CN103492280B - 纤维素防护包装材料 - Google Patents
纤维素防护包装材料 Download PDFInfo
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- CN103492280B CN103492280B CN201280019554.5A CN201280019554A CN103492280B CN 103492280 B CN103492280 B CN 103492280B CN 201280019554 A CN201280019554 A CN 201280019554A CN 103492280 B CN103492280 B CN 103492280B
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Abstract
一种含有复合材料的防护包装材料,所述复合材料包含:i)纤维素层;ii)至少一个金属层,其在碱性条件下溶解;和iii)至少一个聚合物层,其中聚合物在碱性条件下为可水解的。本发明还涉及包含防护包装材料的制品。此外,本发明涉及在碱性条件下为可水解的聚合物作为防护层在防护包装产品中的用途。此外,本发明还涉及一种回收上述防护包装产品的方法。具体地,防护包装产品首先置于含水废纸悬浮液中,将该废纸悬浮液在碱性介质中制浆,和/或在脱墨工艺中在碱性介质中处理,其中然后将金属和聚合物与纤维素层中含有的纤维素纤维分离。
Description
本发明涉及防护包装材料和由其制备的制品的领域。本发明还涉及制备防护包装材料和回收含于所述防护包装材料和制品中的纤维素材料的方法。本发明进一步涉及聚合物用于制备防护包装材料的用途。
在液体食品包装中提供聚合物涂覆的纤维素纸盒是已知的。该类产品通常包含纤维素材料层(例如纸或卡纸板),其置于两个聚合物层之间。该类产品适用于新鲜牛乳和其他新鲜液体食品,但没有显示出就氧和水蒸气而言足够的防护性能。因此,这些类型的包装不适用于需要良好防护的长期储存牛乳。
为了储存液体食品如灭菌牛乳和果汁,总需要使用具有高的氧和水蒸气防护性能的包装产品。这些包装产品通常称为防护包装。该类包装产品对潮气和氧的不透性是必要的,以防止其中所含食品变坏。
防护包装材料通常由纤维素层如纸或卡纸板(涂覆有至少一个复合材料层)构造。复合材料层在两个聚乙烯层之间包含非常薄的铝层。然而,该类复合材料产品通常难以回收且倾向于通过煅烧或掩埋而处置。结果是防护包装产品中含有的纤维素材料由此损失。
德国专利申请4328016涉及含有塑料、金属箔和/或纤维素材料的层的可分层复合材料。所述复合材料含有至少三层,其具有置于两个上述材料层之间的至少一个聚合物层,所述聚合物可溶于非中性如碱性含水介质中。该类包装据说可容易地回收。
欧洲专利申请855266描述了能够保持液体且具有热封性能的合适包装材料。所述包装材料包含外部液密的、可热封的塑料涂层,其由已施加至纤维材料基芯上的苯乙烯与丙烯酸酯或甲基丙烯酸酯的共聚物形成。该包装材料据说适用于回收。
WO2007109222公开了氧防护组合物和由其制备的制品,其基于聚(羟基链烷酸酯),优选聚乳酸,衍生自乳酸(也称为2-羟基丙酸)的聚合物,和过渡金属。已发现该活性防护组合物消耗或清除氧且可用于适用于含有对氧敏感的食品的整体和多层包装制品中,由此提高食品的质量和储存期。该类产品据说为可生物降解的且适用于回收。
日本专利申请20008265117描述了适用于储存食品的多层层压膜。多层层压产品包含聚琥珀酸丁二醇酯层的浅色防护,其含有黑色颜料。该层仅适用于提供脂肪和芳香防护,但就氧和水蒸气而言的防护性能对于许多高防护应用不够。
在本申请提交日未公布的国际申请PCT/EP2010/066079涉及一种回收施胶的和/或涂覆有聚合物的纸产品的方法,其中将所述纸产品在至少一种水解酶存在下在碱性介质中制浆,和/或在脱墨工艺中在碱性介质中处理。涂覆纸产品的聚合物为可生物降解的。
本发明目的在于提供一种防护包装材料,其具有对需要产品(例如对于储存液体食品如灭菌牛乳和果汁)足够高的对氧和水蒸气的防护,和由其形成的可容易回收的制品。另一目的在于提供一种防护包装材料,其提供至少与常规防护包装材料同样有效和/或更有效和/或更便于回收以回收其中含有的纤维素材料的防护。本发明目的还在于提供该类防护包装产品的合适回收方法。
因此,根据本发明提供一种含有复合材料的防护包装材料,所述复合材料包含:
i)纤维素层;
ii)至少一个金属层,其在碱性条件下溶解;和
iii)至少一个聚合物层,其中聚合物在碱性条件下为可水解的。
纤维素层理想地为纸、卡纸板或纸板。此外,纤维素层可适当地由制造纸、卡纸板或纸板的常规方法形成。特别地,常用于防护包装产品的纸、卡纸板或纸板可用于本发明。
适用于生产这些防护包装产品的纤维素纤维包括通常用于该目的的所有品级,例如来源于所有一年生植物和废纸(也呈涂覆和未涂覆的损纸形式)的机械浆、漂白和未漂白的化学浆、纸浆料。这些纤维可单独使用或者以彼此的任何所需混合物形式使用,以生产由其生产纸产品的纸浆。机械浆例如包括磨木浆、热机械浆(TMP)、化学热机械浆(CTMP)、压力磨木浆、半化学浆、高得率化学浆和盘磨机械浆(RMP)。作为化学浆,合适的例如为硫酸盐浆、亚硫酸盐浆和碱法浆。适于生产纸浆料的一年生植物例如为稻、小麦、甘蔗和洋麻。
金属层可由适用于食品包装的任意金属形成,其能够在碱性条件下溶解。金属优选为铝。金属层可呈箔,优选铝箔的形式或为金属化工艺的产品。该金属层通常为常用于防护包装材料和制品中的任意合适金属层。该层可适当地具有低于250μm,但通常低于20μm的厚度。金属层可具有通常低于10μm的厚度。金属层可具有低至0.01μm的厚度,但通常大于该厚度。
聚合物应能够在防护包装产品,尤其是在食品长期储存中使用的防护包装产品和制品(例如适用于灭菌牛乳和果汁)中赋予合适的防护。
WO2010/034712公开了适用于需要应用如果汁和牛乳包装的非防护纸产品,即没有显示出氧和水蒸气防护的产品,其涂覆有可生物降解聚合物(混合物)。
这些通常为多层涂层,其中在纸涂覆中通常使用2-7层,优选为2或3层。
除了呈碱溶性之外,本发明中使用的聚合物也可为可生物降解的。可生物降解聚合物可适当地在合适水解酶存在下为可水解的。
可生物降解聚合物是本领域熟练技术人员所已知的且尤其公开于Ullmann’s Encyclopedia of Industrial Chemistry(在线版,2009年),Polymers,Biodegradable,Wiley-VCH Verlag GmbH&Co.KG,Weinheim,2009年,第131页中。
在本发明中,防护包装材料的各组分例如可涂覆有根据EN ISO1133(190℃,2.16kg重量)熔体体积速率(MVR)为2-50cm3/10分钟的聚酯和/或包含这类聚酯的聚合物混合物。
防护包装材料的各组分例如可涂覆有根据EN ISO1133(190℃,2.16kg重量)熔体体积速率(MVR)为5-25cm3/10分钟,尤其优选为5-12cm3/10分钟的聚酯。
当然,也可通过所公开的方法回收含有涂覆有不同的可水解聚酯(尤其是例如聚乳酸)与其他可水解聚合物的聚合物混合物的各组分的防护包装材料。已证明有利的是这些聚合物也具有高流动性。
例如,已证实具有根据EN ISO1133(190℃,2.16kg重量)熔体体积速率(MVR)为5-70cm3/10分钟,特别优选9-50cm3/10分钟,尤其优选5-25cm3/10分钟的聚乳酸可用作这类聚合物混合物中的混合组分。此外,可流动聚酯与上述可流动聚合物混合物的混合物也适用于涂覆防护包装材料的纤维素和/或金属层。
基于脂族二醇和脂族/芳族二羧酸的部分芳族聚酯也应理解为意指聚酯衍生物,如聚醚酯、聚酯酰胺或聚醚酯酰胺。所述部分芳族聚酯包括其链不进行扩链的线性聚酯(WO92/09654A1)。特别地,丁二醇、对苯二甲酸和脂族C6-C18二羧酸如己二酸、辛二酸、壬二酸、癸二酸和巴西酸的脂族/芳族聚酯(例如如WO2006/097353至56所述)为合适的混合组分。优选扩链的和/或支化的部分芳族聚酯。后者公开于文献WO96/15173至15176、21689至21692、25446、25448或WO98/12242中,通过引用并入本文。不同部分芳族聚酯的混合物也适于涂覆纸产品。
优选的聚合物为脂族-芳族聚酯。更优选该类聚合物为包含如下组分且具有根据EN ISO1133(190℃,2.16kg重量)熔体体积速率(MVR)为3-50cm3/10分钟的脂族-芳族聚酯:
i)基于组分i至ii为40-70mol%的一种或多种选自琥珀酸、己二酸、癸二酸、壬二酸和巴西酸的二羧酸衍生物或二羧酸;
ii)基于组分i至ii为60-30mol%的对苯二甲酸衍生物;
iii)基于组分i至ii为98-102mol%的C2-C8亚烷基二醇或C2-C6氧亚烷基二醇;
iv)基于组分i至iii总重量为0.00-2重量%的选自二-或多官能异氰酸酯、异氰脲酸酯、唑啉、环氧化物、羧酸酐和/或至少三官能的醇或至少三官能的羧酸的扩链剂和/或交联剂;
v)基于组分i至iv总重量为0.00-50重量%的选自天然或增塑淀粉、天然纤维、锯末的有机填料和/或选自白垩、沉淀碳酸钙、石墨、石膏、导电炭黑、氧化铁、氯化钙、白云石、高岭土、二氧化硅(石英)、碳酸钠、二氧化钛、硅酸盐、硅灰石、云母、蒙脱石、滑石、玻璃纤维和矿物纤维的无机填料;和
vi)基于组分i至iv总重量为0.00-2重量%的至少一种稳定剂、成核剂、润滑剂和脱模剂、表面活性剂、蜡、抗静电剂、防雾剂、染料、颜料、UV吸收剂、UV稳定剂或其他塑料添加剂。
如上所述,所述脂族-芳族聚酯公开于WO2010/034712中。该文献以及其中所引用的文献通过引用并入本文,以作为这些聚酯的组成及其制备方法的参考。
在其中所述的化合物中,优选的共聚物混合物为包含如下组分的那些:(a)5-95重量%,优选30-90重量%,尤其优选40-70重量%的可水解脂族-芳族聚酯;和
(b)95-5重量%,优选70-10重量%,尤其优选60-30重量%的一种或多种选自聚乳酸、聚己酸内酯、聚羟基链烷酸酯、脱乙酰壳多糖和谷蛋白的聚合物以及一种或多种基于脂族二醇和脂族/芳族二羧酸的聚酯,如聚琥珀酸丁二醇酯(PBS)、聚琥珀酸己二酸丁二醇酯(PBSA)、聚琥珀酸癸二酸丁二醇酯(PBSSe)、聚对苯二甲酸丁二醇酯-co-己二酸丁二醇酯(PBTA);和
(c)0-2重量%的增容剂。
组(c)的增容剂为羧酸酐,如马来酸酐,尤其是含有环氧基且基于苯乙烯、丙烯酸酯和/或甲基丙烯酸酯的共聚物。带有环氧基的单元优选为(甲基)丙烯酸缩水甘油基酯。含有环氧基的上述类型的共聚物例如以ADR的商品名由BASF Resins B.V.销售。特别合适的增容剂例如为ADR4368。
因此,特别优选的共聚物混合物包含:
(a)20-90重量%,优选30-50重量%,尤其优选35-45重量%的可水解脂族-芳族聚酯;
(b)80-10重量%,优选70-50重量%,尤其优选65-55重量%的一种或多种选自聚乳酸和聚羟基链烷酸酯的聚合物;和
(c)0-2重量%的含环氧基的聚(甲基)丙烯酸酯。
组(b)的优选聚乳酸为具有如下性能特征的那些:
-根据EN ISO1133在190℃和2.16kg下为0.5-100ml/10分钟,优选5-70ml/10分钟,尤其优选9-50ml/10分钟的熔体体积速率(MVR);
-低于240℃的熔点;
-高于55℃的玻璃化转变温度(Tg);
-小于1000ppm的含水量;
-小于0.3重量%的残余单体含量(丙交酯);和
-大于10000道尔顿的分子量。
优选的聚乳酸例如为6201D、6202D、6251D、3051D,尤其为3251D(获自NatureWorks的聚乳酸)。
组(b)的聚羟基链烷酸酯主要应理解为意指聚-4-羟基丁酸酯和聚-3-羟基丁酸酯;此外还包括上述羟基丁酸酯与3-羟基戊酸酯或3-羟基己酸酯的共聚酯。聚-3-羟基丁酸酯-co-4-羟基丁酸酯是已知的,尤其是由Metabolix已知。其以商品名销售。聚-3-羟基丁酸酯-co-3-羟基己酸酯由P&G或Kaneka已知。聚-3-羟基丁酸酯例如由PHB Industrial以商品名销售以及由Tianan以商品名销售。
所述聚羟基链烷酸酯通常具有100000-1000000道尔顿,优选300000-600000道尔顿的分子量Mw。
这类聚合物和聚合物混合物适用于本发明中聚合物层,正如适用于WO2010/034712中的那些。
至少一个金属层优选置于作为多层复合材料的两个聚合物层之间。在该情况下,聚合物层应与金属层直接接触。包含金属层和聚合物层的多层复合材料应理想地靠近纤维素层的至少一侧而设置。金属/聚合物多层复合材料应优选地与纤维素层的一侧或两侧直接接触。在防护包装产品中,对于金属/聚合物多层复合材料理想的是位于纤维素层内侧上。当金属/聚合物多层复合材料仅位于纤维素层一侧如相当于防护包装产品的内侧的那侧上时,可能理想的是在纤维素层另一侧如相当于防护包装产品的外侧的那侧上具有聚合物层。
挤压涂覆和层压方法都适用于其生产。这些方法的组合也是可以的。
聚合物可涂覆在至少一个金属层上,需要的话,可涂覆在纤维素层上。在该情况下,平均克重通常为10-50,优选15-30g/m2。
克重借助具有通常4.5英寸(114.3mm)直径的打孔圆形物(punchedroundel)测定。圆形物在涂覆之前和之后称重。由重量差且由已知面积可记录克重(g/m2)。
然而,也可能理想的是将聚合物多层涂层施加至金属层和/或纤维素层上。在纤维素层的金属涂层中通常使用2-7层,优选2或3层。多层涂层提供单独优化焊接性能、防护性能和纸、卡纸板、纸板和/或金属层上涂层的粘合的可能性。在该情况下,平均克重通常为10-60,优选15-35g/m2。
外层或顶层通常应理想地例如为耐划痕的和热稳定的且不粘。呈现出粘性的趋势必须简单地降低,以避免生产工艺中膜粘附至冷却辊。所述层优选由40-60重量%脂族-芳族聚酯和60-40重量%聚乳酸和0-10重量%蜡配制剂的混合物组成,所述蜡配制剂包含0-5重量%蜡、0-10重量%分散剂(例如硬脂酸的金属盐、油酸、亚乙基双硬脂酰胺、酰胺(芥酸酰胺、油酰胺)和0-5重量%防结块剂。
中间层通常应理想地为更硬的且也可称为基材层或防护层。在具有薄膜的涂层中,中间层也可完全省去。中间层优选包含50-100重量%聚乳酸和0-50重量%脂族-芳族聚酯。
内层应理想地为与纤维素和/或金属层接触的层。其通常一定为软的且与金属、纸、纸板和/或卡纸板层良好地粘合。其优选由50-100%脂族-芳族聚酯和0-50%聚乳酸组成。
在某些情况下,金属或纤维素层的三层涂层可能是优选的。涂层优选具有如下组成:
i)外层,其包含40-60重量%脂族-芳族聚酯和60-40重量%聚乳酸和0-10重量%蜡配制剂的混合物,所述蜡配制剂包含蜡、分散剂和防结块剂;外层通常占层厚度的20-40%;
ii)中间层,其包含50-100重量%聚乳酸和0-50重量%脂族-芳族聚酯;中间层通常占层厚度的20-40%;和
iii)与金属和/或纤维素层接触的内层,其包含50-100重量%脂族-芳族聚酯和0-50重量%聚乳酸。内层通常占层厚度的20-40%。
在某些情况下,金属和/或纤维素层的两层涂层同样是优选的。涂层优选具有如下组成:
i)外层,其包含40-60重量%脂族-芳族聚酯和60-40重量%聚乳酸和0-10重量%蜡配制剂的混合物,所述蜡配制剂包含蜡、分散剂和防结块剂;外层通常占层厚度的20-50%;
iii)与金属和/或纤维素层接触的内层,其包含50-100%脂族-芳族聚酯和0-50%聚乳酸。内层通常承担支撑功能和/或防护功能。内层通常占层厚度的50-80%。
对于金属和/或纤维素层的多层涂层,通常使用共挤压方法。优选共挤压涂覆。
适用于将2层或更多层膜结合以得到层压材料的层压方法为挤压层压,其同样适合作为涂覆方法。
挤压涂覆也可用于涂覆金属和/或纤维素层。涂层通常可以100-600m/min的速度施加。本发明中使用的聚合物可通过用于聚乙烯的现有挤压涂覆设备加工(J.Nentwig:Kunststofffolien,Hanser Verlag,Munich2006,第195页;H.J.Saechtling:Kunststoff Taschenbuch,Hanser Verlag,Munich2007,第256页;C.Rauwendaal:L Polymer Extrusion,HanserVerlag,Munich2004,第547页)。
包含上述防护包装材料的防护包装制品也形成本发明一部分。
本发明进一步涉及在碱性条件下为可水解的聚合物作为防护层在防护包装产品中的用途。
此外,本发明涉及一种回收含有复合材料的防护包装材料的方法,所述复合材料包含:
i)纤维素层;
ii)至少一个金属层,其在碱性条件下溶解;和
iii)至少一个聚合物层,其中聚合物在碱性条件下为可水解的;
其中防护包装产品首先置于含水废纸悬浮液中,将该废纸悬浮液
a)在碱性介质中制浆,和/或
b)在脱墨工艺中在碱性介质中处理,
然后将金属和聚合物与纤维素层中含有的纤维素纤维分离。
除了实施方案a)和/或b)外,还可能理想的是将含水废纸悬浮液
c)在碱性处理之前或期间在至少一种水解酶存在下制浆。
涉及防护包装材料的上述优选实施方案也适用于在回收工艺中使用的防护包装材料。
在回收含有金属和可水解聚合物的层的防护包装材料的本发明方法中,含水废纸悬浮液首先由这些产品制备。可将通常具有2-40重量%废纸浓度的该废纸悬浮液
a)在碱性介质中制浆,和/或
b)在脱墨工艺中在碱性介质中处理,和/或
c)在至少一种水解酶存在下制浆。
我们已发现可水解聚合物可能倾向于被粉碎并溶于悬浮液的含水部分中,由此与废纸分离。以此方式,纤维素材料基本上完全,优选完全被回收。
本发明的实施方案b)和c)的特征在于所述废纸悬浮液的制浆方法。如在开头处所述的那样,在制浆过程中向所述纸产品中添加水以首先获得废纸悬浮液,且需要的话,可将该悬浮液浓缩或者以不变的浓度制浆。为了制浆,将所述废纸悬浮液在制浆机或转鼓式粉碎机中处理,其中通过机械作用将所述可水解聚合物与所述纸产品分离。同时将该纸产品粉碎。然后通过分选,例如通过筛筒将聚合物残留物与粉碎的纸产品分离。
回收工艺可额外含有常用于废纸回收工艺中的任意其他废纸材料或其他废纤维素材料。
在其中金属层如铝溶解的工艺期间,氢气气体倾向于形成并被释放。氢气气体可作为燃料用于发电,例如通过燃烧,或用于燃料电池。
在实施方案c)中,废纸悬浮液的制浆在水解酶存在下进行。合适的水解酶[EC3.x.x.x]例如为酯酶[EC3.1.x.x]和蛋白酶[EC3.4.x.x]。根据本发明,尤其使用羧酸酯酶[3.1.1.1]和/或脂肪酶[3.1.1.3]和/或角质酶[3.1.1.74]。这些的实例为来自无色杆菌属(Achromobacter sp.)、曲霉属(Aspergillussp.)、假丝酵母属(Candida sp.)、南极假丝酵母(Candida antarctica)、毛霉菌属(Mucor sp.)、青霉菌属(Penicilium sp.)、地霉属(Geotricum sp.)、根霉属(Rhizopus sp.)、少根根霉(Rhizopus arrhizus)、伯克霍尔德氏菌属(Burkholderia sp.)、假单胞菌属(Pseudonomas sp.)、洋葱假单胞菌(Pseudonomas cepacia)、嗜热真菌属(Thermomyces sp.)、猪胰脏或小麦胚芽的脂肪酶或角质酶以及来自芽孢杆菌属(Bacillus sp.)、假单胞菌属(Pseudonomas sp.)、伯克霍尔德氏菌属(Burkholderia sp.)、毛霉菌属(Mucorsp.)、酵母菌属(Saccharomyces sp.)、根霉属(Rhizopus sp.)、褐色高温单孢菌(Thermomonospora fusca)、嗜热放线菌(Thermobifida fusca)、茄病镰刀菌(Fusarium solani)、特异腐质霉(Humicola Insolens)、Thermoanaerobiumsp.、猪肝脏或马肝脏的羧酸酯酶。水解酶的其他实例为聚羟基链烷酸酯解聚酶和/或蛋白酶K和/或savinase。根据本发明,可使用至少一种水解酶,即,当然可使用选自所述水解酶的单一水解酶或所述水解酶中两种或更多种的混合物。然而,优选在实施方案c)或d)中的本发明方法中仅使用一种所述水解酶。
所述水解酶可以游离形式,优选以水溶液或固定形式使用。
在本发明方法的实施方案a)中,优选呈游离形式,优选为水溶液或固定形式(例如获自Novozymes A/S的435)且来自洋葱假单胞菌、Burkholderia capacii、南极假丝酵母或少根根霉、褐色高温单孢菌、嗜热放线菌、茄病镰刀菌、特异腐质霉的脂肪酶或角质酶。
所用水解酶的总量通常在每种情况下基于全部溶液为0.001-40重量%,常常为0.01-15重量%,优选0.1-5重量%。
实施方案c)的特别优点在于所述可水解聚合物在碱性条件下水解,且由此与纸纤维完全分离,尤其是与聚合物层分离。
然而,在实施方案c)的情况下,在实施方案c)之前、期间或更通常是之后,需要额外使用实施方案a)和/或实施方案b),以除去防护包装产品的金属组分。因此,所述方法可理想地包括两步工艺,其包括首先酶促水解,然后碱性处理步骤。
在本发明方法的另一实施方案a)中,所述废纸悬浮液的制浆在碱性介质中进行,即,例如在由8往上,例如10-14,优选12-14的pH值范围内进行。为了调节pH值,将优选选自碱金属氢氧化物和碱土金属氢氧化物的碱添加至所述废纸悬浮液中。作为实例可提及氢氧化钠溶液、氢氧化钾溶液、氢氧化钙和氢氧化镁。当然也可使用其他氢氧化物。尤其优选使用氢氧化钠溶液。
实施方案a)的特别优点在于所述可水解聚合物和金属溶解于该碱性介质中,且由此完全与纸纤维分离。
此外,对于损纸的直接回收而言,实施方案a)和c)是特别有利的。在纸产品的生产中,通常产生这种所谓的损纸,其为具有较低且不希望的品质的纸产品。造纸商无法在生产工艺中再利用该与品质有关的生产损纸。相反,必须将该损纸分离除去并实施现有技术中所述的回收方法。现在,实施方案a)和c)可使造纸商在制浆机或转鼓式粉碎机中现场对其自己的损纸实施制浆。以此方式获得的纸纤维可直接用于生产纸产品的工艺中。
在本发明方法的实施方案b)中,在脱墨工艺中在碱性介质中对所述废纸悬浮液进行处理。
就脱墨而言,本领域熟练技术人员知晓首先为浮选脱墨工艺,其次为洗涤法脱墨工艺。根据本发明,在实施方案b)中可实施该两种脱墨工艺。现在通常首先将供入脱墨工艺中的废纸悬浮液制浆,以至少部分粉碎纸纤维。
根据浮选脱墨工艺,在纤维分离阶段(制浆)之后存在于废纸悬浮液中且与纤维分离的疏水化颗粒通过捕集化学品结合至气泡上,并通过这些传输至浮选槽的表面。撇除该负载有污垢的泡沫,所述泡沫除杂质和聚合物残留物之外还可包含纤维和填料。为了降低纤维损失,在增稠后对所述残留物处理之前,对该排出的泡沫进行纯化。通常将尤其为约2重量%氢氧化钠溶液,约1重量%过氧化氢,约3重量%水玻璃以及少量其他添加剂用作化学添加剂。所有化学品均一起溶于水中且一起添加至纤维分离的(制浆的)废纸悬浮液中。在一些回收工厂中,分开实施漂白。现在通常对所述废纸悬浮液连续两次进行浮选脱墨工艺,由此获得可能最好的杂质和聚合物与纸纤维的分离效果。
洗涤法脱墨工艺的使用范围及其广泛,尤其是在北美。与浮选法相反,洗涤法为脱水和增稠工艺。必须将与纤维分离且尽可能小的聚合物颗粒充分分散以使得在悬浮液的脱水过程中不再发生纤维的结合。为此,在整个工艺期间必须极其精确地保持规定的pH范围。脱水通常在多步骤工艺中进行,其中分离除去包含大大稀释的分离聚合物颗粒的所得滤液。所述洗涤法脱墨工艺的缺点在于填料和纤维的排出量大大高于浮选法。
如上所述,实施方案b)中的本发明方法可以两种脱墨工艺进行。对本发明而言必要的是首先将废纸悬浮液置于碱性介质中,并对该形式实施脱墨工艺。碱性介质意指废纸悬浮液具有由8往上,优选10-14,尤其优选12-14的pH值。
上述碱适于调节pH值,其中尤其优选使用氢氧化钠溶液。
此时,还特别有利的是所述可水解聚合物和金属组分溶解于碱性介质中,且因此完全与纸纤维分离。
本发明方法优选仅在所述实施方案a)或b)之一中进行。然而,也可以实施至少两个实施方案的任意所需组合,例如实施方案c)和实施方案a)和/或实施方案b)或者替代地实施方案c)和实施方案a)和/或b)。然而,所述实施方案b)或c)之一通常就足以实现可水解聚合物和金属与纸纤维的完全分离。
下文实施例旨在阐述而不以任何方式限制本发明。
实施例1
将涂覆有60%PLA和40%脂族-芳族聚酯(聚癸二酸丁二醇酯-co-对苯二甲酸丁二醇酯)的共混物的纸板在碎浆机中在pH12下处理。在15分钟之后,聚合物涂层完全溶解。如通过由再制浆纤维制备的纸的裂断长所测定的纤维质量显示出未受碱性处理不利地影响。
实施例2:
将铝箔(厚度:30μm)在碱性溶液中在环境温度下处理。在pH12下观察到经由氧化溶解的质量损失。在60分钟之后,35%铝膜溶解。
实施例3:
将铝箔(厚度:50μm)在碱性溶液中在50℃下处理。在pH12下观察到经由氧化溶解的质量损失。在60分钟之后,75%铝膜溶解。
实施例4:
将铝箔(厚度:100μm)在碱性溶液中在50℃下处理。在pH13下观察到经由氧化溶解的质量损失。在30分钟之后,25%铝膜溶解。
实施例5:
将包含5层,即60%PLA和40%聚癸二酸丁二醇酯-co-对苯二甲酸丁二醇酯的共混物(10μm)、纸板、60%PLA和40%聚癸二酸丁二醇酯-co-对苯二甲酸丁二醇酯的共混物(10μm)、铝(7μm)以及60%PLA和40%聚癸二酸丁二醇酯-co-对苯二甲酸丁二醇酯的共混物(10μm)的复合材料在碎浆机中在pH12下处理。在30分钟之后,聚合物涂层以及铝层完全溶解。
如通过由再制浆纤维制备的纸的裂断长所测定的纤维质量显示出未受碱性处理不利地影响。
Claims (23)
1.一种回收含有复合材料的防护包装产品的方法,所述复合材料包含:
i)纤维素层;
ii)至少一个金属层,其在碱性条件下溶解;和
iii)至少一个聚合物层,其中聚合物在碱性条件下为可水解的;
其中防护包装产品首先置于含水废纸悬浮液中,将该废纸悬浮液
a)在碱性介质中制浆,和/或
b)在脱墨工艺中在碱性介质中处理,
然后将金属和聚合物与纤维素层中含有的纤维素纤维分离。
2.根据权利要求1的方法,其中至少一个金属层为铝。
3.根据权利要求1的方法,其中聚合物为至少一种包含如下组分且具有根据EN ISO 1133在190℃和2.16kg重量下熔体体积速率为3-50cm3/10分钟的脂族-芳族聚酯:
i)基于组分i至ii为40-70mol%的一种或多种选自琥珀酸、己二酸、癸二酸、壬二酸和巴西酸的二羧酸衍生物或二羧酸;
ii)基于组分i至ii为60-30mol%的对苯二甲酸衍生物;
iii)基于组分i至ii为98-102mol%的C2-C8亚烷基二醇或C2-C6氧亚烷基二醇;
iv)基于组分i至iii总重量为0.00-2重量%的选自二-或多官能异氰酸酯、异氰脲酸酯、唑啉、环氧化物、羧酸酐和/或至少三官能的醇或至少三官能的羧酸的扩链剂和/或交联剂;
v)基于组分i至iv总重量为0.00-50重量%的选自天然或增塑淀粉、天然纤维、锯末的有机填料和/或选自白垩、沉淀碳酸钙、石墨、石膏、导电炭黑、氧化铁、氯化钙、白云石、高岭土、二氧化硅、碳酸钠、二氧化钛、硅酸盐、硅灰石、云母、蒙脱石、滑石、玻璃纤维和矿物纤维的无机填料;和
vi)基于组分i至iv总重量为0.00-2重量%的至少一种稳定剂、成核剂、润滑剂和脱模剂、表面活性剂、蜡、抗静电剂、防雾剂、染料、颜料、UV吸收剂或UV稳定剂。
4.根据权利要求2的方法,其中聚合物为至少一种包含如下组分且具有根据EN ISO 1133在190℃和2.16kg重量下熔体体积速率为3-50cm3/10分钟的脂族-芳族聚酯:
i)基于组分i至ii为40-70mol%的一种或多种选自琥珀酸、己二酸、癸二酸、壬二酸和巴西酸的二羧酸衍生物或二羧酸;
ii)基于组分i至ii为60-30mol%的对苯二甲酸衍生物;
iii)基于组分i至ii为98-102mol%的C2-C8亚烷基二醇或C2-C6氧亚烷基二醇;
iv)基于组分i至iii总重量为0.00-2重量%的选自二-或多官能异氰酸酯、异氰脲酸酯、唑啉、环氧化物、羧酸酐和/或至少三官能的醇或至少三官能的羧酸的扩链剂和/或交联剂;
v)基于组分i至iv总重量为0.00-50重量%的选自天然或增塑淀粉、天然纤维、锯末的有机填料和/或选自白垩、沉淀碳酸钙、石墨、石膏、导电炭黑、氧化铁、氯化钙、白云石、高岭土、二氧化硅、碳酸钠、二氧化钛、硅酸盐、硅灰石、云母、蒙脱石、滑石、玻璃纤维和矿物纤维的无机填料;和
vi)基于组分i至iv总重量为0.00-2重量%的至少一种稳定剂、成核剂、润滑剂和脱模剂、表面活性剂、蜡、抗静电剂、防雾剂、染料、颜料、UV吸收剂或UV稳定剂。
5.根据上述权利要求中任一项的方法,其中聚合物包含共聚物混合物,其为包含如下组分的那些:
(a)5-95重量%的可水解脂族-芳族聚酯;和
(b)95-5重量%的一种或多种选自聚乳酸、聚己酸内酯、聚羟基链烷酸酯、脱乙酰壳多糖和谷蛋白的聚合物以及一种或多种基于脂族二醇和脂族/芳族二羧酸的聚酯;和
(c)0-2重量%的增容剂。
6.根据权利要求5的方法,其中组分(a)为30-90重量%。
7.根据权利要求5的方法,其中组分(a)为40-70重量%。
8.根据权利要求5的方法,其中组分(b)为70-10重量%。
9.根据权利要求5的方法,其中组分(b)为60-30重量%。
10.根据权利要求5的方法,其中组分(b)为聚琥珀酸丁二醇酯、聚琥珀酸己二酸丁二醇酯、聚琥珀酸癸二酸丁二醇酯、聚对苯二甲酸丁二醇酯-co-己二酸丁二醇酯。
11.根据权利要求6-9中任一项的方法,其中组分(b)为聚琥珀酸丁二醇酯、聚琥珀酸己二酸丁二醇酯、聚琥珀酸癸二酸丁二醇酯、聚对苯二甲酸丁二醇酯-co-己二酸丁二醇酯。
12.根据权利要求1-4中任一项的方法,其中除了实施方案a)和/或b)外,将废纸悬浮液
c)在至少一种水解酶存在下制浆。
13.根据权利要求11的方法,其中除了实施方案a)和/或b)外,将废纸悬浮液
c)在至少一种水解酶存在下制浆。
14.根据权利要求1-4中任一项的方法,其中将废纸悬浮液在制浆机或转鼓式粉碎机中制浆。
15.根据权利要求13的方法,其中将废纸悬浮液在制浆机或转鼓式粉碎机中制浆。
16.根据权利要求1-4中任一项的方法,其中碱性介质中废纸悬浮液的pH值为8-14。
17.根据权利要求15的方法,其中碱性介质中废纸悬浮液的pH值为8-14。
18.根据权利要求1-4中任一项的方法,其中废纸悬浮液的pH值通过添加选自碱金属化合物和碱土金属化合物的碱而调节。
19.根据权利要求17的方法,其中废纸悬浮液的pH值通过添加选自碱金属化合物和碱土金属化合物的碱而调节。
20.根据权利要求12的方法,其中水解酶为羧酸酯酶[3.1.1.1]和/或脂肪酶[3.1.1.3]和/或角质酶[3.1.1.74]。
21.根据权利要求13的方法,其中水解酶为羧酸酯酶[3.1.1.1]和/或脂肪酶[3.1.1.3]和/或角质酶[3.1.1.74]。
22.根据权利要求12的方法,其中水解酶为聚羟基链烷酸酯解聚酶和/或蛋白酶K和/或savinase。
23.根据权利要求13的方法,其中水解酶为聚羟基链烷酸酯解聚酶和/或蛋白酶K和/或savinase。
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- 2012-04-16 CN CN201280019554.5A patent/CN103492280B/zh not_active Expired - Fee Related
- 2012-04-16 WO PCT/EP2012/056892 patent/WO2012143323A1/en active Application Filing
- 2012-04-16 EP EP12718122.0A patent/EP2699485A1/en not_active Withdrawn
- 2012-04-16 US US14/112,350 patent/US20140050934A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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WO2012143323A1 (en) | 2012-10-26 |
CA2831965A1 (en) | 2012-10-26 |
EP2699485A1 (en) | 2014-02-26 |
CN103492280A (zh) | 2014-01-01 |
US20140050934A1 (en) | 2014-02-20 |
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