所述的聚合物膜的至少一个层(包括表现出股线和连接区域的无规网络的层)基本上不含压敏粘合剂。在一些实施方案中,表现出股线和连接区域的无规网络的层包含压敏粘合剂。示例性压敏粘合剂包括可例如以商品名“OCA8171”和“OCA8172”购自明尼苏达州圣保罗的3M公司(3M Company,St.Paul,MN)的那些。可挤出的压敏粘合剂可例如以商品名“LIR-290”、“LA2330”、“LA2250”、“LA2140E”和“LA1114”商购自日本大阪的可乐丽公司(Kuraray,Osaka,Japan);以及以商品名“ESCORE”商购自得克萨斯州欧文的埃克森美孚公司(Exxon Mobil,Irving,TX)。压敏粘合剂的粘着性可例如用增粘剂来调节。
其它示例性粘合剂包括异丁烯/异戊二烯共聚物,这些异丁烯/异戊二烯共聚物可例如以商品名“EXXON BUTYL 065”、“EXXON BUTYL 068”和“EXXON BUTYL 268”(据信具有在约1.05摩尔%至约2.30摩尔%的范围内的不饱和度)购自埃克森美孚公司(Exxon MobilCorp.);以商品名“BK-1675N”(据信具有约1.7摩尔%的不饱和度)购自法国韦利济-维拉库布莱的United Chemical Products公司(United Chemical Products,Velizy-Villacoublay,France);以商品名“LANXESS BUTYL 301”(据信具有约1.85摩尔%的不饱和度)、“LANXESS BUTYL 101-3”(据信具有约1.75摩尔%的不饱和度)和“LANXESS BUTYL402”(据信具有约2.25摩尔%的不饱和度)购自加拿大安大略省萨尼亚市的朗盛公司(Lanxess,Sarnia,Ontario,Canada);以及以商品名“SIBSTAR”(可以苯乙烯含量据信基于共聚物的摩尔百分比在约15摩尔%至30摩尔%的范围内的两嵌段和三嵌段形式获得)得自日本大阪的钟化公司(Kaneka,Osaka,Japan)。示例性聚异丁烯树脂可例如以商品名“VISTANEX”商购自得克萨斯州欧文的埃克森美孚公司(Exxon Chemical Co.,Irving,TX);以商品名“HYCAR”商购自北卡罗来纳州夏洛特的古德里奇公司(Goodrich Corp.,Charlotte,NC);以及以商品名“JSR BUTYL”商购自日本关东的Japan Butyl有限公司(Japan Butyl Co.,Ltd.,Kanto,Japan)。
一般来讲,合适的聚异丁烯可具有广泛的分子量和广泛的粘度。在一些实施方案中,聚异丁烯的重均分子量(如使用聚苯乙烯标准物通过凝胶渗透色谱法所测量)为至少约300,000克/摩尔(在一些实施方案中,为至少约400,000克/摩尔或甚至至少500,000克/摩尔或更高)。在一些实施方案中,聚异丁烯的重均分子量低于300,000克/摩尔(在一些实施方案中,为最高280,000克/摩尔、275,000克/摩尔、270,000克/摩尔、260,000克/摩尔、250,000克/摩尔、240,000克/摩尔、230,000克/摩尔、220,000克/摩尔、210,000克/摩尔,或最高200,000克/摩尔)。在一些实施方案中,当由20℃下在二异丁烯中的本征粘度所量度的粘度限定时,聚异丁烯的粘均分子量在100,000克/摩尔至10,000,000克/摩尔(在一些实施方案中,500,000克/摩尔至5,000,000克/摩尔)的范围内。可商购得到许多不同分子量和粘度的聚异丁烯。在一些实施方案中,在制备压敏粘合剂的过程期间,聚异丁烯的分子量发生改变。
在一些实施方案中,包含聚异丁烯的压敏粘合剂还包含氢化烃增粘剂(在一些实施方案中,聚(环烯烃))。在一些实施方案中,氢化烃增粘剂基于压敏粘合剂组合物的总重量计以约5重量%至约90重量%的范围存在。在一些实施方案中,将聚(环烯烃)与基于压敏粘合剂组合物的总重量计约10重量%至约95重量%的聚异丁烯进行共混。在一些实施方案中,压敏粘合剂包含基于压敏粘合剂组合物的总重量计在约5重量%至约70重量%范围内的氢化烃(例如,聚(环烯烃))增粘剂以及基于压敏粘合剂组合物的总重量计约30重量%至约95重量%的聚异丁烯。在一些实施方案中,基于压敏粘合剂组合物的总重量计,氢化烃增粘剂(在一些实施方案中,聚(环烯烃))以低于20重量%(在一些实施方案中,低于15重量%)的量存在。例如,基于压敏粘合剂组合物的总重量计,氢化烃增粘剂(在一些实施方案中,聚(环烯烃))可以5重量%至19.95重量%、5重量%至19重量%、5重量%至17重量%、5重量%至15重量%、5重量%至13重量%或5重量%至10重量%的范围存在。在一些实施方案中,压敏粘合剂不含丙烯酸类单体和聚丙烯酸酯。示例性聚异丁烯压敏粘合剂包括包含氢化聚(环烯烃)和聚异丁烯树脂的粘合剂组合物,诸如在PCT公布WO 2007/087281(Fujita等人)中报告的那些,其公开内容以引用方式并入本文。
用于任选第四层的示例性氢化烃增粘剂可以例如以商品名“ARKON P”和“ARKONM”商购获自日本大阪的荒川化学工业株式会社(Arakawa Chemical Industries Co.,Ltd.)。这些材料在商业文献中被描述为水白色的氢化烃树脂。据说商品名为“ARKON P”(例如,P-70、P-90、P-100、P-115和P-140)的氢化烃增粘剂是完全氢化的,而商品名为“ARKONM”(例如,M-90、M-100、M-115和M-135)的那些是部分氢化的。据说可以商品名“ARKON P-100”购得的氢化烃增粘剂具有约850克/摩尔的数均分子量、约100℃的软化点和约45℃的玻璃化转变温度。可以商品名“ARKON P-140”购得的氢化烃增粘剂具有约1250克/摩尔的数均分子量、约140℃的软化点和约90℃的玻璃化转变温度。可以商品名“ARKON M-90”购得的氢化烃增粘剂具有约730克/摩尔的数均分子量、约90℃的软化点和约36℃的玻璃化转变温度。可以商品名“ARKON-M-100”购得的氢化烃增粘剂具有约810克/摩尔的数均分子量、约100℃的软化点和约45℃的玻璃化转变温度。
用于任选第四层的其它示例性氢化烃增粘剂可例如以商品名“ESCOREZ 1315”、“ESCOREZ 1310LC”、“ESCOREZ 1304”、“ESCOREZ 5300”、“ESCOREZ 5320”、“ESCOREZ 5340”、“ESCOREZ 5380”、“ESCOREZ 5400”、“ESCOREZ 5415”、“ESCOREZ 5600”、“ESCOREZ 5615”、“ESCOREZ 5637”和“ESCOREZ 5690”购自埃克森美孚公司(Exxon Chemical)。
“1300”系列树脂在商业文献中被描述为具有高软化点的脂族树脂。据说“ESCOREZ1315”树脂的重均分子量为约2200克/摩尔,软化点在约112℃至约118℃的范围内,并且玻璃化转变温度为约60℃。据说“ESCOREZ 1310LC”树脂具有浅颜色,其重均分子量为约1350克/摩尔,软化点为约95℃,并且玻璃化转变温度为约45℃。据说“ESCOREZ 1304”树脂的重均分子量为约1650克/摩尔,软化点在约97℃至约103℃的范围内,并且玻璃化转变温度为约50℃。
“5300”系列树脂在商业文献中被描述为水白色的脂环族烃树脂,其重均分子量在约370克/摩尔至约460克/摩尔的范围内,软化点在约85℃至约140℃的范围内,并且玻璃化转变温度在约35℃至约85℃的范围内。
“5400”系列树脂在商业文献中被描述为非常浅颜色的脂环族烃树脂,其重均分子量在约400克/摩尔至约430克/摩尔的范围内,软化点在约103℃至约118℃的范围内,并且玻璃化转变温度在约50℃至约65℃的范围内。
“5600”系列树脂在商业文献中被描述为非常浅颜色的芳族改性的脂环族树脂,其中芳族氢原子的百分比基于树脂中所有氢原子的重量计在约6重量%至约12重量%的范围内。另外,据说“5600”系列树脂的重均分子量在约480克/摩尔至约520克/摩尔的范围内,软化点在约87℃至约133℃的范围内,并且玻璃化转变温度在约40℃至约78℃的范围内。
用于任选第四层的其它示例性合适的氢化烃增粘剂可例如以商品名“REGALREZ1085”、“REGALREZ 1094”、“REGALREZ 1126”、“REGALREZ 1139”、“REGALREZ 3102”和“REGALREZ 6108”购自田纳西州金斯波特的伊士曼化工公司(Eastman,Kingsport,TN)。这些树脂在商业文献中被描述为氢化芳族纯单体烃树脂。其重均分子量在约850克/摩尔至约3100克/摩尔的范围内,软化温度在约87℃至约141℃的范围内,并且玻璃化转变温度在约34℃至约84℃的范围内。“REGALEZ 1018”树脂可用在不生成热的应用中。此增粘树脂的重均分子量为约350克/摩尔,软化点为约19℃,并且玻璃化转变温度为约22℃。
其它的示例性氢化烃增粘剂可例如以商品名“WINGTACK 95”和“WINGTACK RWT-7850”购自宾夕法尼亚州埃克斯顿的克雷威利公司(Cray Valley,Exton,PA)。商业文献将这些增粘树脂描述为通过脂族C5单体的阳离子聚合而获得的合成树脂。可以商品名“WINGTACK 95”购得的增粘树脂为浅黄色固体,并且其重均分子量为约1700克/摩尔,软化点为约98℃,并且玻璃化转变温度为约55℃。可以商品名“WINGTACK RWT-7850”购得的增粘树脂为浅黄色固体,并且其重均分子量为约1700克/摩尔,软化点为约102℃,并且玻璃化转变温度为52℃。
其它的示例性氢化烃增粘剂可例如以商品名“PICCOTAC 6095-E”、“PICCOTAC8090-E”、“PICCOTAC 8095”、“PICCOTAC 8595”、“PICCOTAC 9095”和“PICCOTAC 9105”购自伊士曼化工公司(Eastman)。商业文献将这些树脂描述为芳族改性的脂族烃树脂或芳族改性的C5树脂。可以商品名“PICCOTACK 6095-E”购得的增粘剂具有约1700克/摩尔的重均分子量和约98℃的软化点。可以商品名“PICCOTACK 8090-E”购得的增粘剂具有约1900克/摩尔的重均分子量和约92℃的软化点。可以商品名“PICCOTACK 8095”购得的增粘剂具有约2200克/摩尔的重均分子量和约95℃的软化点。可以商品名“PICCOTAC 8595”购得的增粘剂具有约1700克/摩尔的重均分子量和约95℃的软化点。可以商品名“PICCOTAC 9095”购得的增粘剂具有约1900克/摩尔的重均分子量和约94℃的软化点。可以商品名“PICCOTAC 9105”购得的增粘剂具有约3200克/摩尔的重均分子量和约105℃的软化点。
在一些实施方案中,氢化烃增粘剂为氢化聚(环烯烃)聚合物。聚(环烯烃)聚合物通常具有低的湿气渗透性并可通过例如用作增粘剂来影响聚异丁烯树脂的粘合性能。示例性氢化聚(环烯烃)聚合物包括氢化石油树脂;氢化萜烯基树脂(例如,以商品名“CLEARON”购自日本广岛市的安原化学株式会社(Yasuhara Chemical,Hiroshima,Japan),P、M和K级);氢化树脂或氢化酯基树脂(可例如以商品名“FORAL AX”和“FORAL 105”购自特拉华州威明顿市的赫克力士公司(Hercules Inc.,Wilmington,DE),以及以商品名“PENCEL A”、“ESTERGUM H”和“SUPER ESTER A”购自日本大阪的荒川化学工业株式会社(ArakawaChemical Industries Co.,Ltd.,Osaka,Japan));不成比例的树脂或不成比例的酯基树脂(可例如以商品名“PINECRYSTAL”购自荒川化学工业株式会社(Arakawa ChemicalIndustries Co.,Ltd.));氢化二环戊二烯基树脂(例如,通过使C5级分(如戊烯、异戊二烯或胡椒碱)与通过石脑油的热分解产生的1,3-戊二烯共聚获得的氢化C5类石油树脂(可例如以商品名“ESCOREZ 5300”和“ESCOREZ 5400”购自埃克森美孚公司(Exxon ChemicalCo.)以及以商品名“EASTOTAC H”购自伊士曼化工公司(Eastman Chemical Co.));部分氢化芳族改性的二环戊二烯基树脂(可例如以商品名“ESCOREZ 5600”购自埃克森美孚公司(Exxon Chemical Co.));由通过使C9级分(诸如茚、乙烯基甲苯)与通过石脑油的热分解产生的和α-或β-甲基苯乙烯共聚获得的C9型石油树脂的氢化得到的树脂(例如,以商品名“ARCON P”或“ARCON M”购自荒川化学工业株式会社(Arakawa Chemical Industries Co.,Ltd.));以及由于上述C5级分和C9级分的共聚石油树脂的氢化得到的树脂(可例如以商品名“IMARV”购自日本东京的出光石油化学株式会社(Idemitsu Petrochemical Co.,Tokyo,Japan))。在一些实施方案中,氢化聚(环烯烃)为氢化聚(二环戊二烯),其可以为PSA提供优势(例如低湿气渗透性和透明性)。
氢化烃增粘剂通常具有与聚异丁烯的溶解度参数(SP值)相似的溶解度参数并表现出与聚异丁烯良好的相容性(即混溶性),使得可形成透明的膜,其中溶解度参数为用于表征化合物极性的指数。增粘树脂通常为无定形的并具有不大于5000克/摩尔的重均分子量。如果重均分子量大于约5000克/摩尔,则与聚异丁烯材料的相容性可能降低、粘性可能降低、或者这两者都降低。该分子量常常不大于4000克/摩尔(在一些实施方案中不大于2500克/摩尔、2000克/摩尔、1500克/摩尔、1000克/摩尔或甚至不大于500克/摩尔;在一些实施方案中,该分子量在200克/摩尔至5000克/摩尔、200克/摩尔至4000克/摩尔、200克/摩尔至2000克/摩尔或甚至200克/摩尔至1000克/摩尔的范围内)。
在一些实施方案中,本文所述的聚合物多层膜还包括至少一个连续(即,不包含从一个主表面延伸至另一个主表面的开孔)层。在一些实施方案中,与表现出股线和连接区域的无规网络的层相邻的连续层从股线和连接区域的无规网络变得纹理化(例如,连续层可至少部分地适形于股线和连接区域的无规网络的纹理)。示例性连续层包含以下中的至少一种:聚烯烃材料(例如,聚丙烯和/或聚乙烯)、改性聚烯烃材料、聚氯乙烯、聚碳酸酯、聚苯乙烯、聚酯(包括共聚酯)、聚交酯、聚偏二氟乙烯、(甲基)丙烯酸(例如,聚甲基丙烯酸甲酯)、氨基甲酸酯、丙烯酸氨基甲酸酯、乙烯乙酸乙烯酯共聚物、丙烯酸酯改性乙烯乙酸乙烯酯聚合物、乙烯丙烯酸共聚物、尼龙、工程聚合物(聚酮和/或聚甲基戊烷)、或弹性体(例如,天然橡胶;合成橡胶;含有异戊二烯、丁二烯、或乙烯(丁烯)嵌段的苯乙烯嵌段共聚物;茂金属催化的聚烯烃、聚氨酯;或聚二有机硅氧烷)。
连续层可通过本领域已知的技术(诸如包含连续层组合物的组分的可挤出组合物的热熔融挤出)提供。用于制作可挤出的连续层的示例性方法例如在俄亥俄州辛辛那提的翰泽尔/加德纳出版有限公司(Hanser/Gardner Publications,Inc.,Cincinnati,OH)于1993年出版的Progelhof,R.C.和Throne,J.L.的“Polymer Engineering Principles(聚合物工程原理)”中有所描述,其公开内容以引用方式并入本文。
另选地,例如,可将至少一个层挤出为单独的片材并层压在一起。在一些实施方案中,基底可有利地组合各层中若干树脂的最佳性能,同时使最昂贵树脂的使用最小化,从而导致价值较高且成本较低的图像接受介质。例如,基底层可由具有一般性低成本的树脂制成,这些树脂可被选择来向多层膜提供具体期望的物理性能。这些性能可包括尺寸稳定性、抗撕裂性、适形性、弹性体性能、模切性、刚度和耐热性。
在一些实施方案中,连续层为表层。在一些实施方案中,表现出股线和连接区域的无规网络的至少一个层被设置在两个连续层之间。在一些实施方案中,连续层被设置在表现出股线和连接区域的无规网络的两个层之间。
在一些实施方案中,第一连续层不含压敏粘合剂,并且表现出股线和连接区域的无规网络的层包含压敏粘合剂。在一些实施方案中,第一连续层包含第一压敏粘合剂,并且表现出股线和连接区域的无规网络的层包含第二压敏粘合剂。
在包含表现出股线和连接区域的无规网络的多于一个层的一些实施方案中,至少两个此类层表现出不同的股线和连接区域的无规网络。
在包含表现出股线和连接区域的无规网络的多于一个层的一些实施方案中,表现出股线和连接区域的无规网络的一个层不含压敏粘合剂,并且表现出股线和连接区域的无规网络的另一个层包含压敏粘合剂。
在包含表现出股线和连接区域的无规网络的多于一个层的一些实施方案中,表现出股线和连接区域的无规网络的一个层包含第一压敏粘合剂,并且表现出股线和连接区域的无规网络的另一个层包含不同的第二压敏粘合剂。
在一些实施方案中,本文所述的聚合物多层膜还包括第二连续层,其中表现出股线和连接区域的无规网络的第一层设置在第一连续层和第二连续层之间。
在一些实施方案中,本文所述的聚合物多层膜具有在1微米至1000微米的范围内(在一些实施方案中,在25微米至500微米、50米至250微米、或甚至2微米至10微米的范围内)的厚度。
在一些实施方案中,本文所述的聚合物多层膜具有纵向和横向,其中聚合物多层膜在横向上是有弹性的。
在一些实施方案中,本文所述的聚合物多层膜还包括至少一个衬件。例如,衬件的主表面附接到聚合物多层膜的第一主表面或第二主表面中的任一个。在一些实施方案中,聚合物多层膜的每个主表面具有附接到该主表面的衬件。在一些实施方案中,衬件包括表现出股线和连接区域的无规网络的聚合物多层膜。在一些实施方案中,衬件具有表现出股线和连接区域的无规网络的主表面。在一些实施方案中,聚合物多层膜在衬件的主表面上具有粘合剂(例如,压敏粘合剂)层。对于具有表现出股线和连接区域的无规网络的主表面的衬件,衬件的主表面上的粘合剂的主表面具有衬件的主表面的反转面。在一些实施方案中,聚合物多层膜的附接到衬件的主表面的第一主表面或第二主表面是粘合剂(例如,压敏粘合剂)表面。对于具有表现出股线和连接区域的无规网络的主表面的衬件,聚合物多层膜的附接到衬件的主表面具有衬件的主表面的反转面。
本文所述的聚合物多层膜的实施方案可用于例如带材和图形制品(例如,图形膜)。“图形膜”是吸收具有可见或近红外范围内的波长的至少一些光并且反射其中反射光包含一些图形内容的可见范围内的至少一些光的膜。图形内容可包括图案、图像或其它视觉标记。图形膜可为印刷膜,或图形可通过除印刷之外的方式形成。例如,图形膜可为具有图案化布置方式的孔的打孔反射膜。图形也可通过压印形成。在一些实施方案中,图形膜是部分透射图形膜(例如,在背光源的标牌(例如,背光源的交通标志)中使用)。广告和促销展示通常包括出现在结构表面(诸如卡车侧面和遮篷)上或作为横幅自由悬挂的图形图像。为了准备展示,可在背胶的图像接受介质(有时称为图形标记膜)上形成图像,该图像接受介质然后被粘附到期望的基底。尽管图形展示可旨在用于5年或更长时间的长期安装,但它通常是相对短期(3个月至1年)的室外安装。就短期展示而言,图像接受介质有利地是低成本、耐候性、耐用的图形标记膜,该图形标记膜具有良好的印刷适性和油墨和/或调色剂的粘附性,该图形标记膜容易地施加到表面以及从表面移除。
示例性实施方案
1.一种聚合物多层膜,该聚合物多层膜包括其余表现出股线(在一些实施方案中,长形股线)和连接区域的无规网络(该无规网络具有第一光密度并且该连接区域具有第二光密度,其中该第一光密度大于该第二光密度;在这些连接区域中的至少一些区域中存在开孔(即,没有通孔))的聚合物层,该聚合物层是与其余聚合物多层膜可分离的。
2.根据示例性实施方案1所述的聚合物多层膜,该聚合物多层膜还包括表现出股线和连接区域的无规网络的至少一个附加聚合物层(在一些实施方案中,包括各自表现出股线和连接区域的无规网络的至少2个、3个、4个、5个、6个或甚至至少7个附加聚合物层)。在一些实施方案中,所有的层或这些层中的一些与表现出股线和连接区域的无规网络的另一个层相邻。在一些实施方案中,各自表现出股线和连接区域的无规网络的多个附加聚合物层中的一个包含压敏粘合剂,其中的每一个都可以与第一压敏粘合剂相同或不同,或者彼此相同或不同。
3.根据示例性实施方案1或2所述的聚合物多层膜,其中表现出股线和连接区域的无规网络的层独立地包含以下中的至少一种:聚烯烃材料(例如,聚丙烯和/或聚乙烯)、改性聚烯烃材料、聚氯乙烯、聚碳酸酯、聚苯乙烯、聚酯(包括共聚酯)、聚交酯、聚偏二氟乙烯、(甲基)丙烯酸类(例如,聚甲基丙烯酸甲酯)、氨基甲酸酯、丙烯酸氨基甲酸酯、乙烯-乙酸乙烯酯共聚物、丙烯酸酯改性乙烯-乙酸乙烯酯聚合物、乙烯-丙烯酸共聚物、尼龙、工程聚合物(例如,聚酮和/或聚甲基戊烷)、或弹性体(例如,天然橡胶;合成橡胶;含有异戊二烯、丁二烯、或乙烯(丁烯)嵌段的苯乙烯嵌段共聚物;茂金属催化的聚烯烃、聚氨酯;或聚二有机硅氧烷)。
4.根据任意前述示例性实施方案所述的聚合物多层膜,其中表现出股线和连接区域的无规网络的至少一个层具有至少1%的开孔孔隙度(在一些实施方案中,为至少5%、10%、15%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、或甚至至少80%;在一些实施方案中,在1%至80%的范围内)。
5.根据任意前述示例性实施方案所述的聚合物多层膜,其中该表现出股线和连接区域的无规网络的层基本上不含压敏粘合剂。
6.根据示例性实施方案1至4中的任一项所述的聚合物多层膜,其中该表现出股线和连接区域的无规网络的层包含压敏粘合剂。
7.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包括第一连续层。
8.根据示例性实施方案7所述的聚合物多层膜,其中该第一连续层不含压敏粘合剂,并且其中该表现出股线和连接区域的无规网络的层包含压敏粘合剂。
9.根据示例性实施方案7所述的聚合物多层膜,其中该第一连续层包含第一压敏粘合剂,并且其中该表现出股线和连接区域的无规网络的层包含第二压敏粘合剂。
10.根据示例性实施方案9所述的聚合物多层膜,其中该第一压敏粘合剂具有比该第二压敏粘合剂更大的粘性。
11.根据示例性实施方案7所述的聚合物多层膜,其中该第一压敏粘合剂具有比该第二压敏粘合剂更小的粘性。
12.根据示例性实施方案7所述的聚合物多层膜,其中该第一连续层包含以下中的至少一种:聚烯烃材料(例如,聚丙烯和/或聚乙烯)、改性聚烯烃材料、聚氯乙烯、聚碳酸酯、聚苯乙烯、聚酯(包括共聚酯)、聚交酯、聚偏二氟乙烯、(甲基)丙烯酸(例如,聚甲基丙烯酸甲酯)、氨基甲酸酯、丙烯酸氨基甲酸酯、乙烯乙酸乙烯酯共聚物、丙烯酸酯改性乙烯乙酸乙烯酯聚合物、乙烯丙烯酸共聚物、尼龙、工程聚合物(聚酮和/或聚甲基戊烷)、或弹性体(例如,天然橡胶;合成橡胶;含有异戊二烯、丁二烯、或乙烯(丁烯)嵌段的苯乙烯嵌段共聚物;茂金属催化的聚烯烃、聚氨酯;或聚二有机硅氧烷)。
13.根据示例性实施方案7或12所述的聚合物多层膜,其中该第一连续层为表层。
14.根据示例性实施方案7、12或13中的任一项所述的聚合物多层膜,该聚合物多层膜还包括表现出股线和连接区域的无规网络的第二层。
15.根据示例性实施方案14所述的聚合物多层膜,其中表现出股线和连接区域的无规网络的该第二层具有与包含股线和连接区域的无规网络的该第一层不同的股线和连接区域的无规网络。
16.根据示例性实施方案15所述的聚合物多层膜,其中表现出股线和连接区域的无规网络的该第一层不含压敏粘合剂,并且其中表现出股线和连接区域的无规网络的该第二层包含压敏粘合剂。
17.根据示例性实施方案15所述的聚合物多层膜,其中表现出股线和连接区域的无规网络的该第一层包含第一压敏粘合剂,并且其中表现出股线和连接区域的无规网络的该第二层包含不同的第二压敏粘合剂。
18.根据示例性实施方案15所述的聚合物多层膜,其中该第一压敏粘合剂具有比该第二压敏粘合剂更大的粘性。
19.根据示例性实施方案14至18中的任一项所述的聚合物多层膜,其中该第一连续层设置在表现出股线和连接区域的无规网络的该第一层和该第二层之间。
20.根据示例性实施方案7至18中的任一项所述的聚合物多层膜,该聚合物多层膜还包括第二连续层,其中表现出股线和连接区域的无规网络的该第一层设置在该第一连续层和该第二连续层之间。
21.根据任意前述示例性实施方案所述的聚合物多层膜,其中该聚合物多层膜的该第一主表面或该第二主表面中的至少一者(在一些实施方案中,该第一主表面和该第二主表面中的每一者)表现出股线和连接区域的无规网络。
22.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜具有在1微米至1000微米的范围内(在一些实施方案中,在25微米至500微米、50米至250微米、或甚至2微米至10微米的范围内)的厚度。
23.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包括模头或颜料(例如,赋予颜色,诸如白色、黄色、绿色、蓝色、红色、橙色、棕色、黑色等)中的至少一者。
24.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包含至少一种防静电材料。
25.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包含油墨吸收材料或油漆吸收材料中的至少一种。
26.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包含金属(例如,铝、青铜、不锈钢、锌、铁、锡、银、金和/或钛)颗粒。
27.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包含防粘剂。
28.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包含耐磨材料。
29.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包括滑爽剂或防粘连剂中的至少一种。
30.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包含受阻胺光稳定剂(HALS)。
31.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包含UV稳定剂。
32.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包含亲水性材料。
33.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜具有纵向和横向,其中该聚合物多层膜在该横向上是有弹性的。
34.根据任意前述示例性实施方案所述的聚合物多层膜,该聚合物多层膜还包括具有主表面的衬件,该主表面附接到该聚合物多层膜的该第一主表面或该第二主表面中的任一个。在一些实施方案中,聚合物多层膜的每个主表面具有附接到其的衬件。
35.根据示例性实施方案32所述的聚合物多层膜,其中该衬件包括表现出股线和连接区域的无规网络的聚合物多层膜。
36.根据示例性实施方案34或35所述的聚合物多层膜,其中该衬件具有表现出股线和连接区域的无规网络的主表面。
37.根据示例性实施方案34至36中的任一项所述的聚合物多层膜,该聚合物多层膜在该衬件的主表面上具有粘合剂(例如,压敏粘合剂)层。对于具有表现出股线和连接区域的无规网络的主表面的衬件,衬件的主表面上的粘合剂的主表面具有衬件的主表面的反转面。
38.根据示例性实施方案34至36中的任一项所述的聚合物多层膜,其中该聚合物多层膜的附接到该衬件的该主表面的第一主表面或第二主表面为粘合剂(例如,压敏粘合剂)表面。对于具有表现出股线和连接区域的无规网络的主表面的衬件,聚合物多层膜的附接到衬件的主表面具有衬件的主表面的反转面。
39.一种图形制品,该图形制品包括根据任意前述示例性实施方案所述的聚合物多层膜。
40.一种带材(例如,管带),该带材包括根据示例性实施方案1至38中的任一项所述的聚合物多层膜。
以下实施例进一步说明了本发明的优点和实施方案,但是这些实施例中所提到的具体材料及其量以及其它条件和细节均不应被解释为是对本发明的不当限制。除非另外指明,否则所有份数和百分比均按重量计。
实施例1
使用七层环形堆叠模头(以商品名“COEX 7-LAYER”(LF-400型)获得自泰国北榄府的Labtech Engineering公司(Labtech Engineering,Samut Prakan,Thailand))生产七层膜,这使用了如图3和图3A所示的设备,不同的是仅有七个堆叠的模板。到模头的气流被手动控制以实现约2:1的吹胀比。气泡随后在模头上方约3米(10英尺)塌缩并卷起。馈送材料由具有约30:1的长径比的7个独立的20mm直径的挤出机供应。
第一挤出机用于将低密度聚乙烯(以商品名“PETROTHENE NA217000 5.6 MFI”获得自得克萨斯州休斯顿的利安德巴塞尔公司(LyondellBasell,Houston,TX))熔融并挤出到环形叠堆模头的内部通道中。熔融温度保持在180℃。第二挤出机、第三挤出机、第四挤出机、第五挤出机和第六挤出机用于将相同的树脂馈送到第一树脂的后续外部层中。第七挤出机用于将含有96%的热塑性聚氨酯(以商品名“ESTANE CLR-87A-V”获得自俄亥俄州克利夫兰的路博润先进材料公司(Lubrizol Advanced Materials,Cleveland,OH))与4%的化学发泡剂(以商品名“ECOCELL H”获得自新泽西州罗卡韦的Polyfil公司(Polyfil Corp.,Rockaway,NJ))的共混物馈送至环形叠堆模头的外侧层。保持215℃的熔融温度。模头保持在180℃。针对每个挤出机,使用每分钟30转的螺杆转速。表现出股线和连接区域的无规网络的所得的聚氨酯膜能够与其余聚乙烯膜分离。
在图4和图4A中示出了所得的聚合物多层膜的图像。
实施例2
如实施例1中所述来制备聚合物多层膜,不同的是第一挤出机、第二挤出机、第三挤出机、第四挤出机和第五挤出机仅含有低密度聚乙烯,第六挤出机含有无定形的聚乳酸(以商品名“INGEO 4060D”获得自明尼苏达州明尼通卡的NatureWorks有限责任公司(NatureWorks LLC,Minnetonka,MN)),并且第七挤出机含有相同化学发泡剂与苯乙烯乙烯丁烯苯乙烯(SEBS)共聚物(以商品名“KRATON G 1657”获得自俄亥俄州埃文莱克的普利万公司(PolyOne,Avon Lake,OH))的共混物。表现出股线和连接区域的无规网络的所得膜能够与其余聚乳酸膜和聚乙烯膜分离。在图5(参见股线503和连接区域504的无规网络)和图5A中示出了所得聚合物多层膜的图像。
在不脱离本发明的范围和实质的情况下,本公开的可预知的变型和更改对本领域的技术人员来说将显而易见。本发明不应受限于本申请中为了说明目的所示出的实施方案。
Claims (13)
1.一种聚合物多层膜,所述聚合物多层膜包括表现出股线和连接区域的无规网络的层,所述层是与其余聚合物多层膜可分离的。
2.根据权利要求1所述的聚合物多层膜,所述聚合物多层膜还包括表现出股线和连接区域的无规网络的至少一个附加聚合物层。
3.根据任意前述权利要求所述的聚合物多层膜,其中表现出股线和连接区域的无规网络的至少一个聚合物层具有至少20%的开孔孔隙度。
4.根据任意前述权利要求所述的聚合物多层膜,所述聚合物多层膜还包括第一连续层。
5.根据权利要求4所述的聚合物多层膜,其中所述第一连续层不含压敏粘合剂,并且其中所述表现出股线和连接区域的无规网络的层包含压敏粘合剂。
6.根据权利要求5所述的聚合物多层膜,其中所述第一连续层包含第一压敏粘合剂,并且其中所述表现出股线和连接区域的无规网络的层包含第二压敏粘合剂。
7.根据权利要求6所述的聚合物多层膜,其中所述第一连续层为表层。
8.根据任意前述权利要求所述的聚合物多层膜,其中所述聚合物多层膜的第一主表面或第二主表面中的至少一者表现出股线和连接区域的无规网络。
9.根据任意前述权利要求所述的聚合物多层膜,所述聚合物多层膜具有纵向和横向,其中所述聚合物多层膜在所述横向上是有弹性的。
10.根据任意前述权利要求所述的聚合物多层膜,所述聚合物多层膜还包括具有主表面的衬件,所述主表面附接到所述聚合物多层膜的所述第一主表面或所述第二主表面中的任一个。
11.根据权利要求10所述的聚合物多层膜,其中所述衬件具有表现出股线和连接区域的无规网络的主表面。
12.一种图形制品,所述图形制品包括根据任意前述权利要求所述的聚合物多层膜。
13.一种带材,所述带材包括根据权利要求1至11中的任一项所述的聚合物多层膜。
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2017
- 2017-12-04 EP EP17822101.6A patent/EP3551456A1/en not_active Withdrawn
- 2017-12-04 WO PCT/US2017/064398 patent/WO2018106558A1/en unknown
- 2017-12-04 JP JP2019530825A patent/JP7228513B2/ja active Active
- 2017-12-04 CN CN201780076134.3A patent/CN110049871B/zh active Active
- 2017-12-04 US US16/463,759 patent/US10953623B2/en active Active
Patent Citations (5)
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US20010034173A1 (en) * | 1998-04-29 | 2001-10-25 | Dieter Zimmermann | Painter's masking tape and its use |
US20090186183A1 (en) * | 2008-01-22 | 2009-07-23 | Tesa Ag | Liner and also the use thereof |
JP2013124279A (ja) * | 2011-12-14 | 2013-06-24 | Nitto Denko Corp | 保護材 |
WO2015200743A1 (en) * | 2014-06-26 | 2015-12-30 | Dow Global Technologies Llc | Blown films with improved toughness |
US20160059515A1 (en) * | 2014-09-02 | 2016-03-03 | Mondi Consumer Packaging Technologies Gmbh | Coextruded polyethylene film |
Also Published As
Publication number | Publication date |
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JP2020500752A (ja) | 2020-01-16 |
US10953623B2 (en) | 2021-03-23 |
EP3551456A1 (en) | 2019-10-16 |
WO2018106558A1 (en) | 2018-06-14 |
CN110049871B (zh) | 2021-05-14 |
US20190389173A1 (en) | 2019-12-26 |
JP7228513B2 (ja) | 2023-02-24 |
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