CN1018259B - 片状挠性包装材料 - Google Patents

片状挠性包装材料

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Publication number
CN1018259B
CN1018259B CN89107121A CN89107121A CN1018259B CN 1018259 B CN1018259 B CN 1018259B CN 89107121 A CN89107121 A CN 89107121A CN 89107121 A CN89107121 A CN 89107121A CN 1018259 B CN1018259 B CN 1018259B
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basic unit
filler
basic
packing
astm
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CN1039771A (zh
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艾克·罗森
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Tetra Laval Holdings and Finance SA
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Tetra Pak Holdings SA
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Priority claimed from SE8802777A external-priority patent/SE467926B/sv
Priority claimed from SE8802778A external-priority patent/SE467917B/sv
Application filed by Tetra Pak Holdings SA filed Critical Tetra Pak Holdings SA
Publication of CN1039771A publication Critical patent/CN1039771A/zh
Publication of CN1018259B publication Critical patent/CN1018259B/zh
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    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B65D5/00Rigid or semi-rigid containers of polygonal cross-section, e.g. boxes, cartons or trays, formed by folding or erecting one or more blanks made of paper
    • B65D5/42Details of containers or of foldable or erectable container blanks
    • B65D5/56Linings or internal coatings, e.g. pre-formed trays provided with a blow- or thermoformed layer
    • B65D5/563Laminated linings; Coatings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0053Moulding articles characterised by the shape of the surface, e.g. ribs, high polish
    • B29C37/0057Moulding single grooves or ribs, e.g. tear lines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001Combinations of extrusion moulding with other shaping operations
    • B29C48/0018Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001Combinations of extrusion moulding with other shaping operations
    • B29C48/0019Combinations of extrusion moulding with other shaping operations combined with shaping by flattening, folding or bending
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07Flat, e.g. panels
    • B29C48/08Flat, e.g. panels flexible, e.g. films
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/13Articles with a cross-section varying in the longitudinal direction, e.g. corrugated pipes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/04Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B2553/00Packaging equipment or accessories not otherwise provided for
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

一种用于制造具有良好尺寸稳定性的液封包装容器的片状挠性有折痕的材料,这种材料包括一层或多层相互层迭填充有矿物填料的热塑塑料的基层,其中无机颗粒矿物填料的重量占该混合材料总重量的50至80%,所述的热塑塑料是由ASTM(2.16kg,230℃)熔融指数在0.5至5之间的丙烯基聚合物中选择,并且所述的一个基层或多个基层具有折痕线图案,该图案是通过塑性变形而形成的,该变形是与所述基层挤压共同进行的或在挤压后该基层还处于塑性时紧接着进行的。

Description

本发明涉及一种用于制造具有良好尺寸稳定性的液封包装容器的片状或条带状挠性有折痕材料,所述材料包括一层或多层相互层迭、含有矿物填充物的热塑塑性挤压成形的基层,这种热塑塑料包含的填充物或颗粒无机矿物填料的比例占该混合材料总重量的5%至80%之间。
在包装技术中,不可回收的包装已经用了很长时间,这种包装是由一层其内、外覆盖有热塑塑料的纸或纸板基层材料制造的,在这些所谓不可回收包装材料中也经常置有一些其它材料层,例如:铝箔,或与上述不同的塑料覆盖层。
这种包装材料的结构希望所包装的产品产生尽可能好的保护,同时,作为一种包装,它必须具有要求的机械强度和耐久性,以便使该包装经得住在正常搬运过程中易受到的外部应力的作用,为了获得机械刚性,即一方面给产品以机械保护,另一方面使该包装的尺寸稳固,使其在搬运和人工抓夹时没有困难,这些包装材料常常设置一种较厚的纸或纸板基层。但是,这种材料对液体或气体不具有密封性,而且当它受潮时,很快失去刚性,因此,为了使这种材料具有要求的液封性,该基层在其两边常常提供塑料覆盖层,如果这种塑料是热塑塑料,该覆盖层还通过所谓热封方法相互密封该些塑料覆盖层,这样,通过热封方法将液封的重迭材料面和覆盖的热塑塑料热封在一起,并且以机械方法永久密封连接,使包装永久性密封,并且做成指定的形状。在先有技术中,GB1554143公开了一种有挠性的折痕材料,其折痕是通过传统的折边机 制成的。
这里所指的不可回收包装,大部分情况是借助包装机制成的,该包装机以高速从片材或预制的半成品包装材料进行成形,充填和对加工好的包装封口。例如,从片材制造包装,首先将该片材的纵向边缘以搭接方式连接在一起,形成一管子,接着用实际的容量充填,并在与管的纵向轴线垂直方向上,对该管进行重复的压平和封口,分隔成封闭的包装部件。最后,各部件通过横向各封口区域切割而相互分开,并通过进一步的折弯和密封形成具有要求的几何形状,一般是平行六面体的包装容器。
当以上述方法制造包装时,层迭的材料经受压力,尤其是在材料折弯时,由于基层材料的厚度较大,该压力变得很大,折弯指的是一面塑料覆盖层经受很强延展,同时,另一面的塑料覆盖层沿折弯线受到相应程度的压缩。由于塑料覆盖层具有很大的延展性,所以这种材料的折弯很少导致通过延展在延伸的塑料覆盖层里引起泄漏的裂开或其它的损坏,但如果该材料还包括一层铝箔,问题就严重了,该铝箔与塑料覆盖层比较具有小得多的延展性,并且当该材料被折弯时,常常导致断裂。
虽然该材料一次180℃折弯一般没有任何严重的后果,但当该材料沿二条交叉的折痕线折弯时,则产生很大的困难。不管它们是否由片材或预制的半成品来制造,这是经常出现在这类包装外部封口区域的情况,封口的进行总是在塑料覆盖层面朝包装内沿边缘加热至融化而相互密封,之后,该加热的塑料覆盖层相互靠着压紧,通过在该包装的外表面熔合形成夹在一起的封口片,这种封口片包括二层材料,为了保证它不会形成一种障碍,这种封口片常常折弯、平放贴在该包装的外侧,意指该封口片的一层材料折过了180°,在折下封口片区域里的包装壁包括三层材料,即具有三层折弯材料厚度,这样一种封口片区域里的包装的一个或多个侧面进行,由于这些侧面,例如平行六面体包装的侧面沿 与封口片成直角的折痕线折过180°,在一定区域,该包装的材料厚度上升至层迭材料的六倍,在封口区域的这种180°横向折弯,使最外面覆盖的材料层经受了延伸的非常强的拉伸应力,并且在该材料里增加形成裂开的危险。这些拉伸应力常常是很大的,使裂开不仅出现在包括在该材料中的铝箔内,而且在热塑塑料覆盖层里也伴有包装物品泄漏的危险,该泄漏物迅速被该材料的基层吸收,并削弱其刚性。
由于普通的包装材料基于纸或纸板,明显地具有严重缺点,所以,涉及用在该材料中的纤维层必须是相当的厚,以便使该材料具有机械刚性。很长时间以来,寻找新的包装材料的目的就是要完全摆脱纤维材料,以便制造具良好尺寸刚性的液封包装容器。因此,本发明的一个目的是提供涉及这种不用纸或纸板的包装材料。
本发明的另一目的是提供一种包装材料,这种材料在新型的高生产率的包装机配合下,能迅速制成具有尺寸刚性的液封包装容器,当该材料在容器制造过程中折弯时,没有裂开的危险。
本发明达到了这些目的和其它一些目的,这在于一种用以制造具有良好尺寸刚性的液封包装容器的片状挠性有折痕的材料,该材料包括一层或多层挤压成形、相互层迭、充填有矿物填料的热塑塑料的基层,其中无机颗粒状矿物填料的重量占该混合材料总重量的50%至80%,其特征在于:所述热塑塑料是选自ASTM(2.16kg,230℃)熔融指数为0.5至5之间的丙烯基聚合物,所述的一个基层或若干基层上带有折痕线图案该折痕线图案是由塑性变形而形成的,所说塑性变形是与各基层挤压共同进行的或各基层挤压之后紧接着进行的。
下面参考附图更详细地说明本发明,其中:
图1表示本发明一实施例的片状形式包装材料的一部分;
图2表示图1中沿Ⅱ-Ⅱ线放大的该材料横截面;
图3示意地表示该包装材料的制造设备;
图4表示本发明第二实施例的片状形式包装材料相应于整个包装长度的一部分;
图5a是图4中沿Ⅴ-Ⅴ线放大的该材料横截面;
图5b是本发明另一实施例的对应于图5a包装材料的横截面;
图6示意地表示图4和图5a中包装材料的制造设备。
图1显示用标号1表示本发明片状材料对应于整个包装长度的L部分,该包装容器由片状材料1制造,如前所述,使片状材料1的二条纵边缘区域2以搭接方式相互连接在一起,形成一管子,接着用实际容量充填。在与管子的纵轴线垂直的方向上对该管子进行重复压平,并沿窄小横向密封区域3对该管进行封口,将充填过的管子分隔成单独的容器部件。最后,各个容器部件在横向封口区域3切断,相互分离,并通过进一步的成形和密封操作,获得要求的形状,例如,平行六面体。
本发明这个实施例的材料(如图2所示)包括填充有矿物填料的丙烯基聚合物的基层4,该聚合物的根据美国材料试验手册(ASTM)(2.16kg,230℃)的熔融指数在0.5至5之间。在聚合物中填料的重量为该混合材料总重量的50%至80%,最佳值在65%-75%(重量),就刚性和弹性模量而论,已经发现这种填充量产生该材料的最佳弹性。
所述丙烯基聚合物可以是其ASTM(2.16kg,230℃)熔融指数在1以下的聚丙烯均聚物,但最佳的丙烯基聚合物可选自熔融指数在上述0.5至5范围的丙烯-乙烯共聚物中,因为,它们已经产生出耐折弯和耐弯曲操作的性能,即使在正常出现的将该包装材料制成包装容器的过程中和充注液体食品(例如牛奶)的低温条件下也不会裂开。
在本发明中,填料的选择并非关键,而且特别要说的是,所有经处理的已知矿物填料都可使用,例如,云母、滑石、钙盐如硫酸钙或碳酸钙等,基层包含65%(重量)的颗粒状碳酸钙,颗粒尺寸在10μm以下,无论怎样,在实施中已发现这种组合材料起有效作用,它使得有可能制 造具有要求的良好尺寸刚性的液封包装容器,在实施中,该基层材料的厚度d可以在100和400μm之间,最佳值是300μm。
为了便于将片状材料制成包装容器,基层4上已置有一种任意图案的折痕线5和6,以便折弯,这些折痕线分别平行和横向地在片状材料上纵向伸展,在这个例子中,折痕线5和6是通过基层4塑性变形而形成的。该塑性变形是与所述基层的挤压共同进行的或挤压之后紧接着进行的。
上述的片状材料1可以由示意性表示在图3中的设备制造,该设备包括带有合适尺寸喷嘴8的挤压机7和二个用于充注挤压原材料的供料斗9和10,即ASTM(2.16kg,230℃)熔融指数在0.5至5之间的颗粒状丙烯基聚合物,例如,分别是聚丙烯均聚物或丙烯-乙烯共聚物和矿物填料,该含有填充料量在50%至80%重量(例如65%重量)的热塑塑料被加热至软化或开始熔化(大致在180°-300℃),并通过喷嘴8挤压,形成一条厚100-400μm,例如300μm的薄膜1′。该薄膜1′通过相互配合、冷却的压力辊子11和12之间辊隙挤压,其中一个辊子11的外表面配有以凸起的部分或版型形成的图案,该部分或版型对着薄膜1′压过,在薄膜一面上沉积一附加的表面图案,通过塑性变形而产生所述折痕线5和6,接着,该带有折痕线的冷却薄膜1可以卷在储料筒13上。
图4和图5a表示本发明第二个实施例对应于整个包装长度L的部分,用标号14表示,从片状材料14按前面所述的方法制成填充的液封包装容器,制造时,片状材料14的纵向边缘区域15以搭接方式相互连接,以便形成一管子,接着用指定的容量填充,然后已填充的管子在与管子纵轴线成垂直的方向重复压平,并沿横向封口区域16使管子封口,据此将所说填充的管子分隔成封口的容器部件。此后,通过进一步折弯和密封操作,使各个容器部件获得要求的几何形状,例如,平行六面体。
从图5a可以明显地看到,这个实施例中的材料包括由基层17a 和17b相互层迭组成的基层17,这些基层的制造是通过含有矿物填料和丙烯基聚合物的混合材料挤压成形,丙烯基聚合物的ASTM(2.16kg,230℃)熔融指数是在0.5至5之间,颗粒状无机矿物填料的重量占混合材料总重量的50%至80%,最好是在65%至70%。熔融指数在上述范围内的丙烯基聚合物可以是ASTM(2.16kg,230℃)熔融指数在1以下的丙烯均聚物,但由于前述的原因,最好是丙烯-乙烯共聚物。
用在丙烯基聚合物基层17a和17b中的填料可以是云母、滑石,钙盐,如硫酸钙或碳酸钙等。在该例子中假定朝向指定包装容器内侧的基层17a含有云母填料,而另一基层17b含有颗粒状的碳酸钙填料,其颗粒尺寸在10μm以下,包含在基层17中的基层17a和17b各自的厚度可以在50-200μm之间,但实际考虑的各基层的厚度最好是100μm。
图5b表示对应于图5a包装材料的横截面的本发明另一实施例,根据这个实施例,该材料包括带有与图5a所述的基层17a和17b相同材料的外基层18a和18b,它们通过ASTM(2.16kg,230℃)熔融指数在0.5至5之间的泡沫状的或低密度的丙烯基聚合物中间层18c而相互连接。
基层18的材料总厚度可以变化,但实际考虑的厚度值大致为300μm,包括在基层18的各层最好具有相同的厚度,也就是说100μm。
在上述包装容器的制造方法中,为了便于片状材料14的折弯,其上分别置有任意的纵向和横向折痕线19和20,如图4所示,这些折痕线(在图5a中仅表示出纵向折痕线19)通过在基层17的一面或这个例子中所示的两面上的塑性变形而形成,为了更明了起见,在图5b中基层18上用相同方法获得的对应于图5a的折痕线用相同的标号表示。
图6示意地表示根据本发明制造图4和图5a所示片状材料14的设备,该设备包括一带有合适尺寸喷嘴23的双层挤压机,喷嘴23包括双槽形开口,各层原材料通过该喷嘴23分别挤压出材料的基层17a和17b。 双层挤压出的基层层迭片状材料14当它们处于塑性时,通过二个相互配合的冷压力辊21和22挤压,在辊子21和22的表面上配置有凸起的部分或凸起的版型图案,以便当片状材料14靠在它们的面上通过时,通过塑性变形,在片材两面上产生易于折弯的折痕线图案。接着带有折痕线的冷却片状材料14卷在储料筒上(图中未表示)。此外,用相应的方法,示于图5b的另一实施例片状包装材料也可以制造,在这种情况下,挤压机包括具有三槽形开口的喷咀,以便有可能挤压包括在基层18中的三层18a-18c。

Claims (8)

1、一种用于制造具有良好尺寸稳定性或刚性的液封包装容器的片状或条带状挠性有折痕的材料,该材料包括一层或多层挤压成形的基层(4;17a、17b;18a、18b)与具有ASTM(2.16KG,230℃)熔融指数为1以下的,混合有填料的丙烯均聚物互相层迭,其中所说的填料重量为丙烯均聚物与填料混合物总重量的50-80%,或上述基层与具有ASTM(2.16kg,230℃)熔融指数为0.5-5的,混合有填料的乙烯/丙烯共聚物互相层迭,其中所说的填料的重量为乙烯/丙烯共聚物和填料混合物总重量的50-80%,其特征在于所说的基层带有折痕线(5,6;19,20)图案,该折痕线是通过塑性变形而形成的,所说塑性变形是与各基层挤压共同进行的或在挤压后基层还处于塑性时紧接着进行的。
2、按照权利要求1所述的材料,其特征在于:它包括的两个相互层迭的基层(17a、17b;18a、18b),其中一个基层,最好是面朝指定包装容器的内侧的基层含有云母填料,另一基层含有钙盐填料,最好是硫酸钙或碳酸钙。
3、按照权利要求2所述材料,其特征在于:所述二基层是共挤压成形的。
4、按照权利要求2所述材料,其特征在于:所述二基层的每一层材料厚度为50至200μm,最好是100μm。
5、按照权利要求1所述材料,其特征在于,所述基层(4)的厚度为100至400μm,最好是300μm。
6、按照权利要求2至4中任一项所述的材料,其特征在于:所述的二基层(18a、18b)是通过ASTM(2.16kg,230℃)熔融指数为0.5至5之间的泡沫丙烯基聚合物中间层(18c)相互连接的。
7、按照权利要求6所述材料,其特征在于:所述二基层(18a,18b)和中间层(18c)是通过其挤压成形制造的。
8、按照权利要求7所述材料,其特征在于:所述二基层中的每一层和中间层具有的材料厚度为100μm。
CN89107121A 1988-08-01 1989-08-31 片状挠性包装材料 Expired CN1018259B (zh)

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YU150989A (en) 1991-06-30
PL160551B1 (pl) 1993-03-31
YU46751B (sh) 1994-04-05
CN1039771A (zh) 1990-02-21
ATE119830T1 (de) 1995-04-15
DE68921678D1 (de) 1995-04-20
AR240690A1 (es) 1990-09-28
EP0640461A1 (en) 1995-03-01
RO104653B1 (en) 1993-04-25
DE68921678T2 (de) 1995-07-27
KR900003032A (ko) 1990-03-23
UA13452A (uk) 1997-02-28
JP2848635B2 (ja) 1999-01-20
AU3914689A (en) 1990-02-01
JPH02175141A (ja) 1990-07-06
EP0353496B1 (en) 1995-03-15
CA1333879C (en) 1995-01-10
SK278374B6 (en) 1997-02-05
ES2069552T3 (es) 1995-05-16
EP0353496A1 (en) 1990-02-07
PT91340A (pt) 1990-03-08
US5143764A (en) 1992-09-01
RU1804430C (ru) 1993-03-23
KR940009014B1 (ko) 1994-09-29
HU210360B (en) 1995-04-28
AU614653B2 (en) 1991-09-05
CS458989A3 (en) 1992-04-15

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