CN109265994A - 含有聚合碳二亚胺、环氧化合物和基于聚酯的聚合物的组合物、其生产及其用途 - Google Patents
含有聚合碳二亚胺、环氧化合物和基于聚酯的聚合物的组合物、其生产及其用途 Download PDFInfo
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Abstract
本发明涉及含有聚合碳二亚胺、环氧化合物和基于聚酯的聚合物的组合物、其生产及其用途。本发明的组合物耐水解、有生产成本效益并且显示出减少的排放。
Description
技术领域
本发明涉及含有聚合碳二亚胺、环氧化合物和基于聚酯的聚合物的组合物、其生产及其用于水解抑制的用途。
背景技术
已经证明非常广泛的碳二亚胺在很多应用中是有利的,例如作为用于热塑性塑料、酯基多元醇、聚氨酯、甘油三酯和润滑油等的水解抑制剂。然而,这些碳二亚胺具有排放可能对健康有害的气体的缺点,并且生产非常昂贵并且复杂。
环氧化合物的生产更廉价但是具有即使在非常高的浓度中也不能达到碳二亚胺的水解稳定活性的缺点。这些环氧化合物仅作为酸清除剂并且在更高的温度下仅提供不足的长期稳定性。特别是在例如高的大气湿度和温度条件下的非常苛刻的应用中,这些环氧化合物失去其作为水解抑制剂的活性,因为酯基塑料通常是在超过200℃的温度下加工。DE10349168 A1描述了由环氧化的脂肪酸酯和甘油酯及其与单体碳二亚胺的混合物组成的水解抑制剂。在此描述的稳定剂在油中充当酸清除剂。然而,在上述酯基热塑塑料的加工条件下,它们对于水解的长期稳定性显示出不足。此外,单体碳二亚胺的使用导致有毒气体的排放量增加。
发明内容
因而,本发明的目的是提供了新颖的、有成本效益的组合物,这些组合物耐水解、有生产成本效益并且显示出减少的排放。
现在已经出人意料地发现,当至少一种聚合的芳香族碳二亚胺、至少一种具有至少2个环氧基团的环氧化合物和至少一种基于聚酯的聚合物,特别是使用聚对苯二甲酸亚烷基酯或聚丙交酯的组合时,可以实现上述目的。
因此,本发明提供了含有以下项的组合物:
(a)至少一种式(I)的聚合的芳香族碳二亚胺
R1-R2-(-N=C=N-R2-)m-R1 (I),
其中
m表示从2至500、优选3至20、非常特别优选4至10的整数,
R2表示C1-C12-烷基取代的亚芳基、C7-C18-烷基芳基取代的亚芳基和任选地包含总共7至30个碳原子和亚芳基的C1-C12-烷基取代的C1-C8-亚烷基-桥联亚芳基,优选地
R6、R7和R8各自独立地表示甲基或乙基,其中每个苯环带有仅一个甲基并且n=1至10
并且
R1是-NCO、-NCNR3-NHCONHR3、-NHCONR3R4或–NHCOOR5,
其中,R3和R4是相同或不同的并且表示C1-C12-烷基、C6-C12-环烷基、C7-C18-芳烷基或芳基,并且R5表示C1-C22-烷基-、C6-C12-环烷基-、C6-C18-芳基或C7-C18-芳烷基基团以及具有2-22个碳原子的不饱和烷基基团、或烷氧基聚氧化烯基团,
(b)至少一种环氧化合物,优选地具有至少2个环氧基团,以及
(c)至少一种基于热塑性聚酯的聚合物。
术语亚芳基特别地包含亚苯基、萘、亚蒽基和/或亚菲基基团,优选亚苯基基团。
该聚合的芳香族碳二亚胺a)优选地是式(II)的化合物,
其中,R1选自下组:-NCO、-NHCONHR3、-NHCONR3R4或–NHCOOR5,
其中,R3和R4是相同或不同的并且表示C1-C12-烷基、C6-C12-环烷基、C7-C18-芳烷基基团或芳基基团,
R5表示C1-C22-烷基-、C6-C12-环烷基-、C6-C18-芳基或C7-C18-芳烷基基团以及具有2-22个碳原子、优选12-20、特别优选16-18个碳原子的不饱和烷基基团,或烷氧基聚氧化烯(alkoxypolyoxyalkylene)基团,并且
R6、R7和R8各自独立地表示甲基或乙基,其中每个苯环带有仅一个甲基,并且n=1至10。
根据本发明使用的式(II)的碳二亚胺的碳二亚胺含量(通过用草酸滴定测量的NCN含量)优选地是按重量计2%-14%、优选按重量计4%-13%、特别优选按重量计6%-12%。
此外,根据本发明使用的碳二亚胺优选地具有通过GPC粘度测定法测定的1000g/mol-5000g/mol、优选1500g/mol-4000g/mol、特别优选2000g/mol-3000g/mol的平均摩尔质量(Mw)。
此外,给予优选的是具有多分散性D=Mw/Mn为1.2-2.2、特别优选1.4-1.8的式(II)的碳二亚胺。
这些碳二亚胺优选地是可商购的化合物如例如来自朗盛德国有限公司(LanxessDeutschland GmbH)的名为的聚合碳二亚胺。然而,这些碳二亚胺还可以例如通过在EP14191710.4中描述的方法来生产。
优选的是当该组分b)总共包含每分子至少2个环氧基团,其中优选至少一个环氧基团是末端的。
环氧化的化合物的生产同样是本领域技术人员所熟知的。优选的环氧化的化合物是多缩水甘油醚或聚(β-甲基缩水甘油)醚,优选通过使具有至少两个游离的醇羟基或酚羟基的化合物的反应和/或通过酚羟基与取代的环氧氯丙烷的反应能获得。
优选的多缩水甘油醚或聚(β-甲基缩水甘油)醚衍生自非环醇,特别是乙二醇、二乙二醇以及更高级的聚(氧乙烯)二醇、丙烷-1,2-二醇或聚(氧亚丙基)二醇、丙烷-1,3-二醇、丁烷-1,4-二醇,聚(氧四亚甲基)二醇、戊烷-1,5-二醇、己烷-1,6-二醇、己烷-2,4,6-三醇、甘油、1,1,1-三甲基丙烷、双三羟甲基丙烷、季戊四醇、山梨糖醇,或衍生自聚环氧氯丙烷。
可替代地,优选的多缩水甘油醚或聚(β-甲基缩水甘油)醚衍生自脂环族醇,特别是1,3-或1,4-二羟基环己烷、双(4-羟基环己基)甲烷、2,2-双(4-羟基环己基)丙烷或1,1-双(羟甲基)环己-3-烯,或者它们包含基于N,N-双(-8,2-羟乙基)苯胺或p,p'-双(2-羟乙基氨基)二苯甲烷的芳香核。
优选的环氧化的化合物也基于单核苯酚、多核苯酚。
优选的单核苯酚是间苯二酚或对苯二酚。
优选的多核苯酚是双(4-羟苯基)甲烷、2,2-双(4-羟苯基)丙烷、2,2-双(3,5-二溴-4-羟苯基)丙烷或4,4’-二羟基二苯基砜。
苯酚与甲醛的优选的缩合产物是苯酚酚醛清漆。
优选的芳香族环氧化合物具有2个末端环氧官能团。
优选的具有2个末端环氧官能团的芳香族环氧化合物是双酚A与环氧氯丙烷的低聚反应产物,该低聚反应产物具有根据EN ISO 10927在从900g/mol至1200g/mol范围内的平均分子量以及在从450至600克/当量范围内的环氧指数(根据ISO 3001)。特别优选的是当组分c)是双酚A与环氧氯丙烷的式(III)的低聚反应产物
其中,a是0至10、优选地其中a是1至8、特别优选地其中a是1至6、特别优选地是在从2至3的范围内,其中a表示平均数。
组分c)优选通过根据US2002/0128428 A1的方法生产,并且然后具有根据EN ISO10927在从900g/mol至1200g/mol(在式(III)中对应于在从2至3范围内的a)范围内的平均分子量以及在从450至600克/当量范围内的环氧指数(根据ISO 3001)。
根据本发明可使用的环氧化合物优选具有在从0℃至150℃范围内、特别优选50℃至120℃、非常特别优选在从60℃至110℃的范围内并且特别是在从75℃至95℃范围内的根据DIN 51920的梅特勒(Mettler)软化点。梅特勒软化点是样品流出具有直径为6.35mm的流出开口的圆柱形喷嘴的温度,因此中断位于19mm以下的光闸。为此,在空气中在恒定条件下加热该样品。
优选可使用的环氧化合物根据DIN 16945通过滴定具有在从162g/eq至2000g/eq的范围内、优选在从250g/eq至1200g/eq的范围内、特别优选在从350g/eq至1000g/eq的范围内并且尤其优选在从450g/eq至800g/eq范围内的平均环氧当量重量(EEW,含有一摩尔的环氧键合氧的树脂的克数)。
尤其优选作为组分b)使用的是聚(双酚A-共-环氧氯丙烷)[CAS号25068-38-6],其优选具有通过MALDI-TOF质谱法、通过基质辅助激光解析/电离飞行时间质谱法(根据ENISO 10927)测定的在从600g/mol至1800g/mol的范围内的数均分子量(Mn),例如从洛伊纳公司(Leuna Harze GmbH)可获得的
进一步优选的具有至少2个环氧官能团的环氧化合物是可商购的来自巴斯夫公司(BASF AG)的名称为(例如4368)的环氧化合物系列的化合物,该环氧化合物含有以下任意组合的单元
以及
其中,R9,R10=彼此独立的H、C1-C8-烷基,R11=彼此独立的C1-C8-烷基,x,y=1-20,z=2-20,其中,端基R*表示H、C1-C8–烷基。
该环氧化合物优选地符合式(IV)
其中,R9,R10=彼此独立的H、C1-C8-烷基,R11=彼此独立的C1-C8-烷基,x,y=1-20,z=2-20,其中,端基R*表示H、C1-C8–烷基。
该基于热塑性聚酯的聚合物c)优选地是聚-C1-C8-烷基对苯二甲酸酯、特别优选聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸丙二酯(PTT)、热塑性聚酯弹性体(TPE E)、乙烯乙酸乙烯酯(EVA)、聚乳酸(PLA)和/或PLA衍生物、聚丁二酸丁二酯(PBS)、聚羟基烷酸酯(PHA)及其各种共混物。
聚丙交酯(PLA)是非常特别优选的。
在本发明的一个优选的实施例中,根据本发明的组合物含有
a)按重量计0.2%至2%、优选按重量计0.4%至1.5%、特别优选按重量计0.5%至1.0%;
b)按重量计0.05%至4%、优选按重量计0.1%至2%、特别优选按重量计0.5%至1.5%;
c)按重量计94%至99.75%、优选按重量计96.5%至99.5%、特别优选按重量计97.5%至99.0%。
在本发明的另一个优选的实施例中,这些组合物不含有除了组分a)、b)和c)之外的其他组分,其中a)、b)和c)的比例的总和是按重量计100%。
本发明进一步提供了一种用于生产组合物的方法,根据该方法,将组分a)和b)混合到至少一种基于热塑性聚酯的聚合物c)中。在此给予优选的是挤出机或捏合机,特别优选挤出机。这些是可商购的搅拌和混合组件。
在本发明的一个优选的实施例中,在150℃至300℃的温度下进行组分a)、b)和c)的混合。
在根据本发明方法的另一个实施例中,将另外的添加剂优选成核剂、用于增强的纤维、抗冲击改性剂、流动增强剂和/或UV稳定剂混合到组分a)、b)和c)的混合物中。
本发明进一步涉及一种用于生产水解稳定的制品的方法,该方法通过在至少一种混合组件(优选混料机)中将含有组分a)、b)和c)的组合物加工成模制材料并且使其经受进一步的加工(优选注塑模制法或挤出法)以生产制品。
根据本发明的用于通过挤出或注塑模制来生产制品的方法是在从160℃至330℃的范围内、优选从190℃至300℃的范围内的熔体温度下,并且任选地还在不大于2500巴的压力下、优选在不大于2000巴的压力下、特别优选在不大于1500巴的压力下并且非常特别优选在不大于750巴的压力下进行的。
在挤出中优选的是在型材挤出与顺序共挤出之间进行区分。顺序共挤出包括按交替的顺序对两种不同的材料依次地挤出。以此方式,形成了在挤出方向上具有不同的逐段材料组成的预成型件。有可能通过适当的材料选择对特定物品区段提供确切要求的特性,例如对物品提供软的端部以及硬的中央区段或一体化的软的波纹区(Thielen,Hartwig,Gust,“Blasformen von”[中空塑料体的吹塑模制],Carl HanserVerlag[卡尔汉泽尔出版社],Munich 2006,pages 127-129[慕尼黑2006,第127-129页])。
注塑模制的方法包括:将原料(优选为颗粒形式)在加热的圆柱形腔体中(优选处于粒料形式)熔化(塑化),并且将其作为注塑模制材料在压力下注入到温控式腔体中。作为原材料使用的是根据本发明的组合物,该组合物优选已经通过混炼加工成模制材料,其中所述模制材料进而优选加工成颗粒材料。在该注入到温控式腔体中的模制材料冷却(固化)之后,使该注塑模制的零件脱模。
与注塑模制相比,在挤出机中使用根据本发明的模制化合物挤出连续塑料挤出物,其中该挤出机是用于生产热塑性模制品/制品的机器。可使用的设备包括
·单螺杆挤出机和双螺杆挤出机以及对应的子组,
·常规的单螺杆挤出机、运输型单螺杆挤出机,
·反向旋转双螺杆挤出机和同向旋转双螺杆挤出机。
挤出装置优选地由元件挤出机、模具、下游设备、挤出吹塑模具组成。用于生产型材的挤出装置优选地由以下元件组成:挤出机、型材模具、校准(calibrating)单元、冷却区、履带式输出装置(take-off)和辊式输出装置、分离装置以及斜槽。用于生产膜的挤出装置由以下元件组成:挤出机、冷却区、拉伸机以及辊式输出装置。
根据本发明可获得的制品优选地是曝露于水性介质、大气湿度或喷雾中的材料。
此类水解稳定的制品可以在机动车辆、在电子学、电信、信息技术或计算机工业以及还在家庭、体育、医药或娱乐行业中找到。在一个优选的变体中,使用根据本发明的组合物生产水解稳定的膜,例如用于包装物或太阳能电池。
本发明进一步提供了根据本发明的组合物通过挤出用于生产制品(优选用于包装物或太阳能电池)的用途。
本发明的范围涵盖所有在上文和下文中列举的基团、指数、参数以及它们自身之间的解释的一般或优选的定义,即,包括以任何的组合在对应的范围与优选值之间。
具体实施方式
以下实例用于阐明本发明,但是不具有限制性作用。
示例性实施例:
使用的材料:
1)稳定剂A:基于2,6-二异丙基苯基异氰酸酯、具有按重量计约10.8%的NCN含量的单体碳二亚胺,该单体碳二亚胺从朗盛德国有限公司以名称I可获得。
2)稳定剂B:具有按重量计约11.8%的NCN含量、D=约1.8并且Mw=2300g/mol的式(II)的聚合碳二亚胺,其中n=约3-4,R6、R7、R8各自独立地表示甲基或乙基,其中每个苯环带有仅一个甲基,并且R1=-NHCOOR5并且R5=环己基。
3)稳定剂C:和式(III)的环氧化合物,其中n=在从2-3的范围内,该环氧化合物具有500g/eq至700g/eq的环氧当量重量(DIN 16945)和在75℃与90℃之间的软化点(梅特勒,DIN 51920)。[CAS号25068-38-6]。
4)从Novapet公司可获得的聚对苯二甲酸乙二酯(PET)。
5)从萘琪沃克公司(NatureWorks)可获得的聚乳酸(PLA)。
在聚对苯二甲酸乙二酯(PET)中的水解抑制
为了评估在PET中的水解抑制作用,在以下所述的PET的测量之前在约280℃下,将根据该实例使用的稳定剂(稳定剂A、B和C)通过来自沃纳与弗莱德尔公司(Werner&Pfleiderer)的实验室双螺杆挤出机ZSK25分散到PET中。然后,在Arburg Allrounder 320S150-500注塑模制机上由获得的颗粒材料制备用于测量拉伸强度的F3标准试样。
对于水解试验,将这些F3标准试验样品在水蒸汽中在110℃的温度下储存,并且其拉伸强度以MPa测量。
在聚乳酸(PLA)中的水解抑制
为了评估在PLA中的水解抑制作用,在以下所述的PLA的测量之前在约200℃下,将根据该实例所使用的稳定剂(稳定剂A、B和C)通过来自沃纳与弗莱德尔公司(Werner&Pfleiderer)的实验室双螺杆挤出机ZSK 25分散到PLA中。然后,在Arburg Allrounder320S 150-500注塑模制机上由获得的颗粒材料制备用于测量拉伸强度的F3标准试样。
对于水解试验,将这些F3标准试验样品在水中在65℃的温度下储存,并且其拉伸强度以MPa测量。
这些混合物组分的使用量及其结果在表1和2中列出:
表1:
comp.=来自DE 10349168的对比实例,inv.=本发明的
表2:
comp.=对比实例,inv.=本发明的
表3:
comp.=来自DE 10349168的对比实例,inv.=本发明的
在表1和2中所报道的百分比是相应稳定剂的%重量比。
水解抑制试验的结果表明,单独的环氧化合物显示出很小的稳定效应(如果有稳定效应的话),但是出人意料地,这些环氧化合物与根据本发明的聚合碳二亚胺(例如稳定剂B)一起对水解稳定性表现出明显的正协同效应。相比之下,单体碳二亚胺与这些环氧化合物的组合不会导致此协同作用。
Claims (12)
1.一种组合物,含有:
(a)至少一种式(I)的聚合的芳香族碳二亚胺
R1-R2-(-N=C=N-R2-)m-R1(I),
其中
m表示从2至500、优选3至20、非常特别优选4至10的整数,
R2=C1-C12-烷基取代的亚芳基、C7-C18-烷芳基取代的亚芳基和任选地包含总共7至30个碳原子和亚芳基的C1-C12-烷基取代的亚烷基-桥联亚芳基
并且
R1=–NCO、-NCNR3、-NHCONHR3、-NHCONR3R4或–NHCOOR5,
其中,R3和R4是相同或不同的并且表示C1-C12-烷基、C6-C12-环烷基、C7-C18-芳烷基或芳基,并且R5表示C1-C22-烷基-、C6-C12-环烷基-、C6-C18-芳基或C7-C18-芳烷基基团以及具有2-22个碳原子的不饱和烷基基团、或烷氧基聚氧化烯基团,
(b)至少一种环氧化合物,优选地具有至少2个环氧基团,以及
(c)至少一种选自下组的基于热塑性聚酯的聚合物:聚对苯二甲酸乙二酯、聚对苯二甲酸丙二酯、热塑性聚酯弹性体、乙烯乙酸乙烯酯、聚乳酸和/或PLA衍生物、聚丁二酸丁二酯、聚羟基烷酸酯以及各种共混物、热塑性聚氨酯、聚氨酯弹性体、PU粘合剂以及PU铸塑树脂。
2.根据权利要求1所述的组合物,其特征在于,该聚合的芳香族碳二亚胺是式(II)的化合物
其中,R1选自下组:-NCO、-NHCONHR3、-NHCONR3R4或-NHCOOR5,
其中,R3和R4是相同或不同的并且表示C1-C12-烷基、C6-C12-环烷基、C7-C18-芳烷基基团或芳基基团,
R5表示C1-C22-烷基-、C6-C12-环烷基-、C6-C18-芳基或C7-C18-芳烷基基团以及具有2-22个碳原子、优选12-20、特别优选16-18个碳原子的不饱和烷基基团,或烷氧基聚氧化烯基团,并且
R6、R7和R8各自独立地表示甲基或乙基,其中每个苯环带有仅一个甲基,并且n=1至10。
3.根据权利要求1或2所述的组合物,其特征在于,该环氧化合物是具有至少2个环氧基团的环氧化合物。
4.根据权利要求3所述的组合物,其特征在于,该环氧化合物是双酚A与环氧氯丙烷的低聚反应产物,具有根据EN ISO 10927在从900g/mol至1200g/mol范围内的平均分子量以及根据ISO 3001在从450至600克/当量范围内的环氧指数。
5.根据权利要求3所述的组合物,其特征在于,该环氧化合物是双酚A与环氧氯丙烷的式(III)的低聚反应产物,
其中,a是0至10、优选地其中a是1至8、特别优选地其中a是1至6、非常特别优选在从2至3的范围内,其中a表示平均数。
6.根据权利要求3所述的组合物,其特征在于,该环氧化合物是含有以下单元的化合物:
其中,R9、R10=彼此独立的H、C1-C8-烷基,R11=彼此独立的C1-C8-烷基,x、y=1-20,z=2-20,其中,端基R*是H、C1-C8-烷基,以任何顺序。
7.根据权利要求3所述的组合物,其特征在于,该环氧化合物是式(III)的化合物
R9、R10=H、C1-C8-烷基,R10=C1-C8-烷基,x、y=1-20并且z=2-20,
并且R*=H、C1-C8-烷基。
8.根据权利要求1至7中任一项所述的组合物,其特征在于,所述组合物包含以下比例的a)、b)和c):
a)按重量计0.2%-2%、优选按重量计0.4%-1.5%、特别优选按重量计0.5%-1.0%,
b)按重量计0.05%-4%、优选按重量计0.1%-2%、特别优选按重量计0.5%-1.5%,
c)按重量计94%-99.75%、优选按重量计96.5%-99.5%、特别优选按重量计97.5%-99.0%。
9.一种用于生产根据权利要求1至7中任一项所述的组合物的方法,其特征在于,将组分a)、b)混合到至少一种基于热塑性聚酯的聚合物c)中。
10.一种用于生产根据权利要求9所述的组合物的方法,其特征在于,在160℃-330℃的温度下将组分a)、b)混合到至少一种基于热塑性聚酯的聚合物c)中。
11.一种制品、优选水解稳定的制品,其通过将根据权利要求1至7中任一项所述的组合物混合到至少一个混合组件中、优选混料机中,并且以注塑模制工艺或通过挤出进一步加工以提供模制材料而能获得。
12.根据权利要求1至7中任一项所述的组合物用于通过挤出来生产制品、优选用于包装物或太阳能电池的用途。
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2018
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- 2018-07-13 JP JP2018133098A patent/JP6708703B2/ja active Active
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- 2018-07-16 SG SG10201806051XA patent/SG10201806051XA/en unknown
- 2018-07-16 PH PH12018000199A patent/PH12018000199A1/en unknown
- 2018-07-16 KR KR1020180082562A patent/KR102624356B1/ko active IP Right Grant
- 2018-07-16 JP JP2020502144A patent/JP2020528092A/ja active Pending
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- 2018-07-16 CN CN201880043156.4A patent/CN110809601A/zh active Pending
- 2018-07-16 KR KR1020207001149A patent/KR20200030057A/ko not_active Application Discontinuation
- 2018-07-16 US US16/631,583 patent/US20200165442A1/en not_active Abandoned
- 2018-07-16 UA UAA201807880A patent/UA125434C2/uk unknown
- 2018-07-16 DE DE202018006716.4U patent/DE202018006716U1/de active Active
- 2018-07-16 EP EP18737647.0A patent/EP3655479A1/de not_active Withdrawn
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KR20200030057A (ko) | 2020-03-19 |
TWI780177B (zh) | 2022-10-11 |
WO2019016143A1 (de) | 2019-01-24 |
ZA201804729B (en) | 2019-06-26 |
KR102624356B1 (ko) | 2024-01-11 |
CN109265994B (zh) | 2021-11-02 |
UA125434C2 (uk) | 2022-03-09 |
EP3431538A1 (de) | 2019-01-23 |
CN110809601A (zh) | 2020-02-18 |
RU2018126055A3 (zh) | 2021-09-17 |
JP2020528092A (ja) | 2020-09-17 |
PH12018000199B1 (en) | 2019-03-18 |
KR20190008816A (ko) | 2019-01-25 |
JP2019019323A (ja) | 2019-02-07 |
BR102018014532A2 (pt) | 2019-03-12 |
US20190016853A1 (en) | 2019-01-17 |
BR102018014532B1 (pt) | 2023-04-11 |
MX2018008776A (es) | 2019-02-08 |
BR102018014532A8 (pt) | 2023-01-03 |
PH12018000199A1 (en) | 2019-03-18 |
DE202018006716U1 (de) | 2022-05-05 |
US20200165442A1 (en) | 2020-05-28 |
TW201920481A (zh) | 2019-06-01 |
SG10201806051XA (en) | 2019-02-27 |
EP3655479A1 (de) | 2020-05-27 |
RU2018126055A (ru) | 2020-01-20 |
CA3011457A1 (en) | 2019-01-17 |
JP6708703B2 (ja) | 2020-06-10 |
EP3431539A1 (de) | 2019-01-23 |
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