CN109070410B - 用于制造生物塑料产品的方法 - Google Patents
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Abstract
本发明涉及一种用于制造基于葵花籽皮或葵花籽壳的生物材料产品的方法,所述方法包括提供或制备复合材料(SPC PBS,SPC PBSA),其中材料通过将葵花籽皮材料或葵花籽壳材料与可生物降解的塑料、即聚丁二酸丁二醇酯(PBS)、聚丁二酸己二酸丁二醇酯(PBSA)等复合而获得,并且复合材料优选用于制造注塑产品,例如可生物降解的容器、包装、薄膜等,尤其咖啡胶囊、茶胶囊、瓮、杯、盆栽盆、花盆等。
Description
背景技术
可生物降解的材料已经较长时间已知并且可生物降解的塑料也是已知的。对此,聚丁二酸丁二醇酯,简称PBS也属于可生物降解的生物塑料,所述聚丁二酸丁二醇酯由丁二醇(例如,Bio-BDO)和丁二酸制成,所述丁二酸也能表示为是基于生物的。
聚丁二酸己二酸丁二醇酯(PBSA)也属于相同类别的可生物降解的塑料,所述聚丁二酸己二酸丁二醇酯除丁二酸之外还聚合有己二酸。该塑料也能够根据单体来源而或多或少是基于生物的。
从DE 10 2007017321中已知一种多层薄膜和一种用于其制造的方法并且在该申请中公开的变型形式之一中也使用热塑性聚酯,例如PBS,所述热塑性聚酯单独地或以与其他热塑性聚酯组合的方式使用。
虽然迄今已知的可生物降解的塑料——这也适用于PLA(聚丙烯酸)——是已知的,但其制造始终仍是相对昂贵的并且在其加工、即尤其加工用于注塑最终产品时也需要相对长的机器循环时间。
从DE 10 2013 216 309 A1、DE 10 2013 208 876 A1、WO 2013/072146 A1中已知具有葵花籽皮/葵花籽壳的生物合成物或生物材料,其中PLA用作塑料组分。
为了设定在这种可生物降解的塑料中确定的物理特性,例如脆性、弹性、弹性模量、强度等而采用的措施也是相对耗费并且昂贵的。
发明内容
本发明基于减少或甚至完全避免迄今的缺点的目的。
本发明借助一种用于制造基于葵花籽皮或葵花籽壳的生物材料产品的方法实现目的,所述方法包括:-提供或制备复合材料(SPC PBS,SPC PBSA),其中所述材料通过将葵花籽皮材料或葵花籽壳材料与聚丁二酸丁二醇酯(PBS)或聚丁二酸己二酸丁二醇酯(PBSA)进行复合而获得并且所述复合材料用于制造注塑产品。在下文中描述有利的改进方案。
在本发明中,将已知的聚丁二酸丁二醇酯(PBS)、PBSA等与葵花籽皮纤维(所述葵花籽皮纤维也能够是葵花籽壳纤维)一起化合(在下文中也称作SPC PBS或S2PC PBSA)。
因为葵花籽皮纤维是纯生物产品,葵花籽皮包围葵花籽种子的含油的籽仁,所以为了加工葵花籽皮纤维仅需要对种子剥皮、将壳材料(例如通过研磨工艺)将粉碎到期望的粒度,以及干燥到确定的湿度值并且脱油(减少)到期望的油含量/脂肪含量。
葵花籽皮纤维的粉碎通过研磨工艺进行,其中粒度在3毫米或更小的范围中,优选在0.01mm至1mm的范围中,尤其优选在0.1mm至0.3mm的范围中。
上述粒度数据表示:纤维材料的至少一个期望的百分比,例如80%或更多具有所给出的粒度并且仅仅小部分位于期望的粒度范围之外。
通过将葵花籽皮材料与PBS材料在挤出机、例如双螺杆挤出机中复合而产生复合物,所述复合物是能注塑的并且所述复合物在最终生物材料产品中具有弹性模量和/或抗拉强度,所述最终生物材料产品相对于由纯的PBS构成的生物材料产品明显提高并且具有更好的其他特性。
本发明的一个特殊的使用领域在于制造可生物降解的包装或容器,例如咖啡胶囊、花盆、袋、盒子等。
相对于使用纯的PBS,通过本发明主要能够明显降低制造成本,例如降低超过10%。这是因为:葵花籽皮纤维和其加工比PBS材料的制造明显更便宜。因为葵花籽皮纤维在直至200℃的温度也是热稳定的,所以当咖啡产品在根据本发明的咖啡胶囊中在相对高的压力和/或高的温度下在相应适合于此的咖啡机中制造时,则对于咖啡产品不产生负面的感官性的影响。
通过葵花籽皮纤维对于塑料一定程度上提供“生物纤维增强”的方式,胶囊的壁厚度相对于纯的PBS材料也许也能够减少,这减少了每个容器、包装、咖啡胶囊等的PBS用量并且再次引起节约成本。
附图说明
在下文中结合实施例阐述本发明。
实施例涉及可生物降解的咖啡胶囊或可生物降解的进而可堆肥的盆栽盆(花盆),但能扩展到每个可生物降解的进而可堆肥的包装、容器等。
附图示出:
图1至图4示出奈斯派索(Nespresso)型号的根据本发明的咖啡胶囊的不同视图。
图5和图6示出Tassimo型号的根据本发明的咖啡胶囊的不同视图。
在图7和图8中示出根据本发明的杯与杯容器。
图9示出具有葵花籽皮的、基于PLA与基于PBS的复合物的对比。
图10示出具有葵花籽皮的、基于PLA与基于PBS的复合物的对比。
具体实施方式
对于Tassimo型号的咖啡胶囊使用根据表1的材料配方,对于Nespresso型号的咖啡胶囊使用根据表2的材料组成。
从两个表格可见,咖啡胶囊材料的69%通过Bio-PBS PZ71PM(同样附上其数据页)并且复合材料的30%通过皮粉末(粒度<0.5mm或0.2mm)形成并且此外使用添加剂(增附剂)、即Licocene PP MA 7452。
关于所使用的Bio-PBS PZ71PM的数据在本说明书最后的技术数据页中找到。
其他材料数据,尤其关于根据本发明的、(用于Tassimo型号的咖啡胶囊的)材料S2PC 3071MI或(用于Nespresso型号的咖啡胶囊的)材料S2PC 3071MIF的物理参数在同样附上的材料数据页中找到。
在此,尤其一些值,例如弹性模量的、抗拉强度等的值引人注意。
根据迄今已知的数据,纯的PBS的弹性模量位于300MPa和700MPa的范围中,而反之根据本发明的生物材料SPC PBS/PBSA的弹性模量——见表3和表4中相应的材料数据页——高于1200MPA,在S2PC 3071MIF中所述弹性模量为大约1300MPa,在S2PC 3071MI中所述弹性模量甚至为1468MPa(SPC=葵花塑料复合物)。
由于更好的弹性模量,材料能够更好地用刺或水压穿刺。材料中通过刺或水压形成的孔对于咖啡胶囊是重要的并且(对于传统的胶囊)是已知的。
通过提高复合物中葵花籽皮纤维份额,甚至还能够提高弹性模量。
在同样在此在本申请和本发明中要求保护的盆栽盆中,对弹性模量的要求目前为最小1150MPa,这通过纯的PBS材料无法提供。
如果葵花籽皮粉末一方和PBS另一方的份额变化,则显然也处于本发明的范围中。在该申请中在表格中给出的PBS(69%)与皮粉末(30%)的比例仅可示例性地理解并且其偏差(+/-1%至25%)任何时候都是可行的并且处于本发明的范围中。
也能够改变增附剂、即添加剂Licocene PP MA 7452的量份额(重量百分比),而无需从本发明中导出重量百分比并且也能够使用其他、类似的增附剂。
根据本发明的、由葵花籽皮粉末一方和PBS另一方形成的生物材料的特殊的特性在于:所述生物材料是可完全生物降解的、即可堆肥的。这具体表示为,由于以该方式制备的材料能够通过相应的生物环境(堆肥或土壤/土地)完全降解而存在“家庭可堆肥性”。
根据本发明的材料还具有以下优点:在注塑工艺中的循环时间,亦即:当在注塑设施中使用根据本发明的合成物以便制造相应的最终产品,例如咖啡胶囊或盆栽盆等时的循环时间,即材料在注塑设施中进行注射并且随后取出的时间,能够显著地得以缩短。也就是说,缩短了直至5%至10%或更多。这显著提高了现有的生产装置上的整个注塑工艺的效率,进而又降低了成本。
对于在共同挤出的最终产品的土壤中的“家庭可堆肥性”和最佳的可降解性,本发明也共同提供葵花籽皮粉末作为天然的腐殖质,使得整体上生物降解过程也比迄今更快地进行,因为堆肥所引起的细菌和微生物能够借此通过如下方式分解全部材料:即细菌和微生物首先能够主要定居在葵花籽皮粉末上,以便然后开拓剩余的材料。
借助根据本发明的生物材料也实现明显更高的耐热变形稳定性,因为根据本发明的生物材料处于97℃而纯的PBS处于95℃。这是尤其有利的,因为在所需要的水温下在至少90℃的咖啡胶囊中,改善每摄氏度的耐热变形稳定性是期望的,因为整体上有助于咖啡胶囊也在咖啡制作过程中也足够稳定并且主要绝不引起咖啡产品的味道的(负面的)退化。
只要在本申请中提及皮粉末、即由葵花籽皮/葵花籽壳构成的粉末,那么葵花籽皮材料的所述粉末通过相应的研磨工艺,例如冲压式研磨机制造,借助所述冲压式研磨机使皮材料达到例如0.5mm、0.2mm等的期望的粒度或纤维长度。
SPC PBS材料的皮材料中的油份额在此明显位于10%之下,例如通过脱油位于6%或更少,并且复合材料中的残余湿度通过干燥位于1%之下,优选位于大约0.05%(或更少,但0.1%至0.5%也仍是可接受的)。
还处于本发明的范围中的是:还将另一可生物降解的塑料组分替代PBS并且在需要时还有另一生物纤维、例如木纤维添加给葵花纤维-PBS复合物。第一试验例如得出:于是如果木纤维、大麻或亚麻纤维同样减少到相同的数量级,例如0.1mm至0.5mm的粒度/纤维长度并且共计总产品的5%至10%,根据本该发明的SPC-PBS材料的物理特性、生物特性和化学特性不急剧改变,至少不实质上变差。作为进一步的研究,也许还能够发现其他优选的生物材料,所述生物材料能够与葵花籽皮材料和PBS/PBSA材料最佳地复合,其中在此始终需注意:复合过程中增多的生物材料不达到其热学极限并且也许在此燃烧/碳化,或者还以不同地分解。
如提及的那样,本申请的本发明也包括在进一步利用PBS、PBSA等的情况下制造薄膜作为基于葵花籽皮或葵花籽壳的生物材料产品。
根据本发明的该薄膜能够用已知的薄膜制造机(通常为单螺杆挤出机)制造。在此,厚度能够在大约200μm和1000μm之间,其中优选大约300μm的实施方案。根据本发明的薄膜的特征在于:所述薄膜填充有35%的葵花籽皮粉末(在此,皮粉末具有<200μm的纤维长度/粒度)并且附加地填充有30%的矿物填充材料,例如,但不限于,高岭土。
该薄膜显示出,如果所述薄膜用作用于(例如Nespresso型号等的)咖啡胶囊的例如300μm厚的密封薄膜,则具有尤其期望的断裂特性。借助该薄膜能够确保,所述薄膜仅通过咖啡机(在预设的、先前刻入的部位处的)水压在胶囊中折断。这借助(例如由PE、PVC、PP等构成的)没有填充材料的、传统的塑料薄膜是不可行的,因为所述塑料薄膜通常是过于弹性进而能够承受住水的压力。在咖啡胶囊中使用的密封薄膜通常比如下壁区域更薄(例如同样由保护制成,例如通过注塑或深冲工艺制成),所述壁区域形成咖啡胶囊的下部部分(包括排水口(Ausguss))作为用于咖啡/茶材料的收集容器/杯(见图4的侧视图,图1的顶上视图),其中例如大约500μm(或更小)的材料厚度对于壁区域是完全足够的,但该材料厚度能够单独调节。
出于这些原因,在许多咖啡胶囊中迄今薄的铝薄膜也用作上侧封闭件(所述铝薄膜被预压印)进而在预设的部位处具有能通过水压而断裂的预定断裂部位。铝薄膜同样用于第三方厂商的例如与Nespresso型号兼容的胶囊。但是这种咖啡胶囊是不可兼容的,因为铝在土壤中不具有堆肥特性或降解特性,而是相反会污染堆肥。
如果这种胶囊宣传“生物的”或“可堆肥的”,则还使用不同的纸或纸型。但这些纸的缺点是:所述纸不具有抗氧气的阻挡作用进而胶囊中的咖啡粉末快速损失品质。因此,在上侧和/或在环周装配有根据本发明的薄膜的根据本发明的咖啡胶囊其特征在于其非常良好的氧气阻挡作用。该氧气阻挡作用位于<50cm3/m2*d*bar。上述单位表示,在1巴的压力下每天(d)小于50cm3的氧气穿过1平方米现有的(薄膜材料)。
如果薄膜在多层复合件中制成,则薄膜能够达到直至0.4cm3/m2*d*bar的阻挡作用,在所述多层复合件中使用大约30μm的PVOH或“G聚合物”的中间子层。
立即可见:因此多层复合件中的根据本发明的薄膜的阻挡作用借助PVOH中间子层显著改进。
“G聚合物”是改性的PVOH材料,所述改性的PVOH材料能够尤其有利地用于多层复合件,其中薄膜材料由根据本发明的生物材料形成。来自于Nippon Gohsei公司的G聚合物也作为“Nichigo-G-聚合物”-无定形乙烯醇树脂已知并且在http://www.nippon-gohsei.com/nichigo-g-polymer中描述。
用于在咖啡胶囊中使用的多层薄膜的制造已经是已知的并且这样的薄膜以多层方法产生。这样的多层方法利用S2PC PBS材料也能应用于根据本发明的薄膜。为此,咖啡胶囊以(例如从WO 2016/071036或EP 1576 6515中已知的)共注射方法制成,其中阻挡层由PVOH或G聚合物构成。接触,同样能够达到非常高的氧气阻挡值。如果在此使用由葵花籽皮粉末一方进而SPC PBS或PBSA构成的根据本发明的复合物,则这是本发明的优选的实施方案变型形式。
在表5和表6中示出对比,其中对照SPC-PLA材料与根据本发明的SPC PBS材料的不同物理参数。
这些表格显示出,SPC PLA(在表格中分别在左边)倾向于非常脆性的复合物,但所述合成物同时是非常刚性的,而根据本发明的SPC PBS变型形式(在表格中用S2PC3092MIFT13标记)令人惊讶地具有明显更软的(更小的)弹性模量以及更小的抗拉强度并且同时比SPC PLA具有更高的冲击韧性。
最后,尤其应注意,SPC PLA材料具有仅大约55℃的耐热变形稳定性进而仅受限地适合于咖啡胶囊中的应用(也就是说,水通常以大约90℃±3℃的温度从咖啡机挤压穿过咖啡胶囊),而根据本发明的SPC-PBS材料具有高于90℃的耐热变形稳定性进而明显更好地适合并且咖啡胶囊在咖啡产品中保持稳定。
恰恰由于根据本发明的SPC-PBS材料的尤其高的耐热变形稳定性温度(所述耐热变形稳定性温度比纯的PBS更高),用该材料也能够制造容器,所述容器能够容纳相对高调温的液体/食品,即例如咖啡、茶、汤、面条等。
在图7和图8中示出相应的(咖啡)杯(图7)与杯容器(图8)。在此,杯的高度能够在100mm和250mm之间,90mm的直径是毫无问题可行的并且300ccm或更大的体积也能够毫无问题地实现并且在试验中发现:尽管填充有热的咖啡或茶,但杯在此保持非常稳定。该杯也是可多次使用的,在使用之后能够非常好地清洁(所述杯也是洗碗机中稳定的)并且主要与迄今的塑料杯相反是“家庭可堆肥的”。
虽然已经存在由宣传为可堆肥的生物塑料构成的相应的塑料杯,当然,在那不存在家庭可堆肥性,而仅存在工业可堆肥性,这表示,杯在工业过程中在完全确定的条件下(并且添加其他分解物质)仅能够在工业规模中堆肥,但不像根据本发明的杯或容器那样,所述杯或容器能够在堆肥堆上在短时间之内在自然界中无残余物地分解进而可视为家庭可堆肥的。
只要在本申请中提及咖啡胶囊,借此当然同时也表示利用胶囊的任意其他应用,例如茶胶囊、汤胶囊等。
根据本发明的S2PC-PBS材料的突出的可生物降解的、家庭可堆肥的特性也能够允许:将该材料用于瓮(骨灰瓮)。那么在此,由复合物材料通过相应的制造方法、例如深冲、压印、注塑等制成瓮,然后灰分能够填充到所述瓮中。第一试验能够推测:材料在土壤(大约50cm至100cm的深度)中的完全分解在5年之后就已经完全实现(根据本发明的SPC PBS或SPC PBSA的突出的土壤可降解性)并且在此在土壤中不遗留任何污染残留物。
最后,需指明:SPC PBS材料在深林保护中的优选的应用。如果幼苗以单组栽培方式种植,则必须设法保护植物免受啃咬、尤其被狍子和其他有蹄类动物啃咬。迄今,这用围绕幼苗设置的铁丝栅栏或塑料围栏实现,以便所述幼苗能够尽可能无干扰其顶芽地向上发育,而不通过啃草而损害。迄今的树木保护措施的问题(也存在许多树木保护塑料材料,即例如还有塑料带以及塑料栅栏等,所述塑料带围绕植物缠绕成螺旋)在于:该塑料材料残留在野外,但并不分解,而后果是:所述塑料材料被野兽在玩兴中吃下并且也许由此所述塑料材料的一部分到达野兽的胃肠道中并且危害动物。
由SPC PBS构成的根据本发明的生物材料产品用于制造树木螺旋体、机械的植物防护器和啃咬防护器等的应用也具有如下优点:材料在其围绕植物安装之后无需再次从现有的树林中取出,因为其在几年之内通过堆肥过程而本身解体,其中所述SPC PBS由葵花籽皮材料一方进而复合的PBS材料另一方构成。
只要在本申请中提及机械的啃草防护器,借此就表示指全部相应的产品,如树木螺旋体、树木防护栅栏、生长罩作为用于幼苗、植物、葡萄藤等的保护器。
表1
<u>名称</u> | <u>%</u> | <u>量</u> | <u>单位</u> |
Bio PBS FZ71PM | 69.00 | 690 | Kg |
皮粉末LGM 3(<0.5mm) | 30.00 | 300 | Kg |
Licocene PP MA 7452 | 1.00 | 10 | Kg |
表2
<u>名称</u> | <u>%</u> | <u>量</u> | <u>单位</u> |
Bio PBS FZ71PM | 69.00 | 690 | Kg |
皮粉末LGM 3(<0.2mm) | 30.00 | 300 | Kg |
Licocene PP MA 7452 | 1.00 | 10 | Kg |
表3
表4
Claims (14)
1.一种用于制造基于葵花籽皮或葵花籽壳的生物材料产品的方法,所述方法包括:
- 提供或制备复合材料,其中所述材料通过将葵花籽皮材料或葵花籽壳材料与聚丁二酸丁二醇酯(PBS)或聚丁二酸己二酸丁二醇酯(PBSA)进行复合而获得并且所述复合材料用于制造注塑产品。
2.根据权利要求1所述的方法,其中所述注塑产品是可生物降解的容器、包装、薄膜。
3.根据权利要求1所述的方法,其中所述注塑产品是咖啡胶囊、茶胶囊、瓮、杯、盆栽盆。
4.根据权利要求1所述的方法,
其特征在于,
所述复合材料以注塑方法加工,以制造咖啡胶囊、茶胶囊、盆栽盆、杯。
5.一种葵花籽皮-生物合成物的应用,该应用用于制造可生物降解的包装、容器、薄膜,其中所述生物合成物一方面由聚丁二酸丁二醇酯(PBS)或聚丁二酸己二酸丁二醇酯(PBSA)构成,所述塑料与葵花籽皮材料或葵花籽壳材料复合。
6.根据权利要求5所述的应用,其特征在于,该应用用于制造咖啡胶囊、茶胶囊、盆栽盆、瓮、啃咬防护器、杯。
7.一种容器、一种包装、一种薄膜,其特征在于,其通过根据权利要求1至4中任一项所述的方法制成。
8.根据权利要求7所述的容器、包装、薄膜,其特征在于,其是咖啡胶囊、茶胶囊、盆栽盆、杯、瓮。
9.根据权利要求7所述的容器、包装、薄膜,
其特征在于,
所述容器、包装、薄膜由多层复合件构成,所述多层复合件具有第一层和第二层以及设置在这两个层之间的中间子层,其中所述第一层和所述第二层由葵花籽皮-PBS和/或-PBSA复合物材料构成并且由改性的PVOH材料或PVOH构成的作为阻挡层的所述中间子层起氧气阻挡层作用,所述氧气阻挡层的氧气阻挡作用为<50cm3/m2*d*bar。
10.根据权利要求9所述的容器、包装、薄膜,其特征在于,所述氧气阻挡层的氧气阻挡作用低于10cm3/m2*d*bar。
11.根据权利要求9所述的容器、包装、薄膜,其特征在于,所述氧气阻挡层的氧气阻挡作用为<1cm3/m2*d*bar。
12.一种注塑产品,所述注塑产品由复合材料制成,其中所述材料通过将葵花籽皮材料/葵花籽壳材料与聚丁二酸丁二醇酯(PBS)或聚丁二酸己二酸丁二醇酯(PBSA)进行复合而获得,并且所述葵花籽皮材料/所述葵花籽壳材料在所述复合物中的份额为至少10%。
13.根据权利要求12所述的注塑产品,其中所述葵花籽皮材料/所述葵花籽壳材料在所述复合物中的份额为30%或更多。
14.根据权利要求12所述的注塑产品,其中所述葵花籽皮材料/所述葵花籽壳材料在所述复合物中的份额高于50%。
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DE102018115107A1 (de) | 2018-06-22 | 2019-12-24 | Spc Sunflower Plastic Compound Gmbh | Mehrschichtig aufgebautes Kunststoffprodukt |
DE102018115236A1 (de) | 2018-06-25 | 2020-01-02 | Spc Sunflower Plastic Compound Gmbh | Mehrschichtige Folie, insbesondere Siegelfolie |
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DE102021112867A1 (de) * | 2020-07-08 | 2022-01-13 | Orga.nico GmbH & Co. KG | Behältnis und Spritzgießvorrichtung |
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CN100537661C (zh) * | 2006-04-25 | 2009-09-09 | 邓国权 | 可生物降解的复合及改性树脂及其制备方法和用途 |
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CN105377964A (zh) * | 2013-05-14 | 2016-03-02 | Spc向日葵塑料复合有限责任公司 | 基于葵花籽壳或葵花籽外皮的生物材料产品 |
DE102013208876A1 (de) * | 2013-05-14 | 2014-11-20 | Spc Sunflower Plastic Compound Gmbh | Biokomposit bzw. Biowerkstoff mit Sonnenblumenkernschalen/ - hülsen |
DE102013216309A1 (de) * | 2013-08-16 | 2015-02-19 | Spc Sunflower Plastic Compound Gmbh | Biokomposit bzw. Biowerkstoff mit Sonnenblumenkernschalen/ - hülsen |
CH710340A1 (de) | 2014-11-06 | 2016-05-13 | Fostag Formenbau Ag | Koinjektionsdüse für eine Spritzgussvorrichtung zur Herstellung von mehrschichtigen Spritzgusserzeugnissen. |
JP2016020551A (ja) * | 2015-07-09 | 2016-02-04 | 三菱瓦斯化学株式会社 | 樹脂成形体の製造方法 |
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US10858511B2 (en) | 2020-12-08 |
CN109070410A (zh) | 2018-12-21 |
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BR112018071890B1 (pt) | 2022-11-01 |
CA3022181C (en) | 2024-03-05 |
EP3448649A1 (de) | 2019-03-06 |
JP2019519411A (ja) | 2019-07-11 |
DE102016107654A1 (de) | 2017-10-26 |
EA201892426A1 (ru) | 2019-03-29 |
US20190144664A1 (en) | 2019-05-16 |
UA124968C2 (uk) | 2021-12-22 |
EP3448649B1 (de) | 2022-03-02 |
CA3022181A1 (en) | 2017-11-02 |
KR20190003624A (ko) | 2019-01-09 |
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