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Publication numberCN103124626 A
Publication typeApplication
Application numberCN 201180045591
PCT numberPCT/EP2011/004298
Publication date29 May 2013
Filing date26 Aug 2011
Priority date24 Sep 2010
Also published asDE102010046378A1, DE102010046378B4, EP2618985A1, WO2012038018A1
Publication number201180045591.9, CN 103124626 A, CN 103124626A, CN 201180045591, CN-A-103124626, CN103124626 A, CN103124626A, CN201180045591, CN201180045591.9, PCT/2011/4298, PCT/EP/11/004298, PCT/EP/11/04298, PCT/EP/2011/004298, PCT/EP/2011/04298, PCT/EP11/004298, PCT/EP11/04298, PCT/EP11004298, PCT/EP1104298, PCT/EP2011/004298, PCT/EP2011/04298, PCT/EP2011004298, PCT/EP201104298
InventorsD尤利茨, R赫尔米格, H莱曼
Applicant考特克斯特克斯罗恩有限公司及两合公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Multilayer plastics items with barrier properties and process for producing the same
CN 103124626 A
Abstract
The present invention relates to multilayer plastics items, encompassing at least two layers based on non-polar polyolefins and, located between the said two layers and in direct contact with the same, a layer with barrier properties with respect to hydrocarbons, and also to a process for producing the same.
Claims(13)  translated from Chinese
1.生产多层塑料物品的方法,它包括基于非极性聚烯烃的至少两层挤出层和位于所述两层之间并与之直接接触的对烃类具有阻挡性能的挤出层,其中该方法包括在共挤出的吹塑体系内生产管状多层塑料型坯的步骤,其特征在于只用一个挤出机,由共混物进行具有阻挡性能的层的挤出,所述共混物包括对烃类具有阻挡性能的聚合物且包括具有粘合促进性能的聚合物,并在挤出机中在共混物内部进行对烃类具有阻挡性能的聚合物和具有粘合促进性能的聚合物的至少一些分层时的熔融温度下进行所述挤出。 1. The method of producing a multilayer plastic article, which comprises the extrusion and with a hydrocarbon having a barrier layer between the properties of the nonpolar polyolefin and at least two extruded layers in said two layers based on direct contact, wherein the method comprises the steps of producing a tubular plastic parison in a multilayer coextrusion blow molding system, characterized in that only one extruder, extrusion layer having barrier properties by the blend of the total a hydrocarbon mixture comprising a polymer having barrier properties and comprises a polymer having adhesion promoting properties, in an extruder and within the polymer blends of hydrocarbons having barrier properties and adhesion-promoting properties with the melting temperature of at least some of the layered polymers when next the extrusion.
2.权利要求1的方法,其特征在于具有阻挡性能的聚合物在具有阻挡性能的挤出层内部存在,以颗粒和相互交叠的层状结构的形式非均匀地分布。 The method according to claim 1, characterized in that the polymer having barrier properties in the interior extruded layer having barrier properties exist in the form of particles, and layered structure overlapping the non-uniform distribution.
3.权利要求1或2的方法,其特征在于熔体温度范围为160C _260C,优选范围为200 0C -225 C,优选范围为205 C -215 C,尤其优选范围为208 C _212C。 3. The method of claim 1 or claim 2, wherein the melt temperature range of 160 C _260 C, preferably in the range 200 0C -225 C, preferably in the range of 205 C -215 C, particularly preferably in the range of 208 C _212 C.
4.权利要求1-3任何一项的方法,其特征在于为了挤出具有阻挡性能的层,使用不具有剪切部分和/或混合部分的螺杆挤出机,优选不具有剪切部分且不具有混合部分的螺杆挤出机。 1-3 4. The process of any one of the preceding claims, characterized in that the extruded layer to barrier properties, without the use of a screw having a cutting portion and / or the mixing section of the extruder preferably does not have a cut portion screw extruder having a mixing section.
5.权利要求1-4任何一项的方法,其特征在于基于聚烯烃的至少两层挤出层中的聚烯烃彼此独立地分别选自由下述组成的组:非极性高密度聚乙烯(HPDE),低密度聚乙烯(LDPE),线性低密度聚乙烯(LLDPE),聚丙烯(PP),乙烯-丙烯共聚物和这些的混合物,优选这两层分别是非极性高密度聚乙烯(HDPE)。 1-4 5. The process of any one of the preceding claims, characterized in that at least two extruded polyolefin-based polyolefin layers independently of one another are selected from the group consisting of the following composition: nonpolar high density polyethylene ( HPDE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), ethylene - propylene copolymers and mixtures of these, the two layers are preferably nonpolar high density polyethylene (HDPE ).
6.权利要求1-5任何一项的方法,其特征在于对烃类具有阻挡性能的聚合物是选自由下述组成的组中的聚合物:乙烯-乙烯醇共聚物(EVOH),聚芳基酰胺,聚酰胺(PA),聚乙烯醇(PVOH),和它们的混合物,优选是乙烯-乙烯醇共聚物(EVOH),尤其优选基于共聚物的分子组成,乙烯比例为28-36mol%的乙烯-乙烯醇共聚物。 1-5 6. The method of any one of the preceding claims, characterized in that the group of hydrocarbon polymers having barrier properties selected from the group consisting of polymers: ethylene - vinyl alcohol copolymer (EVOH), polyarylate amide, polyamide (PA), polyvinyl alcohol (PVOH), and mixtures thereof, preferably ethylene - vinyl alcohol copolymer (EVOH), especially preferred copolymers based on molecular composition ratio of 28-36mol% of ethylene ethylene - vinyl alcohol copolymer.
7.权利要求1-6任何一项的方法,其特征在于具有粘合促进性能的聚合物选自用极性基团官能化的聚烯烃,优选乙烯与不饱和羧酸或羧酸酐的共聚物,尤其优选乙烯与马来酸酐的共聚物。 7. The method of any one of claims 1-6, characterized in that the adhesion promoting properties of a polymer having a polar group selected from a functionalized polyolefin, preferably ethylene and an unsaturated carboxylic acid or carboxylic anhydride copolymer , particularly preferably a copolymer of ethylene and maleic anhydride.
8.权利要求1-7任何一项的方法,其特征在于在共混物内具有阻挡性能的聚合物的重量份与具有粘合促进性能的聚合物的重量份之比的范围优选为15:85-40:60,优选20:80-35:75,尤其优选25:75-30:70,在每一情况下基于该共混物的总重量。 1-7 8. The process of any one of the preceding claims, characterized in that the parts by weight of the blend having barrier properties with polymers having a range of properties to promote adhesion of polymer parts by weight ratio is preferably 15: 85-40: 60, preferably 20: 80-35: 75, particularly preferably 25: 75-30: 70, in each case based on the total weight of the blend.
9.权利要求1-8任何一项的方法,其特征在于具有阻挡性能的挤出层的厚度是所述层和两层聚烯烃层的层厚之和的2-10%,优选3-8%,尤其优选5.5-7.5%。 9. A method according to any one of claims 1-8, characterized in that the thickness of the barrier properties of the extruded layer having a thickness of 2-10% of the layer and the polyolefin layer and the two layers, preferably 3-8 %, particularly preferably 5.5-7.5%.
10.权利要求1-9任何一项的方法,其特征在于多层塑料物品包括进一步的挤出层,所述进一步的挤出层彼此独立地通过共挤出施加到聚烯烃基层的一层或两层上,并与对烃类具有阻挡性能的挤出层直接接触。 10. The method as claimed in any one of 1-9, characterized in that the multilayer plastic article comprising extruding a further layer, said further layer are independently extruded through the coextrusion layer applied to the base layer or polyolefin on two floors, and with hydrocarbons having direct contact with the barrier properties of extruded layers.
11.权利要求1-10任何一项的方法,其特征在于用于运输或用于储存液体和/或气态烃类的多层中空塑料体,或者用于所述中空塑料体的零配件,优选燃料容器。 1-10 11. The method of any one of the preceding claims, wherein the means for transport or for storage of liquid and / or multi-layer hollow plastic body gaseous hydrocarbons, or for the hollow plastic body parts, preferably fuel container.
12.多层塑料物品,它包括基于非极性聚烯烃的至少两层,和位于所述两层之间且与之直接接触的对烃类具有阻挡性能的层,其中具有阻挡性能的层包括对烃类具有阻挡性能的聚合物且包括具有粘合促进性能的聚合物,其特征在于,具有阻挡性能的聚合物在具有阻挡性能的层内部存在,以颗粒和相互交叠的层状结构的形式非均匀地分布。 12. The multilayer plastic article, comprising at least two layers based on the non-polar polyolefin layer and a layer with hydrocarbons and having direct contact with the barrier properties, having barrier properties is located between the two layers comprising a hydrocarbon polymer having barrier properties and adhesion promoting properties comprises a polymer, characterized in that the polymer has the barrier properties of the inner layers having barrier properties exist as particles and the layered structure overlapping in the form of non-uniformly distributed.
13.权利要求12的多层塑料物品,其特征在于基于非极性聚烯烃的两层和位于其间且与之直接接触的具有阻挡性能的层分别包括通过权利要求1-12任何一项或多项的方法生产的挤出层。 Multilayer plastic article according to claim 12, wherein the non-polar polyolefin-based layers located therebetween and in direct contact with the layer having barrier properties respectively comprise any one of the claims 1-12 or The method of production of extruded layer items.
Description  translated from Chinese

具有阻挡性能的多层塑料物品及其生产方法 Multilayer plastic article having barrier properties and production method of

[0001] 本发明涉及多层塑料物品,它包括基于非极性聚烯烃的至少两层和包括位于所述两层之间并与之接触的对烃类具有阻挡性能的层,本发明还涉及其生产方法。 [0001] The present invention relates to multilayer plastic articles, comprising at least two layers based on the non-polar polyolefin and the layer of hydrocarbons having barrier properties comprising the two layers located between and in contact with, the present invention also relates to its production process.

[0002] 当今由塑料制成的容器被广泛用于运输和储存危险的液体和气体产品,因为它们具有耐化学性,机械强度,良好的可加工性,具体地包括在复杂成型工艺中的加工性,和低重量。 [0002] The container made of plastics today are widely used for the transport and storage of hazardous liquid and gaseous products, because they have chemical resistance, mechanical strength, good workability, specifically including processing of complex molding process resistance, and low weight. 在车辆的构造中,作为例举,由塑料制成的燃料容器几乎完全替代了先前常规的金属燃料容器。 In the structure of the vehicle, as exemplified, fuel containers made of plastic almost completely replaced the previous conventional metal fuel container. 当今,便携式或非-固定的容器,例如用于可燃液体和类似物的汽油罐(petrolcanister),瓶子,圆筒和油箱也几乎仅仅由塑料生产。 Today, portable or non - fixed containers, such as a gasoline tank (petrolcanister) for flammable liquids and the like, bottle, cylinder and tank are almost exclusively made of plastic production. 特别地在较低重量/体积比,避免腐蚀问题和低成本生产中发现塑料容器的特别的优点。 Particularly at lower weight / volume ratio, particular advantage to avoid plastic containers produced at low cost and corrosion problems found.

[0003] 具体地,在所述应用部分中,对位于容器/油箱内部内的液体和/或气体不可渗透是重要的。 [0003] In particular, in the application section, located in the liquid container / tank within the interior and / or gas impermeable it is important. 因此,作为例举,当今塑料容器必须符合就烃的渗透而言的严格的排放法规。 Therefore, as exemplified in today's plastic containers must meet stringent emissions regulations on hydrocarbons in terms of penetration.

[0004] 聚烯烃树脂,例如聚乙烯,聚丙烯及其共聚物,具有非常良好的可模塑性和可加工性以及高的机械强度。 [0004] The polyolefin resins such as polyethylene, polypropylene and copolymers thereof, with a very good moldability and workability as well as high mechanical strength. 然而,它们对挥发性的非极性有机物质,尤其烃类的渗透性相对高。 However, their non-polar volatile organic substances, especially hydrocarbons of relatively high permeability. 因此,重要的是提供运输和/或储存包括烃类,例如汽油或柴油在内的危险物质用容器合适的处理。 Therefore, it is important to provide transportation and / or storage include hydrocarbons, such as gasoline or diesel dangerous substances, including container suitable processing. 尤其借助氟化,涂布或等离子聚合,由这些聚烯烃制造的塑料容器的阻挡性能可得到显著改进。 In particular, by means of fluorination, coating or plasma polymerization, the barrier properties of polyolefin manufactured from these plastic containers can be markedly improved.

[0005] 表面改性和涂布方法的通常的缺点是,阻挡层必然施加在容器的内部和/或外部表面上,因此未受保护地暴露于环境影响下。 [0005] The usual drawback surface modification and coating method is necessarily a barrier layer applied to the interior and / or exterior surface of the container, and therefore unprotected exposure to ambient effect. 因此,随着时间流逝,可出现上述阻挡层的分离和/或化学改变,和这自然会导致阻挡性能的显著损害。 Thus, over time, there may be isolated and / or chemical change in the barrier layer, and this will naturally lead to significant damage to the barrier properties.

[0006] 因此,目前的研发主要集中在例如通过共挤出工艺,生产并构造多层体系,其中具有阻挡性能的聚合物,主要是乙烯-乙烯醇共聚物(EVOH)和聚酰胺(PA)与聚烯烃和其他成分一体化,得到多层复合材料。 [0006] Thus, the present research focused on the process, for example by coextrusion, multi-layer systems produced and constructed, in which a polymer having barrier properties, mainly ethylene - vinyl alcohol copolymer (EVOH) and polyamide (PA) integration with polyolefins and other ingredients to obtain a multi-layered composite material. 阻挡聚合物的常见位置大致是容器壁的中间;这导致的第一结果是最小化在阻挡聚合物内产生的弯曲应力,其中当施加机械负载时,所述阻挡聚合物大多数相对脆,和第二结果是,基体材料保护阻挡聚合物避免环境影响。 Common position substantially intermediate barrier polymer container wall; a first result of this is due to minimize bending stresses generated within the barrier polymer, wherein when a mechanical load is applied, the majority of the barrier polymer is relatively brittle, and The second result is a protective barrier polymer matrix material to avoid environmental impacts. 同样可能的情况是使用共挤出技术,将仍然进一步的层一体化到多层复合材料内,和因此这一方法得到仅仅使用单一聚合物不可能实现的具有宽泛的各种有利性能的材料。 Also possible is the use of coextrusion techniques, the layer will be still further integrated into the multi-layer composite material, and so this method can not be obtained using only a single polymer having a wide variety of materials to achieve the advantageous properties.

[0007] 然而,缺点是通常作为具有阻挡性能使用的聚合物,例如乙烯-乙烯基共聚物和聚酰胺通常具有极性,且相对于非极性的基础材料,例如聚乙烯和聚丙烯,不具有任何种类的粘合性能。 [0007] However, the drawback is usually used as a polymer having barrier properties, such as ethylene - vinyl copolymers and polyamides typically have polar and non-polar with respect to the base material, such as polyethylene and polypropylene, with any kind of adhesive properties. 即使在熔融状态下共挤出所述材料的两层并“粘合”到彼此上,在冷却工艺之后或者更早,它们也分离成两个空间分离的层。 Even co-extruded in the molten state of the material layers and "bonded" to each other, after the cooling process, or earlier, they split into two spatially separated layer.

[0008] 因此,使用共挤出,在由低成本的聚烯烃制造的基础材料制成的层和由明显更加昂贵的阻挡聚合物制成的阻挡层(它所使用的层厚因此也最小化)之间引入粘合促进层,所述粘合促进层确保在其他情况下不相容的极性和非极性层耐久粘结。 [0008] Thus, the use of coextruded layer and the base material in the manufacture of low-cost polyolefins made significantly more expensive barrier blocking layer made of a polymer (thickness and therefore it is used to minimize the the introduction of adhesion between) promoting layer, the adhesion promoting layer ensures polar and non-polar layer durable bond in other cases incompatible. 作为例举,当今,在机动车辆部分内的容器通常具有通过共挤出获得的六层结构,所述六层结构包括(从容器的内侧到外侧)由“原始(virgin) ”的HDPF制成的基础层,包括循环材料,例如再粉碎材料(实质上同样是HDPE)或由其组成的粉碎材料层,粘合促进层,阻挡层,另一粘合促进层和由“原始”HDPE制成的另一层。 As an example, today, part of the container in a motor vehicle generally has a six-layer structure obtained by co-extrusion, the six-story structure comprises (from the inside to the outside of the container) is made from "raw (virgin)" The HDPF The base layer comprises a loop material, such as pulverized material (essentially the same HDPE) or its pulverized material layers, adhesion-promoting layer, a barrier layer, a further adhesion-promoting layer and the "original" HDPE made another layer. [0009] 然而,例如对于两个额外的挤出机来说,引入至少两层额外的粘合促进层到共挤出物内的装置成本,以及挤出工艺所使用的体系的其他昂贵的重新建造也具有对这类体系的基本建设费用成本巨大增加的影响。 [0009] However, for example, two additional extruders, the introduction of at least two additional adhesion-promoting layer to the coextruded other expensive re-equipment cost was within the extrusion process and system used construction also has an impact on the cost of capital cost of such systems has increased dramatically.

[0010] 另一方法提供使用聚芳基酰胺作为阻挡材料,再者此处需要粘合促进剂,以便确保稳定粘结到基于聚烯烃的基础材料上。 [0010] Another method to provide the use of aramid as the barrier material, the adhesion promoter furthermore required here, in order to ensure a stable bond to the polyolefin-based base material. 然而,在这一情况下,在基础材料和阻挡层之间的两个独立层内没有施加粘合促进剂,而是在加工之前,将其加入到基础材料中。 However, in this case, in two separate layers between the barrier layer and the base material of the adhesion promoter is not applied, but prior to the processing, it is added to the base material. 然而,这一方法要求非常大量的粘合促进剂,这同样昂贵。 However, this method requires a very large amount of an adhesion promoter, which is also expensive.

[0011] 因此,本发明的一个目的是在没有损害塑料物品阻挡性能的情况下,提供简化的工艺,该工艺就材料成本和/或基本建设费用来说是有利的,所述成本和/或费用随着生产具有阻挡性能的多层塑料物品用的每一挤出层的增加而升高。 Case [0011] It is therefore an object of the present invention is in no damage plastic items barrier properties, provide a simplified process, the process on material costs and / or capital costs, it is advantageous to the cost and / or With the cost of producing a multilayer barrier properties of plastic articles with increased each extruded layer rises. 而且还应当优选对塑料物品的耐化学性,耐热性或机械强度没有损害。 But should preferably also for chemical resistance, heat resistance and mechanical strength of the plastic article without damage.

[0012] 令人惊奇地,现已发现,允许生产具有阻挡层的多层塑料物品的方法,所述阻挡层兼有对烃类的阻挡性能和对非极性聚烯烃的粘合促进性能,且它可与(来自其他挤出机的)其他挤出层通过共挤出工艺结合,不过它本身可通过挤出机挤出。 [0012] Surprisingly, it has been found that the method allows the production of a multilayer plastic article having a barrier layer, the barrier layer on the barrier properties of both hydrocarbon and non-polar polyolefin adhesion promoting properties, and which can be used with (from the other extruder) other extruded layer is formed by co-extrusion process combined, but it can be extruded through an extruder itself.

[0013] 通过本发明方法生产的容器对烃类具有良好的阻挡性能,而且,还具有非常好的机械稳定性,所述机械稳定性还适用于(applies to)单独的挤出层之间的粘结强度。 [0013] produced by the process of the present invention, a container of hydrocarbons having good barrier properties, but also has very good mechanical stability, the mechanical stability also applies to (applies to) a separate layer between extruded bond strength.

[0014] 因此,本发明提供生产多层塑料物品的方法,它包括基于非极性聚烯烃的至少两层挤出层和位于所述两层之间并与之直接接触的对烃类具有阻挡性能的挤出层,其中该方法包括在共挤出的吹塑体系内生产管状多层塑料型坯的步骤,和其中通过恰好一个挤出机,由共混物发生具有阻挡性能的层的挤出,所述共混物包括对烃类具有阻挡性能的聚合物和包括具有粘合促进性能的聚合物,并在挤出机中在共混物内部发生对烃类具有阻挡性能的聚合物和具有粘合促进性能的聚合物的至少一些分层(demixing)时的熔融温度下进行所述挤出。 [0014] Accordingly, the present invention provides a method of manufacturing a multilayered plastic article, which comprises hydrocarbons having between barrier based on a non-polar polyolefin layer, and at least two of said extruded layers and in direct contact with the Performance extruded layer, wherein the method comprises the step of producing a multi-layer tubular plastic parison within the blow coextrusion system, and wherein the extruder through exactly one layer having barrier properties generated by extruding a blend of out, the blend comprises hydrocarbons having barrier properties comprising a polymer and a polymer having adhesion promoting properties, and occurs in an extruder within a polymer blend having barrier properties to hydrocarbons and carried out at a melting temperature of at least some of the stratification (demixing) when a polymer having adhesion promoting properties of the extrudate.

[0015] 在所使用的温度下因两种聚合物粘度差别引起的具有阻挡性能的共混物中两种聚合物的分层以下述方式发生,所述方式使得大多数具有阻挡性能的聚合物大致布置在挤出层的中间。 [0015] The barrier layered blend of the two polymers at the temperature used in both polymer viscosity differences caused by the occurrence of such a manner, the way that most of the barrier properties of the polymer has disposed substantially in the middle of the extruded layer.

[0016] 对于本发明来说,措辞“基于非极性聚烯烃的挤出层”是指以重量计,主要由聚烯烃组成的挤出层,其中这些聚烯烃分别可牵涉“原始”聚烯烃,其中聚烯烃的比例占主要量的粉碎材料(“再粉碎材料”),或这些的混合物。 [0016] For this invention, the expression "non-polar polyolefin-based extruded layer" refers to the weight of the extruded layer, composed mainly of a polyolefin, wherein the polyolefin respectively may involve "raw" polyolefin wherein the proportion of polyolefin predominant amount of pulverized material ("pulverized material"), or mixtures of these. 在这一意义上的措辞“非极性”是指不带有任何极性基团,例如酸基,酸酐基,酰胺基,酯基或羟基的聚烯烃。 In this sense the wording "non-polar" means not having any polar groups, such as acid, anhydride groups, amide groups, ester groups or hydroxyl polyolefins.

[0017] 对于本发明的目的来说,措辞“直接接触”是指对烃类具有阻挡性能的层在其上侧和其下侧分别粘结到基于非极性烯烃的层上。 [0017] For purposes of the present invention, the phrase "direct contact" refers to a layer of hydrocarbons having barrier properties are bonded on the upper side and the lower side to the non-polar olefin-based layer.

[0018] 对于本发明的目的来说,措辞“挤出层”是指在共挤出工艺中,可通过恰好一个挤出机挤出的任何层,而与在每一个尺寸上它是否具有均一的结构无关。 [0018] For purposes of the present invention, the expression "extruded layer" refers to any layer in a coextrusion process, by exactly one extruder, and at every size and whether it has a uniform independent of the structure. 相反,对于本发明的目的来说,在所述层内不同的形貌或不均匀度不是挤出层,即使它们本身具有层状的结构。 In contrast, for the purposes of the present invention, in the layers of different shape or unevenness of extruded layers is not, even though they themselves have a layered structure.

[0019] 由于通过本发明实现在共混物内两种聚合物之间的分层,因此具有阻挡性能的聚合物在具有阻挡性能的挤出层内部存在以颗粒和相互交叠的层状结构形式的非均匀的分布。 [0019] Since the present invention is implemented by layering the blend between the two polymers, and therefore the presence of a polymer having barrier properties and layered structure of particles overlap with each other inside the extrusion layer having barrier properties non-uniform distribution form. 这一方法使用仅仅一个挤出机和仅仅一种共混物生产出实现了阻挡效果的可称为涂布/多层结构的制品,在所述结构内,可称为三层壁的结构对应于具有六层壁结构的已知塑料容器所提供的结构。 This method uses the structure corresponding to only one extruder and blend to produce only one to achieve a barrier effect may be referred to a coating / multilayer structure of the article, in the structure, it may be called three walls Plastic containers are known to have a structure of six wall structure provided.

[0020] 对于本发明的目的来说,措辞“多层交叠的层状结构”是指主要平行于挤出层所在平面的结构,所述结构空间有限且优选借助相互接触形成最大连续性的内聚材料层。 [0020] For purposes of the present invention, the expression "multi-layered structure overlapping" means that the structure of the main plane parallel to the extrusion layer is located, the configuration space is limited and is preferably in contact with each other by means of the formation of the largest continuous cohesive material layer.

[0021] 在本发明的方法中,在具有阻挡性能的层的挤出过程中的熔融温度范围优选为1600C _260C,优选范围为180C _240C,优选范围为200C -225C,尤其优选的范围为2050C _215C,和尤其范围为208C _212C。 [0021] In the method of the present invention, the melt temperature range during extrusion layer having barrier properties is preferably 1600C _260 C, preferably in the range of 180 C _240 C, preferably in the range of 200 C -225 C, particularly preferably in the range of 2050C _215 C, and in particular in the range of 208 C _212 C. 然而,若温度高于260C,则在具有阻挡性能的挤出层内两种聚合物混合物和所得层具有明显较差的阻挡性能。 However, if the temperature is higher than 260 C, then the barrier properties of the extrusion having an inner layer of a mixture of two polymers and the resulting layer was poor barrier properties.

[0022] 为了在本发明的方法中挤出具有阻挡性能的层,优选使用不具有剪切部分和/或混合部分的螺杆挤出机,和尤其优选使用不具有剪切部分且不具有混合部分的螺杆挤出机。 [0022] The barrier layer for extrusion in the method of the present invention, it is preferable to use does not have a cut portion and / or the mixing section screw extruder, and particularly preferably having no cut portion and does not have a mixing section screw extruder.

[0023] 在本发明的方法中,基于聚烯烃的至少两层挤出层中的聚烯烃优选彼此独立地分别选自由下述组成的组:非极性高密度聚乙烯(HDPE),低密度聚乙烯(LDPE),线性低密度聚乙烯(LLDPE),聚丙烯(PP),乙烯-丙烯共聚物和这些的混合物,和此处可使用或者“原始”材料,或者粉碎材料(“再粉碎材料”),或者要么这些的混合物。 Group [0023] In the method of the present invention, at least two extruded polyolefin-based layer is a polyolefin preferably independently of one another are selected from the group consisting of: nonpolar high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), ethylene - propylene copolymers, and mixtures of these, and here you can use or "raw" material or pulverized material ("pulverized material "), or either of these mixtures. 优选这两层分别基于非极性高密度聚乙烯(HDPE)。 The two layers are preferably based on non-polar high density polyethylene (HDPE).

[0024] 作为对烃类具有阻挡性能的聚合物,优选使用在210C的温度下和在2160g的负载下,溶体流动速度为2-10g/10min,优选3_5g/10min的聚合物(根据ISOl 133测定)。 [0024] As a hydrocarbon polymer having barrier properties, is preferably used at a temperature of 210 C and at a load of 2160g, a melt flow rate of 2-10g / 10min, preferably 3_5g / 10min polymer (according to ISOl 133 assay). 聚合物的密度优选为约1.0-1.3g/cm3(根据IS01183测定)。 The density of the polymer is preferably from about 1.0-1.3g / cm3 (measured in accordance with IS01183). 所使用的阻挡聚合物的熔点范围优选为1600C _200C,优选范围为1800C -190。 Melting range used barrier polymer is preferably 1600C _200 C, preferably in the range of 1800C -190. . (根据IS011357测定)。 (Measured in accordance with IS011357).

[0025] 作为对烃类具有阻挡性能的聚合物,本发明方法中所使用的聚合物优选是选自由下述组成的组中的聚合物:乙烯-乙烯醇共聚物(EVOH),聚芳基酰胺,聚酰胺(PA),聚乙烯醇(PVOH),聚对苯二甲酸乙二酯(PET),和它们的混合物。 [0025] As the hydrocarbon group having barrier properties of a polymer, the method of the present invention is used in the polymer is preferably selected from the group consisting of polymers: ethylene - vinyl alcohol copolymer (EVOH), polyarylate , polyamide (PA), polyvinyl alcohol (PVOH), polyethylene terephthalate (PET), and mixtures thereof. 对烃类具有阻挡性能的聚合物尤其优选是乙烯-乙烯醇共聚物(EVOH),和尤其优选基于共聚物的分子组成,乙烯比例为28-36mol%的乙烯-乙烯醇共聚物。 A hydrocarbon polymer having barrier properties is particularly preferably an ethylene - vinyl alcohol copolymer (EVOH), and especially preferred copolymers based molecules, 28-36mol% ethylene ratio of ethylene - vinyl alcohol copolymer. 在一个尤其优选的实施方案中,具有阻挡性能的层不包括与乙烯-乙烯醇共聚物一起的聚酰胺。 In a particularly preferred embodiment, the layer having barrier properties excluding ethylene - vinyl alcohol copolymer together with the polyamide.

[0026] 具有粘合促进性能的聚合物优选选自用极性基团官能化的聚烯烃,优选用不饱和羧酸或用羧酸酐官能化的聚乙烯。 [0026] The polymer having the adhesion promoting properties with a polar group is preferably selected from functionalized polyolefin, preferably with an unsaturated carboxylic acid or carboxylic acid anhydride-functionalized polyethylene. 这类聚合物的实例是乙烯与不饱和羧酸或羧酸酐,例如丙烯酸,甲基丙烯酸,马来酸或马来酸酐的共聚物。 Examples of such polymers of ethylene and an unsaturated carboxylic acid or carboxylic acid anhydride, such as acrylic acid, methacrylic acid, maleic acid or maleic anhydride copolymers. 尤其优选乙烯与马来酸酐的共聚物,其中共聚物优选包括基于聚合物的总重量,0.05-5wt%马来酸酐,更优选0.l_lwt%,和尤其优选0.2-0.3wt%马来酸酐。 Particularly preferred copolymers of ethylene and maleic anhydride, wherein the copolymer preferably comprises based on the total weight of the polymer, 0.05-5wt% maleic anhydride, more preferably 0.l_lwt%, and particularly preferably 0.2-0.3wt% maleic anhydride.

[0027] 在共混物内具有阻挡性能的聚合物的重量份与具有粘合促进性能的聚合物的重量份之比的范围优选为15:85-40:60,尤其优选范围为20:80-35:75,和尤其范围为25:75-30:70,在每一情况下基于该共混物的总重量。 [0027] The barrier polymer blend in parts by weight of the adhesion-promoting properties of a polymer having a ratio of parts by weight preferably ranges from 15: 85-40: 60, particularly preferably in the range of 20:80 -35: 75, and in particular in the range of 25: 75-30: 70, in each case based on the total weight of the blend.

[0028] 具有阻挡性能的挤出层的厚度优选是所述层和两层聚烯烃层的层厚之和的2-10%,优选3-8%,和尤其优选5.5-7.5%。 [0028] The barrier thickness of the extruded layer is preferably 2-10% of the thickness of the layer and the polyolefin layer and the two layers, preferably 3-8%, and particularly preferably 5.5-7.5%.

[0029] 通过本发明方法生产的多层塑料物品可与基于聚烯烃的两层和具有阻挡性能的层一起包括进一步的挤出层,所述挤出层彼此独立地通过共挤出施加到聚烯烃-基层的一层或两层上,并与对烃类具有阻挡性能的挤出层直接接触。 [0029] By the method of the present invention is a multilayer plastic article produced with polyolefin-based layers and layer together with barrier properties comprising a further layer of extruded, the extruded layer by co-extrusion are independently applied to the poly olefin - one or two layers on the base layer, and extruded into direct contact with hydrocarbons The barrier layer. 作为例举,在燃料容器情况下,(从内侧起,即从面向燃料的一侧起)可优选下述层结构:HPDE,对于本发明的目的来说,具有阻挡性能的挤出层,包括HDPE作为主要成分,着黑色的HPDE的由再粉碎材料制成的粉碎材料。 As example, in the case of the fuel container, (starting from the inner side, i.e. starting from the side facing the fuel) is preferably the following layer structure: HPDE, for the purposes of the present invention, the extruded layer having barrier properties, comprising HDPE as the main component, the black HPDE by pulverized material pulverized material.

[0030] 同样可能的是,塑料物品中的一层或更多层挤出层,尤其基于聚烯烃的挤出层包括添加剂,例如纤维,填料,颜料,抗氧剂等,但不限于这些。 [0030] Also possible is the plastic article one or more layers of extruded layers, in particular an extrusion layer include polyolefin-based additives, such as fibers, fillers, pigments, antioxidants and the like, but is not limited thereto. 然而,优选具有阻挡性能的挤出层不包括填料,例如称为粘土的材料。 However, preferably the barrier properties of extruded layer does not include a filler, such as clay material known.

[0031] 优选的是,用于运输或用于储存液体和/或气态烃类,尤其燃料,例如汽油或柴油的多层中空塑料体,或者用于所述中空塑料体的零配件构成在本发明的方法中生产的塑料制品,例如填料颈(filler neck),泵,填料管,填充-变平指示器(fill-levelindicators),和通风装置,例如阀门,或固定设备,但不限于这些。 [0031] Preferably, for transportation or for storage of liquid and / or gaseous hydrocarbons, in particular fuels, such as multi-layered hollow plastic body petrol or diesel, or for the hollow plastic body parts constitute at present The method of the invention in the production of plastic products, such as filler neck (filler neck), pump, packing tube, filling - flattened indicator (fill-levelindicators), and ventilation devices, such as valves, or fixtures, but is not limited to these. 多层塑料物品尤其优选包括燃料容器。 Especially preferred multilayer plastic items including fuel container.

[0032] 本发明进一步提供多层塑料物品,它包括基于非极性聚烯烃的至少两层,和位于所述两层之间且与之直接接触的对烃类具有阻挡性能的层,其中具有阻挡性能的层包括对烃类具有阻挡性能的聚合物且包括具有粘合促进性能的聚合物,和其中具有阻挡性能的聚合物在具有阻挡性能的层内部存在以颗粒和相互交叠的层结构形式的非均匀的分布。 [0032] The present invention further provides a multilayer plastic article, comprising at least two layers based on the non-polar polyolefin, and a layer with hydrocarbons and having direct contact with the barrier properties, having located between the two an internal layer comprising a polymer layer barrier properties of a hydrocarbon having barrier properties and comprises a polymer having adhesion promoting properties, and polymers having barrier properties in the presence of layers having barrier properties to the structure of the particles and overlapping non-uniform distribution form.

[0033] 本发明具有阻挡性能的层形成阻挡材料集中在中间的所谓的三层结构,和这是挤出工艺和在挤出工艺过程中共混物的特定分层的结果。 [0033] The present invention has the capability of forming a barrier layer of a barrier material concentrated in the middle of the so-called three-tier structure, and this is the result of the extrusion process and extrusion process blended material layered in particular. 使用仅仅三个挤出机,这一方法得到所谓的五层壁结构。 Use only three extruders, this method to obtain the so-called five-wall structure.

[0034] 本发明的这些多层塑料物品优选通过以上所述的本发明方法生产,以便基于非极性聚烯烃的两层,和在其间且与之直接接触的具有阻挡性能的层分别牵涉挤出层。 [0034] The method of the present invention is a multilayer plastic article of the present invention is preferably produced by the above-described, so that the non-polar polyolefin-based layers, and a layer therebetween having barrier properties and are involved in direct contact therewith squeeze the layers.

[0035] 进一步的步骤,或者加工在本发明方法中生产的型坯得到实际的塑料物品的可能性分别是本领域技术人员已知的。 Possibility [0035] A further step in the method of the present invention, the processing or production of a parison obtained in the actual plastic articles are known to the skilled person.

[0036] 可为了这一目的,按照已知方式,以具有轴向或径向原料的头形式设计在本发明方法中所使用的挤出头,其中从挤出机中出来的熔体物流在心轴周围轴向或径向流动。 [0036] For this purpose can, in a known manner so as to have an axial or radial head in the form of raw materials, design extrusion head in the process of this invention is used, which come out from the extruder melt stream mind axial or radial flow around the axis. 也可通过合适地设计的流动通道,使熔体物流在挤出头内偏离。 Also available through the flow channel suitably designed, the melt stream deviation in the extruder head. 在此处另一可能的布局中,可提供分离装置,侧面切割或细分多层管状型坯,通过多个伸长的、笔直的线形模头间隙,以片材-或网状物形状的型坯形式出现。 In another possible arrangement here, the separating means may be provided, a side cut or broken multi-layer tubular parison by a plurality of elongated, linear straight die gap to the sheet - shaped or mesh parison form.

[0037] 作为例举,因此可按照已知方式,通过挤出吹塑,由所述管状型坯获得燃料容器。 [0037] As example, it can be known manner by extrusion blow molding, the fuel container obtained by said tubular parison. 作为替代方案,也可切割开型坯,得到至少两个片材状的半成品产品,然后热成形,得到半-壳(half-shells),然后焊接,得到中空体,但本发明没有限制到这些以上提及的可能性上。 Alternatively, the parison can be cut open to give at least two sheet-like semi-finished product, and then thermoformed to give half - shell (half-shells), and then welded to obtain a hollow body, but the present invention is not limited to these on the above-mentioned possibility.

[0038] 本发明也可包括挤出半成品产品,所述半成品产品为片材或网状物形式,且拟用于热成形。 [0038] The present invention may also include extruded semi-finished product, the semi-finished product is a sheet or web form and intended for thermoforming.

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