CN1107797A - 用再生塑料共同型的多层塑料容器 - Google Patents

用再生塑料共同型的多层塑料容器 Download PDF

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CN1107797A
CN1107797A CN94113753A CN94113753A CN1107797A CN 1107797 A CN1107797 A CN 1107797A CN 94113753 A CN94113753 A CN 94113753A CN 94113753 A CN94113753 A CN 94113753A CN 1107797 A CN1107797 A CN 1107797A
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internal layer
resin
regenerating resin
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CN1047991C (zh
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D·H·穆尔
小·R·W·M·里特
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Graham Packaging Plastic Products Inc
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered 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
    • B32B27/08—Layered 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 synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
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    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/003—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7158—Bottles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/043—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • Y—GENERAL 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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    • Y10S264/917—Recycling consumer used articles or products by blow molding material recycled from consumer used article or product
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

一个用再生塑料树脂共挤出成型的多层塑料容 器，包括一乙烯聚合物的外观增强薄外层，其改善了 容器的外观，一中间层包括具有或没有塑料的再生树 脂的熔融混合物，一第三层，包括具有混合颜色的再 生树脂的熔融混合物。在一改型和优选的形式中，提 供一纯净乙烯聚合物的第四内层。

Description

本发明涉及共挤出成形的塑料容器，特别是涉及用再生树脂吹制的塑料容器。
在使用塑料材料容器诸如瓶子时，业已发现希望设法再循环或再使用该塑料，其被称作再生塑料（PCP）或再生树脂（PCR）。在采用这种材料制造容器的试验中，业已发现对其性质有不良影响。
当使用再生的高密度聚乙烯均聚物（HDPE）容器的碎片制造容器，业已发现降低了容器的物理性质。用高密度聚乙烯均聚物制造的这种容器用来包装一些类型的液体洗涤剂产品。由于许多类型的液体洗涤剂产品加速了容器产生应力裂纹的事实，已经开始限制使用这种容器包装液体洗涤剂产品。由于容器上出现模糊的裂纹，应力裂纹是明显的，对最终的消费者来讲在审美方面是令人不愉快的，在极端情况下，应力裂纹能导致容器内容物的泄漏，在容器用于液体产品包括液体洗涤剂和液体次氯酸盐的漂白剂时，产生应力裂纹。
由于盛放乳品和水的大体积的容器广泛使用高密度聚乙烯，因为可利用大量的高密度聚乙烯再生树脂，业已建议使用这种再生树脂。用于这种容器的再生树脂含有纸和其它塑料树脂如瓶盖等杂质，使得一般认为其不能令人满意地制造塑料容器。
在一与本申请具有共同受让人的1992年2月27日提交的专利申请07/842，839中，公开了一种塑料容器，该容器由再生树脂和乙烯聚合物熔融的混合物制成，该乙烯聚合物包括均聚物高密度聚乙烯塑料的再生树脂和纯净的高密度聚乙烯共聚物树脂。与至令使用再生树脂降低物理性质的情况相比较，这种容器保持了包括抗应力裂纹在内的物理性质。
根据上述申请，来自再生树脂（PCR）的均聚物高密度聚乙烯树脂的粉末和纯净的高密度聚乙烯共聚物的粉末混合并熔融混合。
容器被吹塑成形并承受应力裂纹、最大载荷和跌落冲击等试验。
在与本申请具有共同受让人的1992年2月27日提交的专利申请07/842，838中，公开了一种塑料容器，该容器由再生塑料和乙烯聚合物熔融的混合物制成，该混合物包括均聚物高密聚度聚乙烯树脂的再生树脂和少量的线性低密度聚乙烯树脂，在另一种形式中，用再生均聚物高密度聚乙烯树脂的混合物制造容器。与至今使用再生树脂降低物理性质的情况相比较，这种容器保持了包括抗应力裂纹在内的物理性质。
大量的塑料树脂用于制造容器，其具有由添加剂提供的诱人的外观，添加剂的作用是提供光泽的或诱人的颜色。这种添加剂是昂贵的。据本发明人所知，由于再生树脂固有的灰暗的颜色，至今还没有人想到可用再生树脂制造塑料容器，而容器具有诱人的光泽或颜色，这需要昂贵的颜料。
本发明的目的之一是提供一种塑料容器，其具有一外表层;该容器不仅使用再生塑料也使用具有不同颜色的再生树脂;其中塑料容器的结构的布置，使具有多种颜色的再生树脂的颜色是不可见的，使得容器具有诱人的外观;其中对暗的、厚的包括容器主体部分的再生树脂层是看不见的，其中容器具有明显诱人的外观颜色;使容器明显节约了树脂。
根据本发明，用再生塑料树脂共挤出成形的多层塑料容器包括：一增强外观的薄外层，其包括乙烯聚合物和增强容器外观的颜料的熔融混合物;一中间层，其包括具有或没有颜料的再生树脂的熔融混合物;一第三层，其包括具有混合的颜色的再生树脂。在一可变型的优选形式中，一纯净乙烯聚合物的第四内层设置在第三内层上：
图1示出本发明的一个塑料容器。
图2是沿图1中2-2线的放大的局部视图，图示出该容器的横截面。
图3是放大的局部视图，图示出该容器另一个变型的部份横截面。
图4是放大的局部视图，图示出该容器另一个变型的部份横截面。
参考图1，应用本发明的一多层中空的塑料容器10，最好由多层型坯共同成形然后吹塑而成，使容器具有基体部份11、底部12、肩部13和具有研磨部15的颈部14。
参考图2，在一优选形式中，容器10包括四层;一薄的外表面增强塑料层A，其包括乙烯均聚物聚合物和改善外观的添加剂的熔融混合物;一相邻的薄塑料层B，其作用是掩盖第三个厚塑料层C的颜色，层C包括可具有混合的颜色的再生树脂的熔融混合物。需要时，在容器的内部设置一纯净乙烯均聚物的第四个薄内塑料层D，其保护容器的内容物。
在图3所示中，内层D被省略。
外层A的塑料树脂可包括乙烯共聚物如线性低密度聚乙烯、低密度聚乙烯、高密度聚乙烯或它们的混合物和改善外观的添加剂的熔融混合物。
用于改善外观的典型的添加剂包括，提供明亮诱人颜色的颜料;提供珠母般的效果的粉末，如碳酸铝或碳酸钙的粉末;以及荧光的染料或颜料，众所周知其可吸收一个波长上的光线和更长波长上的组合光线;以及所选择的分子量的聚合物，其提供了光泽度高的外观。
薄塑料层B可包括乙烯聚合物的熔融混合物，最好是纯净高密度聚乙烯或再生树脂和改善外观的添加剂，其掩盖厚层C的再生树脂。
再生树脂主要含有塑料，这些塑料来自：用于包装乳品的高密度聚乙烯均聚物容器和有颜色的塑料容器以及能用的聚丙烯树脂，这些能用的聚丙烯树脂来自浆糊瓶、多层番茄酱瓶和盖的这种再生树脂可具有下面表1所列的性质。
表1
性质  规定值
材料密度  0.960±0.02天然的
熔体流动-熔体指数  0.5±0.3分克/分
细屑  <0.01%
湿度  <0.05%
杂质
纸  <0.01%
塑料-密度 >1.0克/厘米3<0.1%
当应用薄的内层D时，其包括乙烯共聚物诸如纯净的高密度聚乙烯或线性低密度聚乙烯。
在每一种情况下，容器壁厚的主体部分是再生树脂厚层C的厚度。
本发明的线性低密度乙烯聚合物的密度在大约0.91至大约0.93克/毫升的范围内，较好是在大约为0.92至大约0.93克/毫升的范围内，最好是约为0.925克/毫升。线性低密度乙烯聚合物的熔体指数小于约2.0，最好小于约1.0克/10分钟。最好是该熔体指数接近包括在混合物内的线性高密度乙烯聚合物的熔体指数。这些聚合物是乙烯共聚物，其具有聚合物约2至6最好是4-6摩尔%的α-单链烯，其含有3至12个碳原子，该碳原子具有聚合乙烯的单体平衡。本发明使用的线性低密度乙烯聚合物具有长线性链，沿其整个长度，数量受控制的相当短的支链连接到长线性链上。
低密度聚乙烯均聚物包括应用在外层上，具有至少为2并最好是小于1的熔体指数;其密度不大于0.93克/毫升。
低密度聚乙烯包括外面的高光泽层。低密度聚乙烯具有至少为2最好为小于1的熔体指数，其有0.93克/毫升的最大密度。
纯净的高密度共聚物树脂含有线性高密度乙烯聚合物。线性高密度乙烯共聚物包括在混合物中，其具有至少约为0.94克/毫升的密度，小于约0.5克/10分的熔体指数，并且聚合至少约98摩尔%的带有任一共聚单体的乙烯，其中含有约3至12个碳原子的α-单链烯。这种线性高密度乙烯聚合物是公知的并在现有技术中有记载，并且从许多制造商那儿可得到的。这种线性高密度乙烯聚合物由聚合的乙烯制备，任选在含有4至12个碳原子的α-单链烯共聚单体的情况下，和在一定的金属催化剂的情况下，金属催化剂诸如铬催化剂如支承在氧化硅-氧化铝载体上的三氧化铬，和格勒-纳塔催化剂，如与烷基铝助催化剂共同使用的三氯化钛。在聚合物中要获得必要的密度和熔体指数由适当控制聚合条件得到，这些条件包括温度、压力、共聚单体浓度以及催化（telegenating）试剂如氢的浓度。优选的线性高密度乙烯聚合物有至少约0.94克/毫升的密度。最好是聚合物有至少约0.95克/毫升的密度。按常规进行抗应力裂纹的试验方式是按照塑料瓶研究所1991年修订本第1期的泛英工业公司（PBI）技术公报1978年11期，或美国材料试验标准（ASTM）D2561-70（1989年重新批准）进行。
据本发明的容器的侧壁厚度的典型实例是：
四层  薄层A  2-20密耳
薄层B  2-10密耳
厚层C  5-30密耳
薄层D  1-10密耳
三层  薄层A  2-20密耳
薄层B  2-10密耳
厚层C  5-30密耳
三层  薄层A  3-20密耳
厚层B  8-30密耳
薄层C  1-10密耳
容器中的各层特定组成的实例如下：
例Ⅰ
薄层A-光泽的高密度聚乙烯和珠母般的添加剂
薄层B-再生树脂（乳品）和二氧化钛颜料
厚层C-再生树脂（混合的颜色）并经重新研磨
薄层D-纯净高密度聚乙烯和颜料
例Ⅱ
薄层A-光泽的高密度聚乙烯
薄层B-再生树脂（乳品）和二氧化钛颜料
厚层C-再生树脂（混合颜色）并重新研磨
薄层D-纯净高密度聚乙烯以及颜料
例Ⅲ
薄层A-光泽的低密度聚乙烯
薄层B-再生树脂（乳品）和二氧化钛颜料
厚层C-再生树脂（混合颜色）并重新研磨
薄层D-纯净高密度聚乙烯
金属碎屑  无
其它（玻璃、石子）  无
例Ⅳ
薄层A-纯净的高密度聚乙烯、光泽的高密度聚乙烯和线性低密度聚乙烯
薄层B-再生树脂（乳品）和二氧化钛颜料
厚层C-粘合剂层
-再生树脂并重新三磨
薄层D-尼龙
在图4示出的形式中，内层D′由耐溶剂的材料制成，诸如尼龙，以提供一种结构使容器能用于溶剂产品如石油蒸馏液。
在这种形式中，第三层C′包括再循环再生聚乙烯树脂，经过去毛刺和废品碎屑的加工。一粘合剂层（未示出）设置在层B与层C′之间并也设置在层C′与层D′之间，用于层粘合。该粘合剂层包括一尼龙/聚乙烯粘接剂。
如图所示，层C、C′包括了厚度的主要部分。
可以发现，本发明已提供了用再生塑料树脂共同挤出的多层塑料容器，其包括：一改善外观的薄外层，其包括乙烯聚合物和改善容器外观的颜料的熔融混合物;一中间层，其包括具有或没有颜料的再生树脂的熔融混合物;一第三层，其包括具有混合颜色的再生树脂。在一可变型的优选形式中，一纯净乙烯聚合物的第四内层设置在第三内层上。
可以发现本发明提供的塑料容器具有一外表层;其不仅使用再生塑料，也使用具有不同颜色的再生树脂;该塑料容器的结构和布置使得有多种颜色的再生树脂是不可见的，并使容器具有诱人的外观;其中一相当暗的、厚的、包括容器主体部的再生树脂层是不可见的;容器可具有一明显诱人的外观颜色，使得容器明显地节约了树脂。

Claims (16)

1、一共挤出成形的多层塑料容器包括：
一相对薄的外层包括乙烯聚合物和改善外观的添加剂熔融混合物，
一相对薄的中间不透明层包括具有颜料的再生树脂的熔融混合物，以及
一相对厚的再生树脂的内层，
所述中间层掩盖住再生树脂。
2、根据权利要求1的容器，其中再生树脂包括容器的主体部分。
3、根据权利要求2的容器包括内层上有一纯净聚合物树脂层。
4、根据权利要求3的容器，包括另一内层由耐溶剂的塑料树脂制成。
5、根据权利要求4的容器，其中所述耐溶剂塑料树脂包括尼龙，尼龙包括在不透明的中间层与再生树脂的内层之间的粘接层，以及在再生树脂的内层与耐溶剂塑料的另一内层之间的粘接层，每一所述的粘接层包括尼龙/聚乙烯粘接剂。
6、根据权利要求1至4任一项的容器，其中改善外观的添加剂选自下组中，包括颜料、珠母般的添加剂、荧光添加剂和光泽的分子量树脂。
7、根据权利要求1的容器，其中所述外层包括一光泽的高密度聚乙烯和改善外观的添加剂的熔融混合物;所述中间层包括再生树脂（乳品）和一彩色颜料，所述内层包括再生树脂（混合颜色）并重新研磨。
8、根据权利要求7的容器包括在所述内层上另有一内层，其包括纯净的高密度聚乙烯和颜料的熔融混合物。
9、一种形成共挤出成形的多层塑料容器的方法包括：
共挤出成形一多层型坯，包括一相对薄的外层，其包括乙烯聚合物和改善外观的添加剂的熔融混合物，一相对薄的中间不透明层，该不透明层包括具有颜料的再生树脂的熔融混合物，以及一相对厚的再生树脂的内层，所述中间层掩盖住再生树脂，以及将多层吹塑，然后形成一多层器。
10、根据权利要求9的方法，其中再生树脂包括容器的主体部分。
11、根据权利要求10的方法，包括在内层上有一层纯净的聚合物树脂。
12、据权利要求11的方法，包括由耐熔剂的塑料树脂制的另一内层。
13、据权利要求12的方法，其中所述耐溶剂塑料树脂包括尼龙，其包括在不透明的中间层与再生树脂的内层之间的粘接层，以及在再生树脂的内层与耐溶剂塑料的另一内层之间的粘接层，每一所述的粘接层包括一尼龙/聚乙烯粘接剂。
14、根据权利要求9至12任一项的方法，其中改善外观的添加剂选自下组中，包括颜料、珠母般的添加剂、荧光添加剂和光泽的分子量的树脂。
15、根据权利要求9的方法，其中所述外层包括一光泽的高密度聚乙烯和改善外观的添加剂的熔融混合物;所述中间层包括再生树脂（乳品）和一彩色颜料，所述内层包括再生树脂（混合颜色）并重新研磨。
16、根据权利要求15的方法，包括在所述内层上另有一内层，另一内层包括纯净的高密度聚乙烯和颜料的熔融混合物。
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CN100338351C (zh) * 2003-05-09 2007-09-19 株式会社丰田自动织机 电动泵
CN111113857A (zh) * 2013-03-20 2020-05-08 阿尔温莱纳股份有限两合公司阿尔普拉工厂 挤出吹塑成型管
CN111201120A (zh) * 2017-10-12 2020-05-26 宝洁公司 具有视觉效果的吹塑制品
CN110963172A (zh) * 2018-09-28 2020-04-07 派迪莱工业有限公司 涂抹器组件和用于溶剂胶结剂产品的多层容器
CN115397657A (zh) * 2020-04-10 2022-11-25 宝洁公司 具有独特视觉效果和回收利用的热塑性材料的多层热塑性制品

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ATE175619T1 (de) 1999-01-15
JPH07214737A (ja) 1995-08-15
GR3029892T3 (en) 1999-07-30
CA2131351A1 (en) 1995-03-17
BR9403581A (pt) 1995-05-16
DK0644035T3 (da) 1999-08-30
CA2131351C (en) 2006-11-21
AU7284594A (en) 1995-03-30
ES2126687T3 (es) 1999-04-01
ZA947197B (en) 1995-05-12
EP0644035A1 (en) 1995-03-22
EP0644035B1 (en) 1999-01-13
DE69415901T2 (de) 1999-08-12
CN1047991C (zh) 2000-01-05
DE69415901D1 (de) 1999-02-25
US5712009A (en) 1998-01-27

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