CN106275678A - Foaming bottle and preparation method thereof - Google Patents

Foaming bottle and preparation method thereof Download PDF

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Publication number
CN106275678A
CN106275678A CN 201510293020 CN201510293020A CN106275678A CN 106275678 A CN106275678 A CN 106275678A CN 201510293020 CN201510293020 CN 201510293020 CN 201510293020 A CN201510293020 A CN 201510293020A CN 106275678 A CN106275678 A CN 106275678A
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foaming
bottle
total
layer
thickness
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CN 201510293020
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Chinese (zh)
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宋利君
邓玉明
张雅君
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内蒙古伊利实业集团股份有限公司
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Abstract

The invention provides a foaming bottle and a preparation method thereof. The bottle wall of the foaming bottle is of a multilayer structure, and comprises at least a foaming layer and at least a non-foaming layer. Preferably, the foaming bottle is used for food package, preferably, the total thickness of the bottle wall ranges from 0.2mm to 0.9mm, and the total thickness of the foaming layer accounts for 40%-80% of the total thickness. The foaming bottle provided by the invention has good stiffness and relatively good sealing performance, compared with a container moulded by a sheet material, the foaming bottle is advantaged in that the bottle can be sealed in a cover rotating manner.

Description

一种发泡瓶子及其制备方法 A foamed bottle and preparation method

技术领域 FIELD

[0001] 本发明涉及塑料瓶子生产领域,具体的说,涉及一种发泡瓶子及其制备方法,本发明的发泡瓶子尤其适于食品包装。 [0001] The present invention relates to the field of the production of plastic bottles, specifically, to a method for preparing a foamed bottle and foam of the present invention is particularly suitable for bottles for food packaging.

背景技术 Background technique

[0002] 随着食品的多样性、个性化的发展,对食品包装的要求和挑战也越来越多,多层高阻隔、高避光的功能性的瓶子制品在塑料瓶子领域内的需要越来越大。 [0002] With the development of the diversity of food, personalized food packaging requirements and challenges are more and more multi-layer high barrier, high functionality dark bottle products needed in the field of plastic bottles more be greater. 多层共挤制品的发展促进了多层共挤或注塑塑料成型机的发展。 Promote the development of co-extrusion article or the development of a multilayer coextruded plastic injection molding machine. 近年来,多层共挤或注塑塑料成型机发展的速度很快,同时技术进步也很快,塑料瓶子瓶壁从I层做到7层在技术上已经具备了实现的可能。 In recent years, multi-layer coextrusion or injection speed plastic molding machines developed quickly, while the technological progress quickly, plastic bottles from the bottle wall 7 do I layer includes a layer technically possible.

[0003] 而在当前资源消耗过量的前提下,作为轻量化包装的一种工艺和包装方法,在不改变材料厚度,保持材料挺度的情况下,减小材料密度,以达到减轻重量的效果,提高绝缘性能,同时降低生产成本迫在眉睫,通过在瓶子生产原料中添加微发泡剂,在加热过程中遇热产生0)2和H2O,在经过塑化后的聚合物熔体中形成致密的气孔,而达到降低瓶子密度的效果,完成包装轻量化的目的。 [0003] In the current excess resource consumption under the premise of a process and a packaging method as lightweight packaging, without changing the material thickness of the holding material stiffness, material density decreases, in order to achieve weight savings , improve the insulation performance, while reducing production costs imminent, by adding fine foamer bottle production of raw materials, during heating by heat generation 0) 2 and H2O, to form a dense polymer melt through the plastics in the porosity, and to reduce the effect of the density of the bottles, complete lightweight packaging purposes.

[0004] 但单层结构的微发泡瓶子在实际使用时存在有表面粗糙、产品挂壁、展示效果差等问题,急需解决。 [0004] The micro foamed bottle but a single layer structure is present in practical use has a rough surface, the wall hanging products, showing poor results, it needs to be resolved.

发明内容 SUMMARY

[0005] 本发明的一个目的在于提供一种发泡瓶子;本发明的发泡瓶子性价比比较高,具有低克重、高厚度,表面光滑没有气孔的优点,适合用于包装牛奶、饮料和水等食品。 [0005] An object of the present invention to provide a foamed bottle; bottle foam of the present invention is relatively high cost, low weight, high thickness, smooth surface without pores advantages, suitable for packaging milk, drinks and water and other food.

[0006] 本发明的另一目的在于提供所述的发泡瓶子的制备方法。 [0006] Another object of the present invention is to provide a method of preparing a foamed bottle.

[0007] 为达上述目的,一方面,本发明提供了一种发泡瓶子,所述瓶子瓶壁为多层结构,其中包括至少一层发泡层和至少一层非发泡层。 [0007] To achieve the above object, in one aspect, the present invention provides a foamed bottle, the bottle the bottle wall a multilayer structure, comprising at least one foamed layer and at least one non-foamed layer.

[0008] 根据本发明所述的发泡瓶子,其中优选所述发泡瓶子为食品包装用发泡瓶子。 [0008] The foamed bottle according to the present invention, the preferred bottle is a food packaging foamable foaming bottle.

[0009] 根据本发明所述的发泡瓶子,其中优选瓶壁总厚度为0.2-0.9mm,发泡层总厚度为瓶壁总厚度的40% -80%。 [0009] The foamed bottle according to the present invention, wherein the total thickness of the bottle wall is preferably 0.2 to 0.9 mm, the total thickness of the foam layer is 40% -80% of the total thickness of the bottle wall.

[0010] 根据本发明所述的发泡瓶子,所述发泡层为微发泡聚合物层,其密度为0.6-0.9g/ [0010] The foamed bottle according to the present invention, the foam layer is a microcellular foamed polymer layer, having a density of 0.6-0.9g /

m3o m3o

[0011] 根据本发明所述的发泡瓶子,所述微发泡聚合物是本领域常规材料,为本领域技术人员所熟知,市售任何的微发泡聚合物均可用于本发明;尤其是指以聚合物材料为基体,其中含有泡孔尺寸从小于一微米到几十微米的多孔聚合物材料。 [0011] The foamed bottle according to the present invention, the polymer micro-foam material is conventional in the art, those skilled in the art, any commercially available micro foamed polymer may be used in the present invention; in particular, It refers to the polymeric matrix material, which contains the cell size from less than one micron porous polymer material to tens of microns.

[0012] 根据本发明所述的发泡瓶子,所述瓶壁为至少三层结构,其中所述发泡层的两侧各有一层非发泡层。 [0012] The foamed bottle according to the present invention, the sidewall is at least three-layer structure wherein both sides of the foamed layer each have a layer of non-foamed layer.

[0013] 根据本发明所述的发泡瓶子,优选所述非发泡层外表面无肉眼可见微孔。 [0013] The foamed bottle according to the present invention, preferably the outer surface of the non-foamed layer no visible pores.

[0014] 根据本发明所述的发泡瓶子,优选内外两层非发泡层各自分别占非发泡层总厚度的30% -70%。 [0014] The bottle according to the present invention, the foamed, preferably non-foamed layer and inner layers are each respectively 30% -70% of the total thickness of the non-foamed layer.

[0015] 根据本发明所述的发泡瓶子,所述瓶壁结构为层A/层B、层A/层B/层A、层A/层B/层C、层A/层B/层A/层C或层A/层B/层C/层A排列;其中层B为发泡层,层A和层C各自表示不同的非发泡层。 [0015] The foamed bottle according to the present invention, the sidewall structure Layer A / Layer B, Layer A / Layer B / Layer A, Layer A / Layer B / Layer C, Layer A / Layer B / Layer a / layer C or layer a / layer B / layer C / layer a array; wherein the foam layer is a layer B, the layers a and C each represent different non-foamed layer.

[0016] 根据本发明任意一项所述的发泡瓶子,所述发泡层和非发泡层的材质各自独立选自高密度聚乙烯、聚丙烯和聚苯乙烯中的一种或一种以上的混合。 [0016] According to the present invention, any one of the foam bottle A material of the foamed layer and the non-foamed layer are each independently selected from high density polyethylene, polypropylene and polystyrene, or one in more mixed.

[0017] 本发明所述的高密度聚乙烯为本领域常规材料,通常指密度在0.93-0.96g/m3的聚乙烯材料。 High density polyethylene material according to the conventional art [0017] The present invention generally refers to a material density polyethylene in 0.93-0.96g / m3 of. 任何市售符合上述标准的高密度聚乙烯材料均可用于本发明。 Any commercially available high density polyethylene material meeting the above criteria can be used in the present invention. 即本领域市售用于制备瓶子(尤其是食品包装用瓶子)的高密度聚乙烯材料均可用于本发明。 High density polyethylene material that is commercially available in the art for the preparation of bottles (especially food packaging bottles) can be used in the present invention.

[0018] 本发明所述的聚丙烯和聚苯乙烯为本领域常规材料,任何市售聚丙烯和聚苯乙烯材料均可用于本发明。 [0018] The present invention is polypropylene and polystyrene materials conventional art, any commercially available polypropylene and polystyrene materials can be used in the present invention. 即本领域市售用于制备瓶子(尤其是食品包装用瓶子)的聚丙烯和聚苯乙烯材料均可用于本发明。 I.e., polypropylene and polystyrene material commercially available in the art for the preparation of bottles (especially food packaging bottles) can be used in the present invention.

[0019] 根据本发明任意一项所述的发泡瓶子,所述发泡层是以碳酸盐发泡剂制备得到。 [0019] According to the invention according to any one of foamed bottle, said foamed layer are prepared to give the carbonate blowing agent.

[0020] 其中优选所述碳酸盐为碳酸氢钠。 [0020] wherein said carbonate is preferably sodium bicarbonate.

[0021] 其中所述发泡工艺可以为现有技术常规方法,按照现有常规的发泡工艺制备即可得到用于本发明的发泡层。 [0021] wherein the foaming process may be a conventional prior art methods, the conventional process of preparing foamed conventional foamed layer obtained according to the present invention.

[0022] 其中更优选所述发泡层为微发泡聚合物层。 [0022] More preferably wherein said foam layer is a microcellular foam polymer layer.

[0023] 根据本发明任意一项所述的发泡瓶子,所述发泡瓶子由各原料通过包括挤吹或注拉吹步骤的方法制备得到。 [0023] According to the invention according to any one of foamed bottle, said method comprising preparing a foamed bottle extrusion blow or injection stretch blow feedstock through each step is obtained.

[0024] 根据本发明任意一项所述的发泡瓶子,所述发泡瓶子由包括如下步骤的方法制备得到:将各层的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,再用挤塑机将分配好的各层原料挤出到同一分配器中,经模口挤出,定型即得产品。 [0024] According to the invention according to any one of foamed bottle, the bottle foam prepared by the process comprising the steps of: feed the layers scaled uniformly, stirred sufficiently dry mixing the respective hopper, extruder and then the extruded material layers to the allocated same dispenser, is extruded through a die, shaped product is obtained.

[0025] 根据本发明所述的发泡瓶子,制备时挤塑机机身温度控制在170-250°C。 [0025] The foamed bottle according to the present invention, the preparation of the extruder body the temperature controlled at 170-250 ° C.

[0026] 另一方面,本发明还提供了所述的发泡瓶子的制备方法,所述方法包括如下步骤:将各层的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,再用挤塑机将分配好的各层原料挤出到同一分配器中,经模口挤出,定型即得产品。 [0026] another aspect, the present invention also provides a method for preparing the foamed bottle, said method comprising the steps of: Stir the material layers in the respective proportion in the mixing hopper, sufficiently dried, then extruder with a good distribution of the extruded material layers to the same dispenser, is extruded through a die, shaped product is obtained.

[0027] 根据本发明所述的制备方法,所述发泡层是以碳酸氢钠发泡剂制备得到。 [0027] The production method according to the present invention, the foamed layer are prepared to give a blowing agent sodium bicarbonate.

[0028] 综上所述,本发明提供了一种发泡瓶子及其制备方法。 [0028] In summary, the present invention provides a method for preparing a foamed and bottle. 本发明的发泡瓶子具有如下优点: Foaming bottle of the present invention has the following advantages:

[0029] 1、本发明能够按需要平衡产品的刚性和韧性,使成本更优化,可以循环使用降低产品成本; [0029] 1, according to the present invention enables products to balance rigidity and toughness, to make more cost optimization, can be recycled to reduce product cost;

[0030] 2、本发明相对于片材制得的容器更易于加工,减少加工工艺,缩短生产周期,且对加工设备的要求不高,不需要特殊的充气发泡装置; [0030] 2, with respect to the present invention is a container made of sheet easier to process, reduction process, to shorten the production cycle, and less demanding processing equipment, it does not require special foaming inflator means;

[0031] 3、本发明中的微发泡瓶子,具有良好的挺度和较好的密封性能,和采用片材成型的容器比,可采用旋盖的方式对瓶子进行密封。 [0031] 3, the micro-foam in the bottle of the present invention, has good stiffness and good sealing properties, and the use ratio of the sheet molded containers may be employed for capping bottles sealed manner.

[0032] 4、同样材料同样厚度的瓶子,本发明的微发泡瓶子比未发泡瓶子传热更慢,装温度偏高或偏低的食品,可避免烫手或冰手。 [0032] 4, of the same material of the same thickness of the bottle, the bottle according to the present invention, the micro-foam is slower than the non-foamed bottle heat transfer means high or low temperature food, ice or hot hand can be avoided.

附图说明 BRIEF DESCRIPTION

[0033] 图1为瓶子不意图; [0033] Figure 1 is not intended to be a bottle;

[0034] 图2为瓶子瓶壁结构局部放大图;其中I为外层,2为微发泡层,3为内层; [0034] FIG. 2 is a partial enlarged view of the structure of a bottle sidewall; wherein I is an outer layer, layer 2 is a microcellular foam, the inner layer 3;

[0035] 图3为瓶子瓶壁显微镜放大图。 [0035] FIG. 3 is an enlarged view of a bottle the bottle wall microscope.

具体实施方式 detailed description

[0036] 以下通过具体实施例详细说明本发明的实施过程和产生的有益效果,旨在帮助阅读者更好地理解本发明的实质和特点,不作为对本案可实施范围的限定。 [0036] Example embodiments described below in detail by way of specific embodiment of the process of the present invention and advantageous effects produced, is intended to aid the reader in better understanding of the nature and features of the present invention is not intended to limit the scope of the instant case.

[0037] 实施例1 [0037] Example 1

[0038] 瓶子采用挤吹的工艺生产,瓶壁按照层A/层B排列,其中层A为外层的非发泡层,层A的厚度占总厚度的20%,层B为发泡层,占总厚度的80%,瓶子总厚度为0.5mm。 [0038] The use of bottles extrusion blow molding process to produce bottle wall according Layer A / Layer B are arranged, wherein the outer layer A is a non-foamed layer, 20% of the total thickness of the thickness of the layer A, layer B is a foam layer 80% of the total thickness, the total thickness of the bottle is 0.5mm. 瓶子垂直承压为210N。 Vertical pressure bottle was 210N.

[0039] 所述的层A是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母I ; [0039] The layer A is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, masterbatch I;

[0040] 所述的层B是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母0.5,碳酸氢钠发泡剂1.5 ; [0040] The layer B is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, masterbatch 0.5, 1.5 sodium bicarbonate foaming agent;

[0041] 所述的层A、层B中用到的高密度聚乙烯具有以下特性:在190°C,2160g的负荷下,测定熔融指数为0.33g/10min ;熔融温度为132°C,刚性为8045 kg / cm 2。 [0041] The layer A, layer B used in the high density polyethylene has the following characteristics: the load at 190 ° C, 2160 g measured melt index of 0.33g / 10min; melting temperature of 132 ° C, rigid to 8045 kg / cm 2.

[0042] 制备方法为:采用双螺杆吹瓶机,将每层用到的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,将挤塑机挤出A层螺杆的三个加热段温度分别控制在175°C、1800C、1800C,挤出B层螺杆的三个加热段温度分别控制在175°C、210°C、180°C,再将分配好的各层原料挤出到模头,模头温度控制在180°C,经模头挤出至模口,吹塑定型即得此制品O Preparation of [0042] method: using a twin-screw blow molding machine, the raw material used in each layer in proportion to stir respective mixing hopper, thoroughly dried, the A layer extruder screw extruder three heating zones temperature were controlled at 175 ° C, 1800C, 1800C, screw extruding layer B three heating zones were controlled at a temperature of 175 ° C, 210 ° C, 180 ° C, and then extruded material layers to the allocated mold head, a die temperature is controlled at 180 ° C, extruded through a die to die, blow-styling product to obtain this O

[0043] 以实施例1制得的壁厚为0.5mm的瓶子为例,若瓶内装满4°C的纯水,放置在60°C的水浴中,瓶内水温每升高一度的时间发泡瓶比未发泡瓶平均慢4秒。 [0043] In Example 1 the wall thickness of an example embodiment prepared a bottle of 0.5mm, when the bottle is filled with pure water at 4 ° C, placed in a water bath of 60 ° C, the temperature is increased once the bottle time bottle bottle unfoamed foaming than four seconds slower on average.

[0044] 实施例2 [0044] Example 2

[0045] 瓶子采用挤吹的工艺生产,瓶壁按照层A/层B/层A排列,其中层A为外层的非发泡层,层A的厚度占总厚度的20%,层B为发泡芯层,占总厚度的80%,瓶子总厚度为 [0045] The use of bottles extrusion blow molding process to produce bottle wall A are arranged in layer A / layer B / layer, wherein the layer A is a non-foamed outer layer, 20% of the total thickness of the thickness of the layer A, the layer B is 80% of the expanded core layer, the total thickness, the total thickness of the bottle

0.6mm。 0.6mm. 所得到的瓶子如图1所示,瓶壁结构如图2所示,瓶壁发泡芯层微观图如图3所示。 The obtained bottle 1, the bottle wall structure shown in Figure 2, the bottle wall expanded core microstructure shown in Figure 3. 瓶子垂直承压为270N。 Vertical pressure bottle was 270N.

[0046] 所述的层A是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100、色母I ; [0046] The layer A is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, masterbatch I;

[0047] 所述的层B是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母0.5,发泡剂1.5 ; [0047] The layer B is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, masterbatch 0.5, 1.5 foaming agent;

[0048] 所述的层A、层B中用到的高密度聚乙烯具有以下特性:在190°C,2160g的负荷下,测定熔融指数为0.33g/10min ;熔融温度为132°C,刚性为8045 kg / cm 2。 [0048] The layer A, layer B used in the high density polyethylene has the following characteristics: the load at 190 ° C, 2160 g measured melt index of 0.33g / 10min; melting temperature of 132 ° C, rigid to 8045 kg / cm 2.

[0049] 制备方法为:采用双螺杆吹瓶机、将每层用到的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,将挤塑机挤出A层螺杆的三个加热段温度分别控制在175°C、1800C、1800C,挤出B层螺杆三个加热段温度分别控制在175°C、210°C、180°C,再将分配好的各层原料挤出到模头,模头温度控制在180°C,经模头挤出至模口,吹塑定型即得此制品。 Preparation of [0049] method: using a twin-screw blow molding machine, the raw material used in each layer in proportion to stir respective mixing hopper, thoroughly dried, the A layer extruder screw extruder three heating zones temperature were controlled at 175 ° C, 1800C, 1800C, three screw extruder heating zone B layer were controlled at a temperature of 175 ° C, 210 ° C, 180 ° C, and then extruded material layers to the allocated die , the die temperature is controlled at 180 ° C, extruded through a die to die, blow-styling product to obtain this.

[0050] 以实施例2制得的壁厚为0.6mm的瓶子为例,若瓶内装满4°C的纯水,放置在60°C的水浴中,瓶内水温每升高一度的时间发泡瓶比未发泡瓶平均慢4.5秒。 [0050] In Example 2 was the wall thickness of a bottle of 0.6mm an example embodiment, if the bottle is filled with pure water at 4 ° C, placed in a water bath of 60 ° C, the temperature is increased once the bottle time foaming bottle slower than the non-foamed bottle average 4.5 seconds.

[0051] 实施例3 [0051] Example 3

[0052] 瓶子采用挤吹的工艺生产,瓶壁按照层A/层B/层C排列,其中层A为外层的非发泡层,层A的厚度占总厚度的15%,层B为发泡芯层,占总厚度的75%,层C为内层的非发泡层,层C的厚度占总厚度的10%,瓶子总厚度为0.6_。 [0052] The use of bottles extrusion blow molding process to produce, according to the bottle wall layer A / layer B / layer C are arranged, wherein the layer A is the outer non-foamed layer, 15% of the total thickness of the thickness of the layer A, the layer B is foamed core layer, 75% of the total thickness of the inner layer C is a non-foamed layer, the thickness of layer C is 10% of total thickness, the total thickness of the bottle 0.6_. 瓶子垂直承压为270N。 Vertical pressure bottle was 270N.

[0053] 所述的层A是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母0.5 ; [0053] The layer A is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, 0.5 masterbatch;

[0054] 所述的层B是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母0.5,发泡剂2 ; [0054] The layer B is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, masterbatch 0.5, 2 blowing agent;

[0055] 所述的层C是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母0.5 ; [0055] The layer C is made of the following parts by weight of raw materials: high density polyethylene (HDPE) 100, 0.5 masterbatch;

[0056] 所述的层A、层B、层C中用到的高密度聚乙烯具有以下特性:在190 °C,2160g的负荷下,测定恪融指数为0.31g/10min ;恪融温度为134°C,刚性为9021 kg / cm 20 [0056] The layer A, layer B, layer C used in the high density polyethylene has the following characteristics: the load at 190 ° C, 2160 g, the melt index was measured Ke 0.31g / 10min; melting temperature Verified 134 ° C, the rigidity of 9021 kg / cm 20

[0057]制备方法为:采用三螺杆吹瓶机,将每层用到的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,将挤塑机螺杆挤出A层螺杆的三个加热段温度分别控制在175°C、1800C、1800C,挤出B层螺杆三个加热段温度分别控制在175°C、210°C、180°C,挤出C层螺杆的三个加热段温度分别控制在175°C、180 °C、180 °C,再将分配好的各层原料挤出到模头,模头温度控制在180°C,经模头挤出至模口,吹塑定型即得此制品。 Preparation of [0057] methods: using three-screw blow molding machine, the raw material used in each layer in proportion to stir respective mixing hopper, thoroughly dried, the screws of the extruder screw extruder three heating layer A stage temperature were controlled at 175 ° C, 1800C, 1800C, three screw extruder heating zone B layer were controlled at a temperature of 175 ° C, 210 ° C, 180 ° C, the C layer extruder screw three heating zone temperatures control 175 ° C, 180 ° C, 180 ° C, and then extruded material layers to the allocated die, the die temperature is controlled at 180 ° C, extruded through a die to die, i.e., blow styling get this product.

[0058] 以实施例3制得的壁厚为0.6mm的瓶子为例,若瓶内装满4°C的纯水,放置在60°C的水浴中,瓶内水温每升高一度的时间发泡瓶比未发泡瓶平均慢4.5秒。 [0058] In Example 3 the wall thickness of 0.6mm obtained in the bottle as an example embodiment, when the bottle filled with water at 4 ° C, placed in a water bath of 60 ° C, the temperature is increased once the bottle time foaming bottle slower than the non-foamed bottle average 4.5 seconds.

[0059] 实施例4 [0059] Example 4

[0060] 瓶子采用挤吹的工艺生产,瓶壁按照层A/层B/层A/层C排列,其中层A为外层的非发泡层,层A的厚度占总厚度的15%,层B为发泡芯层,占总厚度的75%,层C为内层的非发泡层,层C的厚度占总厚度的10%,瓶子总厚度为0.6_。 [0060] The use of bottles extrusion blow molding process to produce, according to the bottle wall layer A / layer B / layer A / layer C are arranged, wherein the outer layer A is a non-foamed layer, 15% of the total thickness of the layer A thickness, foamed core layer B, 75% of the total thickness, C is the inner layer of non-foamed layer, the thickness of layer C is 10% of total thickness, the total thickness of the bottle 0.6_. 瓶子垂直承压为250N。 Vertical pressure bottle was 250N.

[0061] 所述的层A是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母0.5 ; [0061] The layer A is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, 0.5 masterbatch;

[0062] 所述的层B是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母0,发泡剂 [0062] The layer B is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, 0 masterbatch, the blowing agent

1.5 ; 1.5;

[0063] 所述的层C是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母0.5 ; [0063] The layer C is made of the following parts by weight of raw materials: high density polyethylene (HDPE) 100, 0.5 masterbatch;

[0064] 所述的层A、层B、层C中用到的高密度聚乙烯具有以下特性:在190 °C,2160g的负荷下,测定恪融指数为0.31g/10min ;恪融温度为134°C,刚性为9021 kg / cm 20 [0064] The layer A, layer B, layer C used in the high density polyethylene has the following characteristics: the load at 190 ° C, 2160 g, the melt index was measured Ke 0.31g / 10min; melting temperature Verified 134 ° C, the rigidity of 9021 kg / cm 20

[0065]制备方法为:采用三螺杆吹瓶机,将每层用到的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,将挤塑机螺杆挤出A层螺杆的三个加热段温度分别控制在175°C、1800C、1800C,挤出B层螺杆三个加热段温度分别控制在175°C、210°C、180°C,挤出C层螺杆的三个加热段温度分别控制在175°C、180 °C、180 °C,再将分配好的各层原料挤出到模头,模头温度控制在180°C,经模头挤出至模口,吹塑定型即得此制品。 Preparation of [0065] methods: using three-screw blow molding machine, the raw material used in each layer in proportion to stir respective mixing hopper, thoroughly dried, the screws of the extruder screw extruder three heating layer A stage temperature were controlled at 175 ° C, 1800C, 1800C, three screw extruder heating zone B layer were controlled at a temperature of 175 ° C, 210 ° C, 180 ° C, the C layer extruder screw three heating zone temperatures control 175 ° C, 180 ° C, 180 ° C, and then extruded material layers to the allocated die, the die temperature is controlled at 180 ° C, extruded through a die to die, i.e., blow styling get this product.

[0066] 以实施例4制得的壁厚为0.6mm的瓶子为例,若瓶内装满4°C的纯水,放置在60°C的水浴中,瓶内水温每升高一度的时间发泡瓶比未发泡瓶平均慢4.5秒。 [0066] In Example 4 the wall thickness of an example embodiment prepared a bottle of 0.6mm, when the bottle is filled with pure water at 4 ° C, placed in a water bath of 60 ° C, the temperature is increased once the bottle time foaming bottle slower than the non-foamed bottle average 4.5 seconds.

[0067] 实施例5 [0067] Example 5

[0068] 瓶子采用挤吹的工艺生产,瓶壁按照层A/层B/层C/层A排列,其中层A为外层的非发泡层,外层层A的厚度占总厚度的10%,内层层A的厚度占总厚度的10%,层B为发泡芯层,占总厚度的50%,层C为内层的非发泡层,层C的厚度占总厚度的30%,瓶子总厚度为0.8mm。 [0068] The use of bottles extrusion blow molding process to produce bottle wall according Layer A / Layer B / Layer C / layer A are arranged, wherein the layer A is the outer non-foamed layer, the thickness of the total thickness of the outer layer A is 10 %, 10% of the total thickness of the layer a thickness, a foamed core layer B, 50% of the total thickness of the inner layer C is a non-foamed layer, the total thickness of the layer C thickness is 30 %, of the total thickness of the bottle 0.8mm. 瓶子垂直承压为260N。 Vertical pressure bottle was 260N.

[0069] 所述的层A是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,色母0.5 ; [0069] The layer A is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, 0.5 masterbatch;

[0070] 所述的层B是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100,发泡剂2 ; [0070] The layer B is prepared from the following raw materials by weight: high-density polyethylene (HDPE) 100, the foaming agent 2;

[0071] 所述的层C是由下述重量份的原料制成:高密度聚乙烯(HDPE) 100 (其中添加50的二次料)。 [0071] The layer C is made of the following parts by weight of raw materials: high density polyethylene (HDPE) 100 (the secondary material 50 added thereto).

[0072] 所述的层A、层B、层C中用到的高密度聚乙烯具有以下特性:在190 °C,2160g的负荷下,测定恪融指数为0.31g/10min ;恪融温度为134°C,刚性为9021 kg / cm 2; [0072] The layer A, layer B, layer C used in the high density polyethylene has the following characteristics: the load at 190 ° C, 2160 g, the melt index was measured Ke 0.31g / 10min; melting temperature Verified 134 ° C, the rigidity of 9021 kg / cm 2;

[0073] 所述的层C中用到的二次料,为层A、层B、层C相同物理指标的水口料。 [0073] The layer C used in the secondary material, a layer A, layer B, the same physical layer C index nozzle material.

[0074]制备方法为:采用三螺杆吹瓶机,将每层用到的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,将挤塑机螺杆挤出A层螺杆的三个加热段温度分别控制在175°C、1800C、1800C,挤出B层螺杆三个加热段温度分别控制在175°C、210°C、180°C,挤出C层螺杆的三个加热段温度分别控制在175°C、185 °C、180 °C,再将分配好的各层原料挤出到模头,模头温度控制在180°C,经模头挤出至模口,吹塑定型即得此制品。 Preparation of [0074] methods: using three-screw blow molding machine, the raw material used in each layer in proportion to stir respective mixing hopper, thoroughly dried, the screws of the extruder screw extruder three heating layer A stage temperature were controlled at 175 ° C, 1800C, 1800C, three screw extruder heating zone B layer were controlled at a temperature of 175 ° C, 210 ° C, 180 ° C, the C layer extruder screw three heating zone temperatures control 175 ° C, 185 ° C, 180 ° C, and then extruded material layers to the allocated die, the die temperature is controlled at 180 ° C, extruded through a die to die, i.e., blow styling get this product.

[0075] 以实施例5制得的壁厚为0.8mm的瓶子为例,若瓶内装满4°C的纯水,放置在60°C的水浴中,瓶内水温每升高一度的时间发泡瓶比未发泡瓶平均慢5秒。 [0075] In Example 5 a wall thickness of 0.8mm obtained in the bottle as an example embodiment, when the bottle filled with water at 4 ° C, placed in a water bath of 60 ° C, the temperature is increased once the bottle time bottle bottle unfoamed foaming than 5 seconds slower average.

[0076] 实施例6 [0076] Example 6

[0077] 瓶子采用挤吹的工艺生产,瓶壁按照层A/层B排列,其中层A为外层的非发泡层,层A的厚度占总厚度的20%,层B为发泡层,占总厚度的80%,瓶子总厚度为0.5mm。 [0077] The use of bottles extrusion blow molding process to produce bottle wall according Layer A / Layer B are arranged, wherein the outer layer A is a non-foamed layer, 20% of the total thickness of the thickness of the layer A, layer B is a foam layer 80% of the total thickness, the total thickness of the bottle is 0.5mm. 瓶子垂直承压为270N。 Vertical pressure bottle was 270N.

[0078] 所述的层A是由下述重量份的原料制成:聚丙烯(PP) 100,色母I ; [0078] The layer A is made of the following parts by weight of the starting material: Polypropylene (PP) 100, masterbatch I;

[0079] 所述的层B是由下述重量份的原料制成:聚丙烯(PP) 100,色母0.5,碳酸氢钠发泡剂1.5 ; [0079] The layer B is made of the following parts by weight of the starting material: Polypropylene (PP) 100, masterbatch 0.5, 1.5 sodium bicarbonate foaming agent;

[0080] 所述的层A、层B中用到的聚丙烯具有以下特性:在190°C,2160g的负荷下,测定熔融指数为0.38g/10min ;熔融温度为165°C,刚性为11412 kg / cm 2。 Layer A [0080] according to, the polypropylene used in layer B has the following characteristics: the load at 190 ° C, 2160 g measured melt index of 0.38g / 10min; melting temperature of 165 ° C, the rigidity is 11412 kg / cm 2.

[0081] 制备方法为:采用双螺杆吹瓶机,将每层用到的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,将挤塑机挤出A层螺杆的三个加热段温度分别控制在185 °C、195°C、190°C,挤出B层螺杆的三个加热段温度分别控制在185°C、210°C、190°C,再将分配好的各层原料挤出到模头,模头温度控制在185°C,经模头挤出至模口,吹塑定型即得此制品O Preparation of [0081] method: using a twin-screw blow molding machine, the raw material used in each layer in proportion to stir respective mixing hopper, thoroughly dried, the A layer extruder screw extruder three heating zones temperature were controlled at 185 ° C, 195 ° C, 190 ° C, the B layer extruder screw three heating zones were controlled at a temperature of 185 ° C, 210 ° C, 190 ° C, and then a good distribution material layers extruded into a die, the die temperature is controlled at 185 ° C, extruded through a die to die, blow-styling product to obtain this O

[0082] 以实施例6制得的壁厚为0.5mm的瓶子为例,若瓶内装满4°C的纯水,放置在60°C的水浴中,瓶内水温每升高一度的时间发泡瓶比未发泡瓶平均慢3.5秒。 [0082] In Example 6 a wall thickness of 0.5mm obtained in the bottle as an example embodiment, when the bottle filled with water at 4 ° C, placed in a water bath of 60 ° C, the temperature is increased once the bottle time foaming bottle slower than the non-foamed bottle average 3.5 seconds.

[0083] 实施例7 [0083] Example 7

[0084] 瓶子采用挤吹的工艺生产,瓶壁按照层A/层B/层C/层A排列,其中层A为外层的非发泡层,外层层A的厚度占总厚度的10%,内层层A的厚度占总厚度的10%,层B为发泡芯层,占总厚度的50%,层C为内层的非发泡层,层C的厚度占总厚度的30%,瓶子总厚度为0.5mm。 [0084] The use of bottles extrusion blow molding process to produce bottle wall according Layer A / Layer B / Layer C / layer A are arranged, wherein the layer A is the outer non-foamed layer, the thickness of the total thickness of the outer layer A is 10 %, 10% of the total thickness of the layer a thickness, a foamed core layer B, 50% of the total thickness of the inner layer C is a non-foamed layer, the total thickness of the layer C thickness is 30 %, of the total thickness of the bottle is 0.5mm. 瓶子垂直承压为310N。 Vertical pressure bottle was 310N.

[0085] 所述的层A是由下述重量份的原料制成:聚丙烯(PP) 100,色母0.5; [0085] The layer A is made of the following parts by weight of the starting material: Polypropylene (PP) 100, 0.5 masterbatch;

[0086] 所述的层B是由下述重量份的原料制成:聚丙烯(PP) 100,发泡剂2; [0086] The layer B is made of the following parts by weight of the starting material: Polypropylene (PP) 100, the foaming agent 2;

[0087] 所述的层C是由下述重量份的原料制成:聚丙烯(PP) 100 (其中添加50的二次料); [0087] The layer C is made of the following parts by weight of the starting material: Polypropylene (PP) 100 (50, secondary materials added thereto);

[0088] 所述的层A、层B、层C中用到的聚丙烯具有以下特性:在190°C,2160g的负荷下,测定熔融指数为0.38g/10min ;熔融温度为165°C,刚性为11412 kg / cm 2; Layer A [0088] the layer B, the polypropylene used in layer C has the following characteristics: the load at 190 ° C, 2160 g measured melt index of 0.38g / 10min; melting temperature of 165 ° C, rigidity to 11412 kg / cm 2;

[0089] 所述的层C中用到的二次料,为层A、层B、层C相同物理指标的水口料。 [0089] The layer C used in the secondary material, a layer A, layer B, the same physical layer C index nozzle material.

[0090]制备方法为:采用三螺杆吹瓶机,将每层用到的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,将挤塑机螺杆挤出A层螺杆的三个加热段温度分别控制在185°C、1950C、1900C,挤出B层螺杆三个加热段温度分别控制在185°C、210°C、190°C,挤出C层螺杆的三个加热段温度分别控制在185°C、195 °C、185 °C,再将分配好的各层原料挤出到模头,模头温度控制在180°C,经模头挤出至模口,吹塑定型即得此制品。 Preparation of [0090] methods: using three-screw blow molding machine, the raw material used in each layer in proportion to stir respective mixing hopper, thoroughly dried, the screws of the extruder screw extruder three heating layer A stage temperature were controlled at 185 ° C, 1950C, 1900C, three screw extruder heating zone B layer were controlled at a temperature of 185 ° C, 210 ° C, 190 ° C, the C layer extruder screw three heating zone temperatures control 185 ° C, 195 ° C, 185 ° C, and then extruded material layers to the allocated die, the die temperature is controlled at 180 ° C, extruded through a die to die, i.e., blow styling get this product.

[0091] 以实施例7制得的壁厚为0.5mm的瓶子为例,若瓶内装满4°C的纯水,放置在60°C的水浴中,瓶内水温每升高一度的时间发泡瓶比未发泡瓶平均慢3秒。 [0091] In Example 7 obtained in the thickness of 0.5mm embodiment of the bottle, for example, when the bottle filled with water at 4 ° C, placed in a water bath of 60 ° C, the temperature is increased once the bottle time foaming bottle slower than the average non-foamed bottle 3 seconds.

[0092] 实施例8 [0092] Example 8

[0093] 瓶子采用挤吹的工艺生产,瓶壁按照层A/层B排列,其中层A为外层的非发泡层,层A的厚度占总厚度的20%,层B为发泡层,占总厚度的80%,瓶子总厚度为0.5mm。 [0093] The use of bottles extrusion blow molding process to produce bottle wall according Layer A / Layer B are arranged, wherein the outer layer A is a non-foamed layer, 20% of the total thickness of the thickness of the layer A, layer B is a foam layer 80% of the total thickness, the total thickness of the bottle is 0.5mm. 瓶子垂直承压为240N。 Vertical pressure bottle was 240N.

[0094] 所述的层A是由下述重量份的原料制成:聚丙烯(PP)80,高密度聚乙烯(HDPE)20,色母I ; [0094] The layer A is made of the following parts by weight of the starting material: Polypropylene (PP) 80, a high density polyethylene (HDPE) 20, masterbatch I;

[0095] 所述的层B是由下述重量份的原料制成:聚丙烯(PP) 80,高密度聚乙烯(HDPE) 20,色母0.5,碳酸氢钠发泡剂1.5 ; [0095] The layer B is made of the following parts by weight of the starting material: Polypropylene (PP) 80, a high density polyethylene (HDPE) 20, masterbatch 0.5, 1.5 sodium bicarbonate foaming agent;

[0096] 所述的层A、层B中用到的高密度聚乙烯具有以下特性:在190°C,2160g的负荷下,测定熔融指数为0.33g/10min ;熔融温度为132°C,刚性为8045 kg / cm 2; [0096] The layer A, layer B used in the high density polyethylene has the following characteristics: the load at 190 ° C, 2160 g measured melt index of 0.33g / 10min; melting temperature of 132 ° C, rigid to 8045 kg / cm 2;

[0097] 所述的层A、层B中用到的聚丙烯具有以下特性:在190°C,2160g的负荷下,测定熔融指数为0.38g/10min ;熔融温度为165°C,刚性为11412 kg / cm 2。 Layer A [0097] according to, the polypropylene used in layer B has the following characteristics: the load at 190 ° C, 2160 g measured melt index of 0.38g / 10min; melting temperature of 165 ° C, the rigidity is 11412 kg / cm 2.

[0098] 制备方法为:采用双螺杆吹瓶机,将每层用到的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,将挤塑机挤出A层螺杆的三个加热段温度分别控制在175°C、1900C、1800C,挤出B层螺杆的三个加热段温度分别控制在175°C、210°C、180°C,再将分配好的各层原料挤出到模头,模头温度控制在180°C,经模头挤出至模口,吹塑定型即得此制品O Preparation of [0098] method: using a twin-screw blow molding machine, the raw material used in each layer in proportion to stir respective mixing hopper, thoroughly dried, the A layer extruder screw extruder three heating zones temperature were controlled at 175 ° C, 1900C, 1800C, screw extruding layer B three heating zones were controlled at a temperature of 175 ° C, 210 ° C, 180 ° C, and then extruded material layers to the allocated mold head, a die temperature is controlled at 180 ° C, extruded through a die to die, blow-styling product to obtain this O

[0099] 以实施例8制得的壁厚为0.5mm的瓶子为例,若瓶内装满4°C的纯水,放置在60°C的水浴中,瓶内水温每升高一度的时间发泡瓶比未发泡瓶平均慢3秒。 [0099] In Example 8 a wall thickness of 0.5mm obtained in the bottle as an example embodiment, when the bottle filled with water at 4 ° C, placed in a water bath of 60 ° C, the temperature is increased once the bottle time foaming bottle slower than the average non-foamed bottle 3 seconds.

Claims (10)

  1. 1.一种发泡瓶子,其特征在于,所述瓶子瓶壁为多层结构,其中包括至少一层发泡层和至少一层非发泡层;优选所述发泡瓶子为食品包装用发泡瓶子;优选瓶壁总厚度为0.2-0.9mm,发泡层总厚度为瓶壁总厚度的40% -80%。 1. A foamed bottle, wherein the bottle sidewall is a multilayer structure, comprising at least one foamed layer and at least one non-foamed layer; preferably the foamed food packaging is a bottle made bubble vial; total thickness of the sidewall is preferably 0.2-0.9mm, the total thickness of the foam layer is 40% -80% of the total thickness of the bottle wall.
  2. 2.根据权利要求1所述的发泡瓶子,其特征在于,所述发泡层为微发泡聚合物层,其密度为0.6-0.9g/m3。 The foamed bottle according to claim 1, wherein said foam layer is a microcellular foamed polymer layer, having a density of 0.6-0.9g / m3.
  3. 3.根据权利要求1所述的发泡瓶子,其特征在于,所述瓶壁为至少三层结构,其中所述发泡层的两侧各有一层非发泡层;优选所述非发泡层外表面无肉眼可见微孔;优选内外两层非发泡层各自分别占非发泡层总厚度的30% -70%。 3. The foamed bottle according to claim 1, wherein said sidewall is at least three-layer structure wherein both sides of the foamed layer each have a layer of non-foamed layer; preferably the non-foamed an outer porous layer surface no visible; non-foamed layer and inner layers preferably each accounted for 30% -70% of the total thickness of the non-foamed layer.
  4. 4.根据权利要求1所述的发泡瓶子,其特征在于,所述瓶壁结构为层A/层B、层A/层B/层A、层A/层B/层C、层A/层B/层A/层C或层A/层B/层C/层A排列;其中层B为发泡层,层A和层C各自表示不同的非发泡层。 Foamed bottle according to claim 1, wherein said sidewall structure Layer A / Layer B, Layer A / Layer B / Layer A, Layer A / Layer B / Layer C, Layer A / layer B / layer a / layer C or layer a / layer B / layer C / layer a array; wherein the foam layer is a layer B, the layers a and C each represent different non-foamed layer.
  5. 5.根据权利要求1〜4任意一项所述的发泡瓶子,其特征在于,所述发泡层和非发泡层的材质各自独立选自高密度聚乙烯、聚丙烯和聚苯乙烯中的一种或一种以上的混合。 The foamed bottle according to any one of claim 1 ~ 4, characterized in that the material of the foamed layer and the non-foamed layer are each independently selected from high density polyethylene, polypropylene and polystyrene the mixing one or more than one.
  6. 6.根据权利要求1〜4任意一项所述的发泡瓶子,其特征在于,所述发泡层是以碳酸盐为发泡剂制备得到;优选所述碳酸盐为碳酸氢钠。 ~ 4 according to claim any one of the expansion bottle, characterized in that said foam layer is obtained for the preparation of a carbonate blowing agent; preferably the carbonate is sodium bicarbonate.
  7. 7.根据权利要求1〜4任意一项所述的发泡瓶子,其特征在于,所述发泡瓶子由各原料通过包括挤吹或注拉吹步骤的方法制备得到。 ~ 4 according to claim any one of the expansion bottle, characterized in that the starting material was prepared by the foamed bottle comprising an extrusion blow or injection stretch blow by step.
  8. 8.根据权利要求7所述的发泡瓶子,其特征在于,所述发泡瓶子由包括如下步骤的方法制备得到:将各层的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,再用挤塑机将分配好的各层原料挤出到同一分配器中,经模口挤出,定型即得产品;优选制备时挤塑机机身温度控制在170-250°C。 After the material layers Stir proportionally respective mixing hopper, sufficiently dried: foaming bottle according to claim 7, wherein said foamed bottle was prepared by a method comprising the steps of , then a good distribution of the extruder extruded material layers to the same dispenser, extruded through a die, shaped product is obtained; extruder body temperature controlled at 170-250 ° C during preferably prepared.
  9. 9.权利要求7或8所述的发泡瓶子的制备方法,其特征在于,所述方法包括如下步骤:将各层的原料在各自的混合料斗中按比例搅拌均匀,充分干燥后,再用挤塑机将分配好的各层原料挤出到同一分配器中,经模口挤出,定型即得产品。 9. The production method of claim 7 or claim 8 foamed bottle, characterized in that the method comprises the steps of: after the layers of material in proportion to stir respective mixing hopper, sufficiently dried, then the extruder extruding the material layers a good distribution of the same dispenser, is extruded through a die, shaped product is obtained.
  10. 10.根据权利要求9所述的制备方法,其特征在于,所述发泡层是以碳酸盐类发泡剂制备得到。 10. The production method according to claim 9, characterized in that said foamed layer are prepared to give the carbonate foaming agent.
CN 201510293020 2015-06-02 2015-06-02 Foaming bottle and preparation method thereof CN106275678A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5819991A (en) * 1994-12-21 1998-10-13 Wella Ag Bottle-type plastic container
US20020004110A1 (en) * 1997-06-06 2002-01-10 James River Corporation Of Virginia Heat insulating paper cups
US20060065992A1 (en) * 2004-04-16 2006-03-30 Hutchinson Gerald A Mono and multi-layer articles and compression methods of making the same
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US20080185301A1 (en) * 2007-02-02 2008-08-07 Rick Merical Containers Intended for Moisture-Sensitive Products
CN102935752A (en) * 2012-08-31 2013-02-20 芜湖市弘瑞包装制品有限公司 Micro-foaming sheet for food cup
CN103552291A (en) * 2013-11-06 2014-02-05 上海译科实业有限公司 Barrier foaming hose and preparation method thereof
CN103832031A (en) * 2014-03-17 2014-06-04 罗景明 Foaming regeneration environment-friendly plastic sheet and preparation method thereof
CN205034440U (en) * 2015-06-02 2016-02-17 内蒙古伊利实业集团股份有限公司 Foaming bottle

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5819991A (en) * 1994-12-21 1998-10-13 Wella Ag Bottle-type plastic container
US20020004110A1 (en) * 1997-06-06 2002-01-10 James River Corporation Of Virginia Heat insulating paper cups
US20060065992A1 (en) * 2004-04-16 2006-03-30 Hutchinson Gerald A Mono and multi-layer articles and compression methods of making the same
US20080185301A1 (en) * 2007-02-02 2008-08-07 Rick Merical Containers Intended for Moisture-Sensitive Products
CN101157286A (en) * 2007-08-29 2008-04-09 东莞市格羚塑胶有限公司 A multi-layer foam material as well as its preparing method
CN102935752A (en) * 2012-08-31 2013-02-20 芜湖市弘瑞包装制品有限公司 Micro-foaming sheet for food cup
CN103552291A (en) * 2013-11-06 2014-02-05 上海译科实业有限公司 Barrier foaming hose and preparation method thereof
CN103832031A (en) * 2014-03-17 2014-06-04 罗景明 Foaming regeneration environment-friendly plastic sheet and preparation method thereof
CN205034440U (en) * 2015-06-02 2016-02-17 内蒙古伊利实业集团股份有限公司 Foaming bottle

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