CN1398339A - 混有干燥剂的聚合物 - Google Patents
混有干燥剂的聚合物 Download PDFInfo
- Publication number
- CN1398339A CN1398339A CN99808743.2A CN99808743A CN1398339A CN 1398339 A CN1398339 A CN 1398339A CN 99808743 A CN99808743 A CN 99808743A CN 1398339 A CN1398339 A CN 1398339A
- Authority
- CN
- China
- Prior art keywords
- desiccant
- poly
- mer
- container
- duct
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
本发明包括制造混有干燥剂、吸收水汽的聚合物的方法以及制得的结构。通常采用加热使聚合物(25)呈熔融状态,然后使孔道形成剂(35)共混在聚合物中并发生反应,以使孔道形成剂分布在产物内。然后将干燥剂(30)共混入产物中使干燥剂分布在产物内。将产物固化以使孔道形成剂在产物中形成让水汽通过、进入产物中与混在产物中的干燥剂相接触的通道(45)。固化产物可用来成形密闭容器的塞子型嵌件和内衬,或者可成形为任何形状的制品。
Description
所属技术领域
本发明一般涉及在包装中使用干燥剂;本发明尤其涉及含干燥剂的包装材料。再更具体地说,本发明涉及混有能在聚合物中反应的干燥剂的聚合物。本发明还涉及利用一种方法使处于聚合物结构内部的干燥剂显露在聚合物本体所处外部湿气中的、混有干燥剂的聚合物。本发明混有干燥剂的聚合物特别适用于制造包装需要低湿环境的物品的容器和包装材料。
发明背景
有许多应优选在尽可能没有水汽的环境中贮存、装运和/或使用的物品。因此,已经认识到希望有能吸收存在于容器或包装件中过量水汽的容器和/或包装件。对于药效会因水分而受损的药物的装运和贮存来说,采用吸湿性容器是理想的。药物最初放置在密封无水汽的容器中通常是可人为控制的。此外,保存药物还应选择透湿性低的容器。因此,药物通常在被送到最终使用者前是防潮的,然而一旦消费者得到药物,为了取药就需重复打开和闭上容器。在每次开闭容器时,携带水汽的空气往往被引入容器中,而当容器关闭时水汽就被密封在容器中了。除非将大气中或容器上部空间的水汽除去,否则水汽就会被药品吸收。为此,在装药品的容器中与药品一起装入一个干燥剂单元,这是众所周知的。
在另一个实施例中,电子元件可能需要低湿条件才能保持最佳性能。这些元件可密封在容器中,但必需将最初封入容器中的过多水汽除去。此外,盖子可能不是完全密闭隔潮的,因而水汽还有可能渗入容器中。这种水汽也必须被阻隔开而不与所装电子元件相接触。为此,重要的是,要在盖内放置于燥剂来吸收和阻隔残留水汽。由于需隔潮的元件很精密,所以不能使用会污染和损害元件性能的“粉尘性”干燥剂,这是很重要的。因此,已经认识到将干燥剂放在这类容器的内部空间,而同时将元件屏蔽起来使之实际上不能与干燥物质(包括可能从干燥剂产生的干燥剂粉尘)相接触是有利的。
在其它情况中,置于容器中或密封在包装件中待装运和/或贮存的物品中也可能会释放出水汽。这类物品的主要实例是在装运和贮存时会释放出水汽的食品。对经密封、基本上不透水汽的容器来说,物品中释放出来的水汽会保留在容器内。如果水汽不除去的话,释放出来的水汽会对释放水汽的物品产生有害影响。业已发现,某些食品在制造和包装后的第一个48小时内,会释放出大量水汽。这些水汽会一直保留到被除去。如果释放出来的水汽不及时除去的话,会使食品降级至不能销售的程度。对这种情况来说,可将干燥剂与物品一起包封在容器中以连续地吸收释放出来的水汽直到容器被开封。这样,贮存物品的周围就能保持相对干燥的环境。
以前已经认识到需要从密封的容器内除去水汽。为达到这一目标早期所做的工作包括将装有干燥剂的织物口袋或类似口袋与要装运或贮存的物品相混合,一起装在容器内。然而,当干燥剂从口袋中漏出并与消费物品掺和在一起时,会出现影响消费者的问题。如果在打开包装时没有仔细、周密地操作的话,就不能将干燥剂与所消费物品相分开,从而使人们在不知不觉中摄入了干燥剂而受到伤害。
几位发明者已经取得了专利:这些专利包括借助各种包装形态的干燥剂吸收水汽的结构和方法。最基本的实施例已公开在Dolan等人的美国专利3326810(题为干燥剂包装袋,1967年6月20日授权)。该专利公开了一种非粉尘性硅胶干燥剂袋。硅胶是装在由两片尼龙制网状织物粘合而成的口袋中的。另一种熟知的方法是将干燥剂置于容器内部的一个部分敞开的特殊小侧室中。这类发明的实例已公开在Sacherer等人的美国专利4834234(题为装试条的容器,1989年5月30日授权)。Sacherer为放置分析体液用的试验试条的容器上盖部设置了一个干燥剂小盒,该干燥剂小盒是为透水蒸汽的纸板盘所覆盖的,从而使该小盒与容器内部分隔开。类似的实例已公开在Jackisch等人的美国专利5114003(题为瓶底有干燥剂的药片瓶,1992年5月19日授权)。Jackisch公开了一种用以保证容器底部内侧干燥的干燥剂罐。装有干燥剂的干燥剂罐最初是密封的以防止吸收水汽,在使用前将干燥剂罐刺破,进入容器中的水汽就会扩散至干燥剂而被吸收。
在另一个实例中,提供了制造成本高、置于包装件中的独立的干燥剂胶囊。Cullen等人的美国专利4783206(题为吸收剂筒,1988年11月8日授权)公开了一种以聚乙烯、聚酯或聚丙烯制的呈细长形的空心圆筒体,干燥剂置于该圆筒内以使干燥剂与置于普通容器中的物品保持隔离状态。采用筒形结构是为了使水汽只通过由纺粘型聚烯烃制的管端盖帽,而不会通过刚性的高密度塑料的圆筒形侧壁。干燥剂胶囊已公开在Yard的美国专利2638179(1953年5月12日授权)中。Yard的干燥剂胶囊包含包裹在透水汽外皮内的干燥剂,容纳在胶囊中的干燥剂从外皮吸收水汽,而不是直接从胶囊外的大气中吸收水汽。明胶胶囊可用作控制干燥剂吸收水汽速率的调节剂。
另一个是干燥剂与聚合物相混合制成的层合塑料片的实例,此片中的不透氧内层要求避免受到会损害该内层隔氧特性的水汽的影响。这种以层合结构利用干燥剂的实例可在已转让给American CanCompany of Greenwich(Connecticut)和Kuraray Co.Ltd.ofKurashiki(日本)的美国专利中查到。这些美国专利包括4407897、4425410、4464443、4770944和4792484。在这几个专利的公开内容中,层合结构具有一层由如乙烯-乙烯醇共聚物(EVOH)这类聚合物制造的、用作隔氧层的内层,对于每一种情况,EVOH是只用来作为隔氧层的。只要EVOH层的含水量保持在某一水平以下,这些EVOH层就能作为隔氧层。对于这些专利中所述的至少一种用途来说,层状包装材料可用来包装那些必须经杀菌锅杀菌的食品,此时,食品与包装材料一起进行蒸汽处理。在进行蒸汽处理过程中,通常由聚丙烯和聚乙烯制的、在低温下不透水汽的保护外层,在杀菌锅的高温下则可让水汽透过。但含水量高于一定水平时,EVOH层就会丧失其隔氧特性。因此,要向邻接EVOH层的粘合剂层添加干燥剂,以控制层合片材内阻氧层内的含水量,使隔氧层可保持其隔氧性能。这些专利发明的唯一目的是使层合结构中的EVOH内层保持较低的含水量以保证其作为阻氧层的隔氧性能。
与聚合物粘合材料相混合的干燥剂实例可在Degen等人的美国专利4665050(题为含固定的无机吸着剂微粒的自承结构及其制备方法,1987年5月12日授权)中查到。根据说明,吸着剂微粒是混入软化的、但未熔融的热塑性材料例如聚乙烯或聚丙烯中的。只将聚合物介质软化,可防止吸着剂材料被“掩蔽”,即吸着材料的外表部分必须显露、不能被周围的聚合物所覆盖。按这种模式,水汽可被输送到吸着材料的未被粘结聚合物所覆盖的那些部位。由此说明了,聚合物应该只软化到稍微发粘的程度,而不能成为可流动的粘流状。
吸湿性物质与热塑性树脂的混合物已公开在Shigeta等人的美国专利5078909(题为吸湿剂组合物和模制品,1992年1月7日授权)。其中,涉及的热塑性树脂包括聚乙烯、聚丙烯以及其它可用来配制该组合物的热塑性树脂。为了得到干燥剂产生的吸收效果,需要采用各种吸湿剂。
将干燥剂直接混入塑料和橡胶中也是已知的方法。这类混入方法的实例可在O’connor等人的美国专利3245946(题为橡胶与塑料的配方和加工,1966年4月12日授权)中查到。其中,在制造过程中,向橡胶、塑料和树脂配料中混入干燥剂的方法已被利用来吸纳由这些材料在制造过程中所产生的水汽,否则这种水汽会对制得的材料产生不利的影响。
柔性的干燥剂本体已公开在Taylor的美国专利4013566(1977年3月22日授权)中。其中,干燥剂材料均匀地分布并粘结在透水汽的脂族环氧聚合物基体上。其中,已经认识到聚丙烯袋不适宜作容器材料,因为在使用期间由于聚丙烯袋的熔化或热塑性质,存在潜在的损耗问题。
在本发明之前,关于在整个混有干燥剂的聚合物中形成孔道是未知的。本发明已对由通常用作阻湿层的固态、刚性态的聚合物构成的结构进行了研制,并根据本发明制造出了其间混有干燥剂的、能吸收聚合物之外水汽的聚合物结构。
发明概述
如前所述,聚合物基质中混入干燥剂的主要缺点是,在这种结构中的单个干燥剂微粒周围形成了不透水汽的聚合物包膜。本发明公开了一种在整个聚合物基质中形成用于沟通混入的干燥剂与处于塑料本体外适当区域的通道,从而使位于塑料结构外的水汽向位于塑料结构内部的干燥剂微粒迁移的方法和形成的结构。此外,用来通过水汽的这些孔道或缝隙可充填吸收、输送水汽的速率高于干燥剂的试剂或化合物。输送剂起着沟通塑料本体表面与位于塑料结构内的干燥剂微粒的桥梁作用。
附图的简要说明
图1是由孔道、混有干燥剂的聚合物构成的塞子、嵌件或小片的透视图,所示的在塞子外表面的孔道开口的尺寸是放大了的。
图2是由与孔道形成剂反应并共混有干燥剂的聚合物成形的固化塞子的放大剖面图。
图3是由与孔道形成剂反应并共混有干燥剂的聚合物成形的固化塞子的放大了的部分剖面图。
图4是由与孔道形成剂和极性干燥剂经共混、反应的聚合物成形的固化塞子的放大了的部分剖面图。
图5是一种容器的放大了的部分剖面图,该容器是由作为隔潮层的聚合物构成的,并在容器底部置有一个混有干燥剂的塞形嵌件。
图6是一种容器的放大了的部分剖面图,该容器是由作为隔潮层的聚合物构成的,并在容器底部共模塑有一个混有干燥剂的塞子。
图7是一种容器的放大了的部分剖面图,该容器是由作为隔潮层的聚合物构成的,并在容器内壁置有一个混有干燥剂的内衬嵌件。
图8是一种容器的放大了的部分剖面图,该容器是由作为隔潮层的聚合物构成的,并在容器内壁共模塑有混有干燥剂的内衬。
图9是一种与由起隔潮作用的聚合物构成的阻隔片层相邻配置的干燥片材或区域的放大了的剖面图。
图10是一种干燥片材或干燥区域的放大了的剖面图,这种片材的内侧已共模塑了阻隔片层,所以该产品是整体模塑在一起的,是均一的层合结构。
连同这些已公开的优点和改进,本发明的其它目的和优点都可通过以下的说明、附图而获知。附图是本说明书的一部分,包括了本发明的例证性实施方案,并说明了本发明的目的和特征。
发明的详细说明
根据需要,本文公开了本发明的详细实施方案,但公开的实施方案只是本发明具体化的许多方案中的若干示例,这是不言而喻。附图是不必按比例绘制的,某些特征可以放大以显示出具体组件的细节。因此,不能把本文公开的特定的结构性和功能性的细节当作一种限制,只是作为权利要求书的基础和作为向采用本发明的技术人员提供的代表性说明的基础。
业已发现,本文称为孔道形成剂的某些化合物可与用来成形一定形状制品的聚合物基质发生反应。实际上,混有孔道形成剂的、随后发生反应的聚合物基质包括:例如任何一种酸酐或胺或酸或氰酸酯或异氰酸酯或羟基官能化的聚合物。
在一个实施方案中,在孔道形成剂与聚合物发生反应前,在聚合物基质处于熔融状态或处于熔融状态前,将干燥剂和孔道形成剂添加到聚合物中去,使干燥剂与孔道形成剂共混并与聚合物基质充分地混合,以保证所有物料在形成熔融相之前充分地混合。例如,这一技术适用于干燥剂、孔道形成剂和聚合物基质都是粉料的情况。
在另一实施方案中,孔道形成剂与聚合物是在添加干燥剂前进行混合、反应的。孔道形成剂既可在聚合物熔融前也可在聚合物处于熔融状态后添加。例如,干燥剂可在塑性材料热成形为片材的过程中添加到已经与孔道形成剂反应的聚合物基质中。
在这些物料充分共混、反应后,孔道形成剂在整个聚合物中形成了作为迁移湿气的通道的缝隙或孔道。适用的孔道形成剂包括聚二醇如聚乙二醇,乙烯-乙烯醇共聚物(EVOH),聚乙烯醇(PVOH),甘油多胺,聚氨基甲酸酯以及包括聚丙烯酸或聚甲基丙烯酸在内的聚羧酸。在本发明的一个实施方案中,当采用的聚合物基质是含酸和/或酸酐基团的聚合物时,孔道形成剂应选自包括聚二醇、多元醇或多胺的孔道形成剂。在本发明的另一个实施方案中,当采用的聚合物基质是含胺基团的聚合物时,孔道形成剂应选自包括聚羧酸的孔道形成剂。
通过形成本发明组合物,聚合物基质与孔道形成剂不会分离为处在不同水平或相态,即一种物质在另一物质之上的情况,而孔道形成剂形成的缝隙一直伸入到聚合物基质内部,从而形成了通向聚合物内部的孔道或通路。孔道在聚合物结构表面是开口的,从而为水汽进入聚合物基质内部提供了入口。
各种各样的干燥剂在技术上是众所周知的,并可用于本发明中。一般来说,可用于本发明的干燥剂主要有三类。
第一类包括能形成含水结晶的化合物。此类干燥剂的实例是往往会吸收水或水汽而形成稳定盐的无水盐。在与水汽发生反应的过程中,形成了稳定的化合物,此时水汽就被保留在化合物中,从而阻止了水汽的释放。
第二类干燥剂化合物是那些被认为是有反应活性的化合物。这些化合物通常与水或水汽经化学反应并形成水结合其中的新化合物。这些新形成的化合物通常在低温下是不可逆的,需要足够的能量才能再生,从而可再作为干燥剂使用。这些反应活性干燥剂主要用于溶剂干燥和作为必须保持在低湿状态下的聚合物的添加剂。这些反应活性类化合物特别适用的一种用途是在如上所述的含EVOH的多层片材中的应用,其中EVOH层是层合在两层一般不透水汽材料(如聚乙烯或聚丙烯)的保护层之间的。如上所述,这类片材或包装材料可用来包装后续还要经蒸煮进行杀菌的食品,其中经包装的食品是直接受到热蒸汽杀菌的。在高温下,外层是允许水汽通过的,并兼有EVOH内层的隔氧效能。由于混有反应活性干燥剂,水汽就被干燥剂吸收,并被保留在干燥剂中而远离EVOH层,因而EVOH层能保持隔氧特性。
第三类干燥剂是通过物理吸收来达到吸收水汽的。吸收作用是由干燥剂微粒的毛细管力推动水汽通过毛细管而产生的。毛细管的孔径及毛细管的密度决定了该干燥剂的吸收性能。这类物理吸收干燥剂的实例包括分子筛、硅胶、白土及淀粉。由于这类物理吸收干燥剂是惰性的又是非水溶性的,因此它们是许多用途中的首选。连同其它理由,尤其是这些无害的特性特别适合于可包封在由混有干燥剂的聚合物制的容器中或者至少显露在这种容器中的食品和药品。然而,如上所述,三类干燥剂中任何一类都可用于制造本发明混有干燥剂的聚合物的聚合物基质中。适用的干燥剂包括硅胶、分子筛及包括蒙脱土在内的天然存在的白土。同样,所有三类干燥剂都与被采用的大多数孔道形成剂是相容的。
在一个实施方案中,干燥剂选自能使干燥剂与孔道形成剂间产生亲和力的极性干燥剂。这种极性干燥剂的实例是对孔道形成剂比对聚丙烯或聚乙烯聚合物基质更具吸引力和更相容的硅胶。为此,在加工期间,当在整个聚合物基质内形成孔道时,可认为干燥剂也会向吸引它的孔道形成剂区域迁移。照此,据从理论上推测,孔道形成剂在处于聚合物结构外部的水汽与处在聚合物内部的干燥剂之间起了沟通作用。实际上,干燥剂是被束缚在充有孔道形成剂的通道内的。在再一个实施方案中,在混合物中添加了极性增塑剂如甘油,以提高干燥剂在孔道形成剂中的分散或混合程度。主要分布在孔道形成剂中的干燥剂能吸收由孔道形成剂输送并保留在孔道形成剂中的水汽。这样,水汽就会迅速进入到整个孔道或通道中而为分散在整个塑料体中的干燥微粒或干燥剂所吸收。
据认为,混合物中干燥剂浓度越高,由此形成的塑性结构的吸收能力越强。然而,干燥剂浓度越高会使塑料体越脆,还会使该混合物更难热成形、挤塑或注塑。为此,据信,最大的干燥剂添加量约为聚合物基质重量的80%(重量)。在另一实施方案中,干燥剂添加量为聚合物基质的10%-20%,20%-40%和40%-60%(重量)。
通常,能用来制造本发明结构的本发明基质聚合物基本上可以是包括酸酐或胺或酸或氰酸酯或异氰酸酯或羟基官能化聚合物的任何官能化的热塑性塑料。适用于本发明的基质聚合物的实例包括丙烯马来酸酐共聚物、乙烯马来酸酐共聚物、苯乙烯马来酸酐共聚物、乙烯丙烯酸共聚物、聚乙烯-聚氨基甲酸酯、聚乙烯-EVOH以及聚乙烯-尼龙。其它适用的热塑性材料包括接枝聚烯烃、聚碳酸酯、聚酰胺、乙烯-醋酸乙烯酯部分水解聚合物、乙烯-甲基丙烯酸酯部分水解聚合物、接枝聚氯乙烯、接枝聚苯乙烯、聚酯、聚酯酰胺、聚丙烯酸部分水解的酯、丙烯酸、聚氨酯和聚缩醛或它们的混合物。
用于本发明的孔道形成剂通常是任何亲水物质。在一个实施方案中,亲水物质是具有至少两个羟基的极性化合物。适用于本发明的孔道形成剂包括聚二醇如聚乙二醇和聚丙二醇以及它们的混合物。其它适用的物质包括EVOH、甘油、季戊四醇、PVOH、聚乙烯吡咯烷酮、乙烯吡咯烷酮或N-甲基吡咯烷酮,而多糖基化合物如葡萄糖、果糖和它们的醇以及甘露糖醇也都是适用于本发明目的的,因为这些都是有多个羟基基团的亲水化合物。
基质聚合物与孔道形成剂之间的反应条件的选择要使聚合物与孔道形成剂的反应完全。因此,要采用足够的反应时间和温度以使各组分完全反应。在本发明的一个实施方案中,先将孔道形成剂与聚合物共混在一起,接着使该混合物在约400-450°F下反应约1-约5分钟。任何适用的反应器都可用于本发明,包括连续反应器(如挤塑机)或间歇反应器(如连续搅拌的罐式反应器),这是显而易见的。
在本发明的另一个实施方案中,各组分先在混合机(如Henschel混合机)中干混,然后供入配混机中。例如,可采用Leistritz双螺杆挤塑机或Werner Pfleider混合机以在约400°F下达到令人满意的熔体混合、反应。然后,可将熔体挤塑成形为例如薄膜或切成粒料等制品,在振动传送机上以干燥的冷空气冷却。然后,例如可将包含孔道的粒料注塑成珠粒、分子筛或与聚丙烯(作为容器的内层)进行共挤塑。
在一个实施方案中,由于混有干燥剂的聚合物通常比不含干燥剂的聚合物脆,因此,包装材料可模塑成内侧部分为混有干燥剂的,而外侧部分为纯聚合物的或干燥剂含量低的混有干燥剂的塑料。例如,一种具有由混有干燥剂的聚合物构成的内侧部分和以纯聚合物构成的外侧部分的包装材料,不仅比较耐久、脆性较低,而且还能起阻止水汽从该包装材料的外侧迁移到内侧的阻湿层作用。照此,干燥剂吸收水汽的能力由于干燥剂只显露在包装材料的内侧而提高,由此,水汽被除去而保留在干燥剂中。
如前所述,本发明混有干燥剂的聚合物有多种用途。一个实施方案是制造适于容纳体积较小的产品如食品和药品的硬质容器。在许多情况下,这类产品必须在低湿度的环境中装运和贮存。在另一个实施方案中,可将混有干燥剂的聚合物成形为根据本发明的、嵌在容器内部的嵌件。一种嵌件形态的实例是由混有干燥剂的聚合物成形的任何呈适用形状的塞子。虽然这种塞子仅是用来放置在防湿容器内的,但它也可被固定在容器内壁而不能在容器的空间内移动。在再一个实施方案中,可以预期,成形为一定形状和大小的圆盘形塞子可压配于聚合物成形的容器底部。
在另一个实施方案中,可将混有干燥剂的聚合物成形为外表面大体上符合容器本体内表面的内衬。跟圆盘形塞子一样,形成内衬的大小应使内衬能紧密地压配在容器本体内,以防止从容器上松脱。或者,在再一个实施方案中,先成形塞子或内衬并使其固化,然后,沿其周围构成容器本体,以不含干燥剂的有较大收缩特性的聚合物本体沿塞子或内衬周围构成紧缩配合的容器本体,而使容器中的塞子或内衬不易松脱。在还有一个实施方案中,以塞子或内衬形态的嵌件基本上是可与聚合物容器本体同时共模塑的,因此相互间是整体接合的。即使对共模塑方法来说,充满干燥剂的嵌件的粘度与聚合物容器本体的粘度一般也应是大致相等的,这样有利于使两相液体即两相模塑在一起的熔融材料处在适当的符合要求的位置上。
在又一个实施方案中,混有干燥剂的聚合物可用来成形为与另一未混合干燥剂的聚合物片材相接合的片材。在至少一个实施方案中,该片材有效层合为一层叠在另一层上,使其外层与混有干燥剂的基本上不透水汽的层相邻接。于是该层合片材可用来包装需要在低湿度环境中贮存的物品。可通过热挤塑工艺这种方法来实施这种接合步骤。
在本文所述本发明的每一实施方案中,较之先有技术方法和结构的优点和改进之处在于发现能在整个混有干燥剂的聚合物中形成通道,而又使混入的干燥剂显露在湿气环境中,并由该聚合物构成了刚性体。此外,还在于采用了为聚合物本体外的水汽向位于聚合物内的干燥剂提供迁移通道的孔道形成剂,从而大大提高了该结构迅速除去位于其外部的水汽的能力,同时又较大限度地利用了混在聚合物中干燥剂的干燥能力的优点。
本发明的一个实施方案包括制造含有吸收水汽的干燥剂的聚合物的方法。该方法包括任何一种胺或酸或羟基官能聚合物与孔道形成剂在适宜的共混、反应条件下共混并反应。或者在反应前,或者在反应后,将干燥剂共混入聚合物中,以使干燥剂分布在聚合物中,使孔道形成剂分布在聚合物中。接着,组合物固化后,孔道形成剂在组合物中形成可供水汽通过并向混在组合物中的干燥剂迁移的通道。在另一个实施方案中,聚合物、孔道形成剂和干燥剂以干燥粉末状态充分混合在一起,然后将该聚合物混合物熔融、反应并以模塑方法形成所需的形状。此时孔道形成剂在组合物中形成可供水汽通过并向混在组合物中的干燥剂迁移的通道。
在另一个实施方案中,用混有干燥剂的组合物成形一种嵌在由隔潮材料制的包装件中的塞子。在再一实施方案中,混有干燥剂的组合物用来成形一种嵌入由隔潮材料制的容器中的内衬。在还有一个实施方案中,混有干燥剂的组合物用来成形一种干燥片材。该干燥片材可任选与隔潮材料制的阻隔片材相复合用作包装材料。在再一个实施方案中,混有干燥剂的组合物用来成形供容器用的吸湿嵌件。
附图1图示了由混有干燥剂的聚合物20制的嵌件。对本发明公开内容来说,当名词“混有”、“含有”及“共混”用来指混在聚合物基质25中的干燥剂30时,它们是可互用的。以塞子55形态的嵌件可以放入容器本体60(图5)中,从而形成干燥容器61(图5)。图2图示了塞子55的剖面图,该塞子是由包含共混有聚合物基质25、干燥剂30和孔道形成剂35的聚合物混合物构成的。在例证性图2中,本发明组合物已固化,因此,在整个聚合物组合物中形成的缝隙或孔道45已构成了整个固化塞子55的通道。正如图1与图2所示,通道一端在塞子55外表面的孔道开口48处。
图3图示了塞子55,该塞子与图2塞子55有类似结构和成分,其中孔道或缝隙是非常细的。这种结构是因采用聚二醇作为孔道形成剂,或同时采用增塑剂和不怎么优选的孔道形成剂而造成的。当组合物固化时,形成的通道具有较高的分布密度和较小的孔隙度,因而在整个塞子55形成了分布较密的通道。当聚二醇用作孔道形成剂时,由于聚二醇与憎水的热塑性塑料(如聚烯烃)通常有相容性,因而易产生相同的效果。孔道或通道的形成为水汽从固化塞子55外部迁移到混有干燥剂30的内部区域提供了通道。由于阻止水汽渗透的聚合物25的憎水性特征,因此可作为隔潮层,因而需要通道。为此,其间混有干燥剂30的聚合物25本身可被称为隔潮材料。然而,为了使混在聚合物25内部的干燥剂30显露出来,还需在该聚合物内形成通道45。如果没有通道45,只有较少量的水汽被干燥剂30所吸收。只能吸收少量的水汽是由于显露在外表面上的干燥剂微粒30的数目有限,因此只有极少量水汽通过基本上不透水汽的聚合物25。由于这些特性,即使该聚合物25不能完全阻止水汽透过,仍被称为隔湿层。在图3示例中,通道47可借助增塑剂得以增多,但干燥剂30仍均匀地分布在整个聚合物基质中。因此,至少部分干燥剂30会被混在阻止水汽透过的聚合物25中,从而使那些干燥剂30的微粒被封闭在聚合物25内而不能吸收水汽。
图4图示了固化塞子55,其中选择干燥剂30以使其极化,因此对孔道形成剂35有吸引作用。因此,在固化过程中,干燥剂30聚集在孔道形成剂35中,并且混入其中的浓度高于在聚合物25中的浓度。因此,有较高百分数的、混在孔道形成剂35中的干燥剂30能与塞子55外部的水汽相接触,从而提高了塞子55的吸收水汽的能力。
在至少一个实施方案中,孔道形成剂35应选择具有促使水汽透过性能的物质。水汽透过孔道形成剂35的速率高于透过聚合物25的速率。这有助于使水汽(如果存在的话)移向混在孔道形成剂35中的干燥剂30和移向混在聚合物25中但邻近孔道形成剂35并显露在孔道形成剂35中的干燥剂30。具有这种特性的孔道形成剂35的实例是聚二醇、EVOH、和PVOH,它们输送水汽的速率高于聚合物25和干燥剂30。因此,孔道形成剂35起了沟通塞子55外部的水汽与混在塞子55内部的干燥剂30的作用。
图5图示了塞子55,该塞子已放置在容器本体60中,从而构成了吸收容器61。容器本体60有内表面65,基本上由隔潮性聚合物25制成。照此,当容器60关闭时,水汽就被阻隔而不能透过容器60壁。从图5可见,塞子55已被压配在容器60的底部。可以设想,塞子55可以只是松松地放入容器60中,但以塞子55固定在容器60本体内的这种配合方式为佳。塞子55与容器本体60之间的配合有利于防止塞子55发生相对移动和错位。这种连接方式可以通过塞子55与容器本体60的内表面65之间的紧密压配来达到,或者以机械方式连接如粘合剂粘合方式或以在塞子55周围延伸的尖叉、凸缘或隆起的脊使塞子55固定在其位置上。在还有一个实施方案中,可以设想,容器本体60可围绕塞子55周围模塑,以使在容器本体60固化过程中,容器本体60围绕塞子55收缩,从而在两个构件之间建立收缩配合。这种类型的配合也可采用共模塑工艺或顺序模塑工艺来达到,因为混有干燥剂的塞子55的收缩率低于构成容器本体60的聚合物25。
图6图示了包含混有干燥剂的塞子55的干燥容器61,与图5所示容器的结构相似,塞子55位于容器60底部,但塞子55与容器本体60是共模塑而成的,因而容器61是一体化的,在塞子55与容器本体60组件之间几乎没有明显的界面。
图7和图8图示了与图5和图6相似的设计概念,但容器内塞子55的比例增大了,以致形成了覆盖干燥容器61中大部分内表面65的内衬70。内衬70不只局限在容器本体60的底部,而是向上延伸并覆盖了容器61的部分内壁。跟塞子55一样,内衬70可单独模塑,随后与容器本体60进行复合,或者如图8所示,也可与容器60共模塑成一个整体。
图9和图10图示了本发明的一个实施方案,其中干燥层75是与阻隔片层80相复合的。这种片材的特征与塞子55、内衬70和容器本体60的特征是相似的。即图9所示的实施方案中,干燥层75与阻隔片层80是分别模塑后再复合成内表面具有干燥特性而外表面具有阻水汽特性的包装材料的。图10图示的是共模塑工艺,其中干燥片层75与阻隔片层80之间的界面没有图9实施方案那样明显。这种产品可通过热成形工艺制得。在这种热成形工艺中,聚合物层经熔融并在经压塑或挤塑恰好通过热成形机中的缝口前与淀积在该薄层顶面上的干燥剂30一起部分成形为片材。可以设想,图9中的片材75、80可借助粘合剂或其它适用方法接合在一起形成片材75、80的多层层合结构。或者,可由热挤塑工艺制造片材75、80,从而可同时制造两片材75、80并有效共挤塑成形为图10所示的实施方案片材。
鉴于对本发明有关可能的实施方案的上述文字说明及对实施方案的图示说明,本文还公开下述实施方案。在一个实施方案中,本发明包括制造混有吸收水汽的干燥剂的聚合物20的方法。通常采用加热和使聚合物熔融使反应产物熔融呈熔融态,然后将干燥剂30混入反应产物中,以使干燥剂30分布在组合物中。使最终组合物固化,从而使孔道形成剂35在混合物中形成可供水汽通过并向混在组合物中的干燥剂30迁移的通道。
水汽易于在孔道形成剂35中扩散,因而在孔道形成剂中的扩散速率大于在干燥剂30或在聚合物25中的扩散速率。
干燥剂30较孔道形成剂35或聚合物25有更高的吸湿能力(以重量计)。干燥剂30对孔道形成剂35的吸引力大于对聚合物25的吸引力。因此,当组合物固化时,干燥剂30在孔道形成剂35中的浓度高于在聚合物25中的浓度。
在本发明的另一个实施方案中,塞子55是由混合物成形的,是用来嵌入以隔潮材料制成的容器60内的。
在一个实施方案中,将塞子55置于由隔潮性材料制成的容器本体60中,照此,制得了干燥容器61。
塞子55可与容器本体60的内表面相配合,以使塞子55相对容器60是固定的。
另一方面,可由隔潮材料围绕塞子55进行模塑而构成容器60,其中使至少部分塞子55显露在容器60内。
根据本发明制的干燥用塞子55也可与隔潮材料进行共模塑而构成容器60,其中使至少部分塞子55显露在容器60内。
在另一个实施方案中,内衬70可由混合物40成形,然后被置于由隔潮材料构成的容器60中。内衬70通常(但不是必须)有一个与容器60的内表面65相匹配接合的外表面。
内衬70与容器60经压入匹配相接合可制得干燥容器61,其中容器的至少大部分内表面65为内衬70所覆盖。
内衬70可由混合物40成形,然后可由隔潮材料围绕内衬70进行模塑而构成容器60,其中使至少部分内衬70显露在容器60内,而容器60的大部分内表面65为内衬70所覆盖。
或者,内衬70与容器本体60一起共模塑成一个统一体。
干燥片材75与由隔潮材料构成的阻隔片材80相复合,以用作包装材料。
片材75、80可通过热挤塑而形成层合结构。
在本发明的还有一个实施方案中,提供了一种制造干燥容器61的方法。该方法包括由基本上不透水汽的材料成形容器60,以使在该容器的内表面与外表面之间形成阻隔水汽的阻隔层。以混有干燥剂的聚合物成形的一种嵌件具有与容器60的至少部分内表面65相匹配接合的外表面。将该嵌件插入容器60内,使嵌件的至少部分外表面与容器60的内表面65呈面对面接合。这种接合使嵌件相对于容器60固定并可防止嵌件与容器60脱开。嵌件拥有通道45,因此嵌件内的干燥剂30是显露在容器60内的,以便吸收水汽。该嵌件是以足够的力压入容器60内部而紧密配合在容器60内,从而可防止与容器脱开。嵌件是按一定大小和形状制造的,以便将嵌件紧密贴合在容器内而保持在应设置的位置上。
在另一个实施方案中,嵌件是按紧密贴合在容器60内底部的塞子55的大小和形状成形的,从而可保持在底部位置上。
在还有一个实施方案中,嵌件成形为具有与容器60的内表面65相一致的外表面的内衬70,以便使内衬70的大部分外表面与容器60的内表面65能面对面的接合。容器60与内衬70具有相似的构形,因此容器60的内表面65与内衬70的外表面能紧密贴合在一起,从而可防止内衬70与容器60脱开。
在另一实施例中,容器60可由基本上不透水汽的塑料模塑而成,因此可阻止水汽透过容器60的内外边界。内衬70可由能吸收和保持水汽的混有干燥剂的塑料20模塑而成。
另一个实施例涉及可用来关闭容器60的可卸式盖子装置。照此,由于容器上方安装了盖子装置,内衬70基本上被密封在盖有盖子的容器60内。容纳在容器60内的水汽可通过干燥剂30而被除去。将产品密封在容器61中,就可使产品贮存在有内衬的、基本上没有水汽的容器61中。
在再一个实施方案中,提供了一种制造干燥容器61的方法。容器是由基本上不透水汽的材料制造的,从而在容器60的内外间形成了隔潮层。一种基本上呈固态的扁片或塞子55是由含干燥剂的支承材料20成形的,扁片55的大小与容器60的内部相适配。然后,将扁片55放置在容器60内,从而当容器60封闭时,就形成了一种使容器60内部干燥的方法。
在本发明的另一个实施方案中,提供了一种制造干燥性包装材料的方法。一层外表层、薄片或外层80是由基本上不透水汽的片材制成的,从而在表层的里外两侧形成了隔潮层。内表层、薄片或内层75是由含干燥剂的支承材料20成形的,位于外表层80的一侧。将产品或物品密封在不透水汽的外层80和邻近产品一侧的干燥性内表层75中,就形成了围绕一种产品或物品的干燥包装件。通过真空模塑将外表层80和内表层75模塑在一起成形为干燥性层合材料,继而可成为干燥性包装材料。
在本发明的一个实施方案中,提供了一种干燥性包装容器61。该包装容器包括由基本上不透水汽的材料成形的容器60,因此,在容器60的内侧与外侧之间形成有隔湿层。内衬70是由干燥剂支承材料20成形的,因而具有与容器60的至少部分内表面65相匹配接合的外表面。因此,当内衬70嵌入容器60内时,内衬的至少部分外表面就能与容器60的内表面65呈面对面贴合,这种贴合使内衬70相对于容器60固定,从而可防止内衬70从容器60脱开。
在本发明还有一个实施方案中,一种用于可封闭容器60的干燥嵌件是一种装入可封闭容器60内的、有一定形状的干燥嵌件。该嵌件是由混有干燥剂30的热塑性塑料25制成的,干燥剂30基本上是均匀地分布在整个嵌件内的。嵌件内的通道从其外表面一直延伸至内部。因此,当水汽迁入孔道或通道时,处于嵌件外部的水汽就可与处在嵌件内的干燥剂30的显露部分相接触而被吸收、保留。
本文说明了混有干燥剂的塑料结构以及构成该结构的化合物。如前所述,本文已公开了本发明的详细实施方案。然而,大家都知道,这些公开的实施方案只是例证性的,实施本发明的形态可以有许多种。在不违背本发明下述权利要求规定的本发明技术、精神和范围的前提下,对本发明作各种改进和其它变更,这对技术熟练人员来说是不难的,这也是显而易见的。
下面将通过具体实施例对本发明作更详细的说明。所有实施例都是说明性的,并不意味着这是对本发明公开内容或权利要求的限制,这是不言而喻的。除另有说明外,实施例和本说明书中其它部分一样,所有百分比都是指重量百分比。
实施例1
本实施例说明了一种含约45(重量)%聚乙烯醇、约5(重量)%甘油和约55(重量)%丙烯马来酸酐共聚物的产品。使聚乙烯醇(购自DuPont)与甘油(液态,购自Dow)混合至被甘油均匀润湿。然后将丙烯马来酸酐共聚物(购自Hoechst)与上述混合物共混。其后将所得共混物供入双螺杆挤塑机,使混合物发生反应。挤塑机操作温度为约400°-约450°,停留时间为约20-45秒,熔体挤塑成薄膜后,随后被磨成细粉,将该细粉与硅胶混合。然后将细粉-硅胶混合物挤塑成薄膜,薄膜中硅胶起吸收水分的作用。
或者,也可在挤塑机中的反应完成后,将干燥剂直接供入挤塑机中。然后将混有干燥剂的聚合物挤塑成薄膜。
实施例2
本实施例说明了一种含有约90(重量)%丙烯马来酸酐共聚物和约10(重量)%甘油的产品。将丙烯马来酸酐共聚物与甘油在约400°F共混并反应约5分钟。接着,使干燥剂(如硅胶)与反应产物共混,然后将共混物挤塑成形为所需形状的制品。
实施例3和4
实施例3说明了一种含有约90(重量)%聚丙烯酸和约10(重量)%聚乙二醇的产品。实施例4说明了含有约90(重量)%聚丙烯或聚乙烯或它们的共混物和10(重量)%聚二醇与马来酸酐共混物的产品。使各组分在适当的共混和反应条件下进行共混和反应。将干燥剂与反应产物混合。然后,产物经熔融、挤塑而成形为一定形状的制品。
Claims (16)
1.一种制造混有干燥剂的聚合物的方法,该方法包括:
(a)将官能化聚合物与孔道形成剂相共混;
(b)使聚合物与孔道形成剂相反应;
(c)将干燥剂混入聚合物—孔道形成剂的反应产物中;和
(d)使混有干燥剂的聚合物—孔道形成剂的反应产物固化。
2.权利要求1的方法,其中聚合物选自酸酐、胺、酸、氰酸酯、异氰酸酯和羟基官能化的聚合物。
3.权利要求2的方法,其中聚合物选自丙烯马来酸酐共聚物、乙烯马来酸酐共聚物、乙烯丙烯酸共聚物、聚乙烯-聚氨基甲酸酯、聚乙烯-EVOH、聚乙烯尼龙以及聚酰胺。
4.权利要求1的方法,其中孔道形成剂是含有一个或多个羟基基团的极性化合物。
5.权利要求4的方法,其中孔道形成剂选自聚乙二醇、聚丙二醇、乙烯-乙烯醇共聚物、聚乙烯醇以及甘油。
6.权利要求1的方法,其中聚合物在与孔道形成剂共混、反应前被熔融。
7.制造一种混有干燥剂的聚合物的方法,该方法包括:
(a)将干燥剂、孔道形成剂和官能化聚合物相共混;
(b)使共混物反应,以形成混有干燥剂的聚合物;
(c)使混有干燥剂的聚合物固化,以形成一定形状的制品。
8.权利要求7的方法,其中聚合物选自酸酐、胺、酸、氰酸酯、异氰酸酯和羟基官能化的官能化聚合物。
9.权利要求1的方法,其中干燥剂是分子筛。
10.权利要求1的方法还包括:
由上述产物成形为一种用于嵌在由隔潮材料制的容器中的塞子。
11.权利要求10的方法还包括:
将塞子放置在由隔潮材料成形的容器内,从而制成干燥容器;及
使塞子与干燥容器的内表面相适配,以使塞子相对于容器固定。
12.权利要求10的方法,其中成形塞子的步骤还包括:
将隔潮材料制的容器与塞子共模塑,以使至少部分所述塞子显露在容器内部。
13.权利要求1的方法,其中固化产物被成形为片材。
14.权利要求13的方法还包括:
将干燥片材与由隔潮材料构成的阻隔片材结合。
15.一种可封闭容器用的干燥嵌件包括:
具有一定形状的可装置在可封闭容器中的干燥嵌件;
由权利要求1的方法成形的所述嵌件;以及
具有从所述嵌件外表面延伸至所述嵌件内部的、水汽可通过的通道的,从而使处于所述嵌件内部的所述干燥剂部分显露在所述嵌件外部的水汽中,以使干燥剂能吸收和保持那些外部水汽的所述嵌件。
16.权利要求1的方法,其中固化产品的形态为选自薄膜、套筒和珠粒的具有一定形状的制品。
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US5773105A (en) * | 1996-03-07 | 1998-06-30 | United Catalysts Inc. - Desiccants | Absorbent packet |
US5814136A (en) * | 1997-04-15 | 1998-09-29 | Stanhope Products Company | Desiccant container |
-
1998
- 1998-05-29 US US09/086,880 patent/US6080350A/en not_active Expired - Lifetime
-
1999
- 1999-05-25 WO PCT/US1999/011523 patent/WO1999063288A1/en not_active Application Discontinuation
- 1999-05-25 AU AU42035/99A patent/AU745516B2/en not_active Expired
- 1999-05-25 CA CA002336408A patent/CA2336408A1/en not_active Abandoned
- 1999-05-25 CN CNB998087432A patent/CN1134644C/zh not_active Expired - Lifetime
- 1999-05-25 EP EP99925822A patent/EP1086347A4/en not_active Withdrawn
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106925084A (zh) * | 2017-04-24 | 2017-07-07 | 苏州苏米欧贸易有限公司 | 一种干燥剂 |
CN110582452A (zh) * | 2017-05-02 | 2019-12-17 | Csp技术公司 | 作为穿刺元件的夹带矿物的塑料配制品 |
CN112312992A (zh) * | 2018-04-24 | 2021-02-02 | Csp技术公司 | 吹塑容器及其制造方法 |
CN116535759A (zh) * | 2023-01-10 | 2023-08-04 | 江苏世德南化功能包装材料有限公司 | 一种具有高吸湿性能的高分子复合材料 |
Also Published As
Publication number | Publication date |
---|---|
CN1134644C (zh) | 2004-01-14 |
US6080350A (en) | 2000-06-27 |
CA2336408A1 (en) | 1999-12-09 |
AU4203599A (en) | 1999-12-20 |
EP1086347A1 (en) | 2001-03-28 |
AU745516B2 (en) | 2002-03-21 |
EP1086347A4 (en) | 2006-05-10 |
WO1999063288A1 (en) | 1999-12-09 |
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