CN101410243A - 由对接熔接膜形成的包装 - Google Patents

由对接熔接膜形成的包装 Download PDF

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Publication number
CN101410243A
CN101410243A CNA2007800110601A CN200780011060A CN101410243A CN 101410243 A CN101410243 A CN 101410243A CN A2007800110601 A CNA2007800110601 A CN A2007800110601A CN 200780011060 A CN200780011060 A CN 200780011060A CN 101410243 A CN101410243 A CN 101410243A
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China
Prior art keywords
film
band
layer
welding
packing
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CNA2007800110601A
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English (en)
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CN101410243B (zh
Inventor
J·托马塞
斯蒂法尼·马修
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Aisapack Holding SA
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Aisapack Holding SA
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Priority claimed from EP06118170A external-priority patent/EP1884348A1/fr
Priority claimed from EP06118199A external-priority patent/EP1884349A1/fr
Application filed by Aisapack Holding SA filed Critical Aisapack Holding SA
Publication of CN101410243A publication Critical patent/CN101410243A/zh
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    • 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
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/50Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like
    • B29C65/5042Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like covering both elements to be joined
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • 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
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/44Joining a heated non plastics element to a plastics element
    • 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
    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/43Joining a relatively small portion of the surface of said articles
    • B29C66/432Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms
    • B29C66/4322Joining a relatively small portion of the surface of said articles for making tubular articles or closed loops, e.g. by joining several sheets ; for making hollow articles or hollow preforms by joining a single sheet to itself
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    • 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
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
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    • B29C66/723General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/7371General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined oriented or heat-shrinkable
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Abstract

一种由热塑性膜的末端对接生产的包装,所述的膜由数层构成,其包括至少第一可熔接层和仅存在部分对接熔接或无对接熔接的第二层,且至少有一条薄的条带覆盖所述末端并直接连接至第二层的一面上,第一层和其他层之间的熔点差大于20℃。

Description

由对接熔接膜形成的包装
技术领域
本发明涉及由塑料膜形成的包装领域。更具体地,本发明涉及其端部为对接熔接的包装。
本发明还涉及一种由热塑性膜生产的其端部为对接熔接的包装的方法。
背景技术
由膜制成的包含至少一层塑料层而形成如袋,管,或其他长方形包装的包装在现有技术的范畴内。这种包装的特别之处在于是通过将膜的末端熔接在一起而制成。
第一种熔接方法包括产生一个被称之为“错边到错边”接合处的接合处,在这里膜的靠下的一面与自身熔接在一起。该接合处示于图1中。
第二种熔接方法包括产生一个被称之为“错边到正确边”接合处的接合处,在这里膜末端发生重叠而所述膜的靠下的一面熔接到所述膜的靠上的一面。该接合处示于图2中。
第三种方法被称之为“对接接合”,包括将膜的末端熔接在一起但不将它们重叠。该方法示于图3,并在专利文献WO 2005/095105A1和US 5569144和US 4733800中进行了描述。
例如,美国专利US 4733800描述了如何由多层塑料膜生产具有柔性铝管的死褶特性的柔性管。该专利提出了使用熔接至管内侧或外侧并在熔接处接合的条带,所述的条带包括提供死褶特性的金属箔。上述专利指明了条带中金属箔的厚度大于多层膜中金属箔的厚度。该专利的主要缺点在于难以密封住所形成的管状体的末端。未来生产出用于糊状产品(如牙膏)的管,通常是将注射模塑的管头熔接到管状体的末端上。将管头熔接于按这篇美国专利US 4 733 800中教导获得的管状体上尤其难以完成。熔接条带的末端在管状体的内表面产生了不连续性,从而有渗漏出现的可能。另外该专利还建议将所述的条带熔接到管的外部。然而,这个包含铝层的大而厚的条带明显地使包装的美观受到影响。
美国专利US 5569144描述了一种用于对接融合膜末端的装置。由该装置得到的管具有改善的外观性能,几乎看不到熔接区。然而,管在熔接区的低强度是的将这些管投入商业应用存在较大风险。
国际专利申请WO 2005/095105描述了一种方法以改进对含有不可熔接的层的多层膜的对接熔接。该方法包括一层压制件的使用,该层压制件包括在靠上和靠下的一面可熔接的膜;夹在可熔接膜之间的不可熔接的层退于膜末端之后,从而在对接熔接期间,可熔接层环绕在不可熔接的层末端从而能够使膜在整个厚度上发生熔接。该方法对多层膜的对接熔接进行了改进,然而根据在申请WO 2005/095105提出的方法生产出的多层管在熔接处的强度低于膜的强度。
对接熔接的主要难点在于获得强度与膜强度接近的熔接区。尤其希望克服的是当向熔接处施加拉升应力时在对接熔接中观察到的脆性断裂。
本发明使得从含有至少一层不可熔接层的多层膜生产对接熔接包装成为可能;根据本发明获得的包装具有与膜强度至少相同等熔接区强度,以及改善的美学特性。
发明内容
本发明涉及由多层膜构成的对接熔接膜,包括至少一层功能性层和一层可熔接层,所述功能性层最多是部分熔接的。在膜的末端加入条带从而弥补在熔接区失去的强度;强度的失去与所述功能性层的末端最多是部分熔接的或可熔接层在熔接时性能下降有关。
本发明的各个方面将由对以下的附图和它们的详细描述得到更好的理解。
附图说明
图1-4描述了现有技术中用于接合膜末端的主要方法。
图1描述了被称之为错边到错边熔接的熔接方法,其包括将所述膜2的末端5接合到它的靠下的一面4上,所述靠下的一面位于包装的内部。
图2描述了被称之为错边到正确边或重叠熔接的熔接方法,其包括将所述膜2的末端5;膜2的靠上的一面3,其接合到膜2的靠下的一面4上接合在一起;所述靠下的一面和靠上的一面分别位于包装的内部和外部。
图3示出了被称之为膜2的末端5的对接熔接的熔接方法。
图4示出了现有技术中已知的一种接合类型。
图5示出了本发明中优选的一种方法,其包括膜2的末端5的接合处1;该膜2是由至少一层可熔接层8和一层功能层7形成,所述末端5仅在可熔接层8处被对接熔接;在膜2的靠上的一面3上粘结一薄条带6并接合层7的不可熔接的末端。
图6示出了在其末端5部分发生对接熔接的膜2的接合,条带6被加到接合处的靠上一面3上,形成包装的外表面;第二个条带10被加到包装的靠下的一面4上,形成包装的内表面;所述条带6和10接合至部分熔接的末端5
图7示出了涂层11可加到外表面3上以覆盖膜2和条带6的整个表面。该涂层11形成了包装的外表,而条带6陷入多层结构当中。
图8描绘了根据本发明的优选模式的管状体的生产。
具体实施方式
对在发明内容中使用的术语的定义:
-熔接:熔融下将具有相同性质或者熔融状态下易混合的两种材料进行连接的操作,所述易混合性通过分子链的扩散和渗透展现;然后冷却所述材料从而冻结住分子渗透到状态。
-粘结:将不具有相同性质或者熔融状态下不易混合的两种材料进行连接的操作,粘结可通过化学机制(链末端的反应,交联),或通过物理机制(范德瓦尔斯力,蒸发)进行。粘结是可在室温下进行或对材料加热进行的连接操作。
-可熔接层:其主要特征是在熔接下能够和有助于制备包装的层。
-功能层:其主要特征是提供熔接能力之外的性能的层。使用的功能层通常具有较小的厚度,例如为提高包装的外表(印刷层,透明层),为改善包装的强度(双轴取向层,技术层),为提供阻碍性能(对氧,香料)或为提供功能性(使包装易于撕开)。
可熔接层通常是基于聚烯烃(聚乙烯,聚丙烯)。对接熔接使非常少量的材料接触,从而更难获得强的接合处。已观察到由80%的线性低密度聚乙烯和20%的自由基低密度聚乙烯共混物构成的可熔接层能够获得强的熔接。
功能层是基于各种不同的树脂(例如:PET,PA,PS,EVOH,PVDC),对它们的选择取决于对性能的期望。当今使用的主要功能层为具有阻碍性能的单轴取向的或双轴取向的(PP,PET,PA,PS)层或膜(沉积了SiOx,PVDC,EVOH,PA涂层的PET)。功能层也可以是由铝或纸制成。
由本发明可获得在熔接区厚度变化可忽略不计以及具有熔接区强度与膜强度相同的熔接包装。获得的包装可在其整个表面上进行印刷而不会在熔接区发生印刷中断。
图5示出了本发明的优选的模式。该优选的模式包括膜2的末端5的接合处1,该膜2含有至少一个可熔接层8作为靠下的一面4和一个功能层7作为靠上的一面3;所述靠上的一面3形成了包装的外表面,而所述靠下的一面4形成了包装的内表面。末端5的对接熔接使得膜2的末端形成部分连接,即功能层7没有被熔接接合。为了连接所述层的不可熔接的末端并对接合处进行加强,一条带6被粘结或熔接至膜靠上的一面3。条带6通常是粘结至功能层3上,而将条带熔接至所述功能层的表面3上通常不可能完成。所述条带6可进行印刷或为透明的,它可含有阻碍层来弥补熔接区中阻碍层可能存在的不连续性。条带6的厚度与膜2的厚度相比是很小的。条带的厚度优选在10-60微米之间。条带可在对接熔接层压制件之前或之后加上。形成包装内表面4的可熔接层8保障了包装内部以及连接处的卫生特性。
图5中所示的根据本发明优选模式制备的包装的优点尤为明显并具有创新性。根据本发明的这种优选的模式可制备出仅含两层的对接熔接膜包装,其第一层为可熔接的,第二层为功能性的。根据该方法制备的包装可在其整个表面上进行印刷而不会在熔接区发生印刷中断。为了不改变包装的外观,条带6优选为透明的和厚度薄的。条带6上也可以进行印刷。
图5中展示出的优选的模式对包括熔点相差超过20℃的层的对接熔接膜来说是有利的。根据该优选方法的膜中的连接包括将所述膜加热至接近可熔接层熔点的温度以及通过粘结或熔接条带而将所述膜的末端连接起来。
图6示出的情况是第一条带6被加到包装外表面之上,而第二条带10被加到包装内表面之上。图8中所示的接合处在可熔接层8的厚度较小时体现出优势。条带6通常是粘结至功能层7的靠上的一面3上,而条带10最好是熔接至形成包装内表面的层8的靠下的一面4上。
本发明的一种变形展示于图7中,包括将合成树脂层11沉积以涂布在膜2的外表面上;所述合成树脂层11涂布在膜2的整个表面3以及条带6的表面,从而使条带6陷于接合处1内。图7中展示出的接合处特别在制备那些接合区不是完全看不见的且在接合区具有高强度的管状体时体现出优势。涂层16优选挤出至膜2的表面上,且所述层经选择而粘附于膜2的表面和条带6涂层11可含有若干层以改进对膜2的粘附性,改进包装的阻碍性能或表面性能。
图8描绘了根据本发明的优选方法通过对接熔接膜生产出的管状体。由于仅由包含第一层是可熔接的和第二层是功能性的两层膜制备,这种管状体特别具有优势。由于现有技术无法实现将所述膜的靠上的一面熔接至靠下的一面,因此在现有技术中这种膜不能用于制备管状体。通过本发明可生产出更强和更美观的包装,并且可使用各种不同类型的多层膜。
上面描述的膜的对接熔接由于赋予了所制成的包装以改进的美学特性而尤为有利;包装在美学方面上改善与熔接区很难可视以及包装的壁在熔接区具有可忽略的额外裕留量有关。
本发明并不限于图5-8中示出的例子。可根据在图5-7中展示的方法生产出管状体。通过将在图5-7中展示的方法进行组合得到的其他方法也可构成部分发明用于等同用途。
本发明可生产出既经济厚度又薄和强度又高的包装。本发明不仅可用于连接多层塑料膜,而且还可用于包含铝层,纸张或纸板层的膜。
条带的厚度与膜的厚度相比较薄。一般而言,条带的厚度比膜厚小5-10倍。所述条带的厚度优选在10-60微米之间。条带上可以进行印刷或可以是透明的;它可粘结或熔接至层压制件的表面上;它可包含一阻碍层来改善接合处的阻碍性能。条带可在对接熔接层压制件之前或之后加上。条带可以是一具有粘合性的条带,对其在室温下进行涂布,条带可通过将粘合剂涂布纸膜和所述条带之间的界面上而进行粘结,条带也可通过加热所述条带进行粘结,条带还可被熔接。膜表面上的条带的粘结强度是决定接合处强度的一个因素。粘结强度过低将导致接合处在对包装施加压力,张力,弯曲,冲击或疲劳应力下发生断裂。因此,期望在条带和膜之间获得强度粘结力从而所述条带不会从所述膜上分离。
条带可熔接或粘结到膜的表面上。通常于将条带粘结至位于接合处靠上的一面上的膜,从而形成包装的外表面。可以设计出许多的粘合和粘结的方法。例如,第一种方法包括将条带加到已事先涂布了粘合剂之处。对这种方法的第一种变形是可在室温下涂布的粘合性条带,第二种变形是可通过加热进行粘结的粘合性条带。粘合性条带的使用得到了易于控制和易于扩大到工业规模的方法。另一种方法包括在连接时将粘合剂涂布纸条带或膜上。双组分活性粘合剂的使用使得能够获得强的粘合水平。一般而言,粘结操作并不需要对接合区进行任何特殊的表面处理,然而,也可以在粘结之前进行表面处理(例如电晕处理)。
当条带粘结至膜的表面上时,有时倾向于在到达管状体末端前终断条带。因此,条带仅延伸至管状体长度的一部分。当连接管状体的末端和管头时,通常优选在接合区中无条带存在。
根据应用的方法和需要提供性能,有各种不同类型的条带供选择。
1-条带被熔接:它含有如可熔接的(共挤出的,无定形的,涂膜的)PET层,共挤出的OPP,PE,PP或可热封的涂层。
2-条带被粘结或用粘合剂涂布。它唯一的区别性特征是在表面具有一层粘合剂层,这种粘合剂可以是在高温下或低温下使用的粘合剂。粘合剂可嵌入地沉积或沉积在条带上。然后将条带以卷的形式储存,接着用硅树脂纸或膜保护粘合剂。硅树脂可以选择地直接沉积到条带的外表面上从而能够避免定位条带时移除硅树脂。
任何类型的材料均可用作该条带,特别是在第1和2点中描述的材料,在这些材料上可加入纸或铝。对条带的定义将根据期望的屏障,机械抵抗力和外观特性来指导进行。
3-条带被粘结但本身没有用粘合剂涂布。粘合剂可沉积在膜2上或嵌入地沉积。可采用的材料与以上第1点中的相同。
为了提供阻碍性能,条带可包括铝层,PET或OPP阻碍层(与PVOH,PVDC,SiOx,AlOx或金属化的涂层或任何其他可通过商业渠道获得的膜一同),或与EVOH类型的障碍共挤出的层。
通常,未来确保产品性能的连续性,增强的条带可包括与用作包装的膜2相同的功能层,即包括PET,OPP,OPA,障碍PET,金属化的PET,障碍OPP,金属化的OPP,铝纸,PE,PP等。
条带也可由若干层构成。例如这可以是由OPP,PET,纸,PE,PP,OPA,PA,PET/PE,OPP/PE,OPA/PE,纸/PE,PET/Al,OPP/Al,OPA/Al,PET/Al/PE,PET/Al/PP,OPP/Al/PE,OPP/Al/PP,OPA/Al/PE,OPA/Al/PP,纸/Al/PE,纸/PET,纸/Al等制成。这里仅提及了产品的通用名称。这一名称覆盖率全部的产品家族。因此,PET可以是传统的双轴取向的PET,无定形的PET,共挤出的PET,SiOx PET,AlOx PET,金属化的PET等。而PE包含了所有的基于PE的共挤出的膜;它们除了别的之外,包含了EVOH或PA层。这在其他参考文献中是一样的。
从更广泛的角度讲,市场上所有的厚度在10-60微米的膜均可单独或作为多层出现在这些条带中。
本发明对于制备化妆品,药物或食品用柔性管尤其具有优势。
实施例
在下面的实施例中,从包装的靠外的一面向靠里的一面对多层结构进行描述,即从接合处靠上的一面向靠下的一面进行描述。为了使本发明更容易理解,未示出加在膜2的可熔接层和功能层处的粘合剂层。只示出了提供条带6或10与膜2之间粘结性的粘合剂层。
实施例1
根据本发明优选的方法形成的接合处,其展示于图5中:
接合处1:        PET/粘合剂-PET/PE
膜2:            PET/PE
功能层7:        PET-厚30微米
可熔接层8:      PE-厚180微米
条带6:          PET/粘合剂-厚40微米
粘合剂:         Bostik Vitel 1912
实施例2
根据本发明优选的方法形成的接合处,其展示于图5中:
接合处1:      BOPP/粘合剂-BOPP PVOH/PE
膜2:          BOPP PVOH/PE
功能层7:      BOPP PVOH-厚40微米
可熔接层8:    PE-厚200微米
条带6:        PET/粘合剂-厚60微米
粘合剂:       Bostik TLH 2013
实施例3
根据图6中展示的方法形成的接合处:
接合处1:        PA/PE-PE/PA/PE
膜2:            PE/PA/PE
功能层7:        PA-厚40微米
可熔接层8:      PE-厚200微米
条带6:          PA/PE-厚60微米
实施例4
根据图7中展示的方法形成的接合处:
接合处1:        PE/铝/PE-PE
膜2:            PE/铝/PE
功能层7:        铝-厚8微米
可熔接层8:      PE-厚80微米
可熔接层9:      PE-厚120微米
条带6:          PE-厚60微米
实施例5
根据图8中展示的方法形成的接合处:
接合处1:        PET/粘合剂-KRAFT/铝/PE-PE
膜2:            KRAFT/铝/PE
功能层7:        KRAFT/铝
可熔接层8:      PET-厚40微米
条带6:          PET/粘合剂-厚60微米
粘合剂:         Bostik TEE 222
条带10:         PE-厚40微米
其他实施例:
一些可用于对接熔接用的膜的非穷尽的例子有:
PE EVOH PE,PE/Al/PE,PET/Al/PE,PET/PE,OPP/Al/PE,OPP/PE,Kraft/PE,Kraft/Al/PE。
采用可熔接的PP代替PE也可生产出相同的结构。
这里仅提及了产品的通用名称。这一名称覆盖率全部的产品家族。因此,PET可以是传统的双轴取向的PET,无定形的PET,共挤出的PET,SiOx PET,AlOx PET,金属化的PET等。而PE包含了所有的基于PE的共挤出的膜;它们除了别的之外,包含了EVOH或PA层。
从更广泛的角度来讲,只要接合处包含至少一层可熔接膜,则市场上所有的膜均可出现在对接熔接的膜中。

Claims (9)

1.一种由热塑性膜的末端对接生产的包装,所述的膜由数层构成,其包括至少第一可熔接层和仅存在部分对接熔接或无对接熔接的第二层,且至少有一条薄的条带覆盖所述末端并直接连接至第二层的一面上,第一层和其他层之间的熔点差大于20℃。
2.根据权利要求1所述的包装,包括连接至膜的末端并分别置于膜两侧的两个条带。
3.根据权利要求1或2所述的包装,其中条带是粘结的。
4.根据前述权利要求中任一项所述的包装,其中第二层和条带被一层合成树脂覆盖。
5.一种生产前述权利要求中任一项的所述包装的方法,包括将由数层构成的膜的末端进行对接熔接,所述膜包括至少第一可熔接层和仅存在部分对接熔接或无对接熔接的第二层;所述方法的特征在于,膜的末端位置设置成使得它们在邻接后相继被加热和冷却从而将所述第一层的末端熔接,并在第二层上连接至少一个条带以覆盖所述末端。
6.根据权利要求5所述的方法,其特征在于,条带是在所述加热和冷却操作之前连接至第二层的。
7.根据权利要求5所述的方法,其特征在于,条带是在所述加热和冷却操作之后连接至第二层的。
8.根据权利要求5所述的方法,其特征在于,条带是在进行所述加热和冷却操作的同时连接至第二层的。
9.根据权利要求5-7中任一项所述的方法,其中至少一种合成树脂层沉积覆盖于由所述膜和由所述条带形成的接合处的表面。
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WO2007113780A2 (fr) 2007-10-11
RU2437765C2 (ru) 2011-12-27
EP2007567B1 (fr) 2011-08-17
CN101410243B (zh) 2011-10-12
JP2009532296A (ja) 2009-09-10
PL2007567T3 (pl) 2012-01-31
BRPI0709941A2 (pt) 2011-08-02
US20090092792A1 (en) 2009-04-09
CA2645081A1 (fr) 2007-10-11
JP5466000B2 (ja) 2014-04-09
KR101374126B1 (ko) 2014-03-20
CA2645081C (fr) 2014-01-21
EP2007567A2 (fr) 2008-12-31
WO2007113780A3 (fr) 2008-01-10
US8852705B2 (en) 2014-10-07
RU2008143420A (ru) 2010-05-20
BRPI0709941B1 (pt) 2018-09-04
ATE520601T1 (de) 2011-09-15
KR20080110798A (ko) 2008-12-19
HK1127764A1 (en) 2009-10-09

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