CN118043197A - 生物可降解的层压膜 - Google Patents
生物可降解的层压膜 Download PDFInfo
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- CN118043197A CN118043197A CN202280065380.XA CN202280065380A CN118043197A CN 118043197 A CN118043197 A CN 118043197A CN 202280065380 A CN202280065380 A CN 202280065380A CN 118043197 A CN118043197 A CN 118043197A
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- laminate film
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Abstract
本发明涉及一种具有层结构A/B的生物可降解的层压膜,其中,0.5μm至7μm厚的层A包含聚氨酯胶粘剂或丙烯酸酯胶粘剂;5μm至150μm厚的层B包含脂肪族聚酯和/或脂肪族‑芳香族聚酯,所述脂肪族‑芳香族聚酯的组成成分如下:b1‑i)以成分b1‑i和b1‑ii为基础,30mol%至70mol%的C6‑C18二羧酸;b1‑ii)以成分b1‑i和b1‑ii为基础,30mol%至70mol%的对苯二甲酸;b1‑iii)以成分b1‑i和b1‑ii为基础,98mol%至100mol%的1,3‑丙二醇或1,4‑丁二醇;b1‑iv)以成分b1‑i和b1‑iii为基础,0mol%至2mol%的扩链剂和/或支化剂。
Description
本发明涉及一种具有层结构A/B的生物可降解的层压膜,其中,0.5μm至7μm厚的层A包含聚氨酯胶粘剂或丙烯酸酯胶粘剂;5μm至150μm厚的层B包含脂肪族聚酯和/或脂肪族-芳香族聚酯,所述脂肪族-芳香族聚酯的组成成分如下:
b1-i)以成分b1-i和b1-ii为基础,30mol%至70mol%的C6-C18二羧酸;
b1-ii)以成分b1-i和b1-ii为基础,30mol%至70mol%的对苯二甲酸;
b1-iii)以成分b1-i和b1-ii为基础,98mol%至100mol%的1,3-丙二醇或1,4-丁二醇;
b1-iv)以成分b1-i和b1-iii为基础,0mol%至2mol%的扩链剂和/或支化剂。
此外,本发明还涉及上述层压膜用于涂覆诸如纸或纸板之类的基材的用途,以及一种层压膜的制造方法,其中上述层压膜压在基材上。
软包装尤其用于食品工业。它通常由使用适当胶粘剂粘合在一起的复合膜组成,其中粘合在一起的膜中至少一层是高分子膜。对使用后可堆肥处理的生物可降解的复合膜包装的需求量很大。
迄今为止,文献中已经提出了多种方法:
WO 2010/034712描述了一种使用生物可降解的聚合物来挤出涂覆纸张的方法。该方法一般不使用胶粘剂。WO 2010/034712中描述的方法可获得的涂布纸并非适用于所有应用,这是因为纸张的粘附性、机械性能、阻隔性能和纸张复合材料的生物降解性能有限。
WO 2012/013506描述了水性聚氨酯分散体胶粘剂用于制造复合膜的用途,这种复合膜可部分工业堆肥。在工业堆肥厂中,降解是在高空气湿度、存在某些特定微生物且约55℃的温度下进行的。对软包装生物降解性的要求在不断提高,因此,如今许多应用都要求具有家庭堆肥性。WO 2012/013506中描述的复合膜并不能充分满足这一标准,而且在机械性能和阻隔性能方面也不适用于软包装的所有应用。
因此,本发明的目的是提供在生物降解性方面有所改进的复合膜,这些复合膜优选地可家庭堆肥,与基材(优选纸张)具有良好的粘附性,同时还能满足现代软包装的其他要求。
令人惊讶的是,上述这些复合膜满足这些标准。
下文将详细描述本发明。
层A也可称为粘接层,在层B和基材之间形成连接。层A的层厚度为0.5μm至7μm,包含聚氨酯胶粘剂或丙烯酸酯胶粘剂。
优选地,层A中的胶粘剂基本上由至少一种分散在水中的作为聚合物接合剂的聚氨酯和可选的添加剂(如填料、增稠剂、消泡剂等)组成,详见WO 2012/013506中的描述。下文列出了WO 2012/013506中所描述的、明确引用的聚氨酯胶粘剂的基本特征:
优选地,聚合物接合剂以分散体的形式存在于水中、或水和水溶性有机溶剂的混合物中,该混合物的沸点优选低于150℃(1巴)。特别优选地,水作为唯一的溶剂。在胶粘剂成分的重量数据中,水或其他溶剂的重量没有计算进去。
优选地,聚氨酯分散体胶粘剂是可生物降解的。例如,根据ISO 14855(2005)标准测量,20天后以CO2形式释放的气态碳与所用材料总碳含量的比率至少为30%,优选地至少为60%或至少为80%,即具有本申请中所指的生物可降解性。
优选地,聚氨酯一方面主要由多异氰酸酯、尤其是二异氰酸酯组成,另一方面以聚酯二元醇和双官能羧酸作为反应物。优选地,聚氨酯由至少40wt%,特别优选至少60wt%,非常特别优选至少80wt%的二异氰酸酯、聚酯二元醇和双官能羧酸构成。
聚氨酯可以是无定形的,也可以是半结晶的。如果聚氨酯是半晶体,熔点优选低于80℃。优选地,聚氨酯中聚酯二元醇的含量高于10wt%、高于50wt%或至少80wt%(以聚氨酯为基础)。巴斯夫公司以商标名销售的聚氨酯分散体尤其适用。
总的来说,聚氨酯优选地由以下成分组成:
a)二异氰酸酯
b)二元醇,其中
b1)10mol-%至100mol-%(以二元醇(b)总量为基础)为聚酯二元醇,其分子量为500g/mol至5000g/mol,
b2)0mol-%至90mol-%(以二元醇(b)总量为基础),分子量为60g/mol至500g/mol,
c)至少一种双官能羧酸,所述羧酸选自由以下项组成的组:二羟基羧酸和二氨基羧酸,
d)可选地,除单体(a)至(c)外,还可以是具有反应基团的多价化合物,这些反应基团可以是醇羟基、伯氨基或仲氨基或异氰酸酯基,以及
e)可选地,除单体(a)至(d)外,还可以是具有反应基团的单价化合物,这些反应基团可以是醇羟基、伯氨基或仲氨基或异氰酸酯基。
特别优选的是如PCT/EP2021/054570(以WO 2021/175676 A1文件公开)中所述的层A中的可家庭堆肥的胶粘剂。下文列出了PCT/EP2021/054570中所描述的、明确引用的聚氨酯胶粘剂的基本特征:
PCT/EP2021/054570的水性聚氨酯分散体胶粘剂适用于制造复合膜,这些复合膜在家庭堆肥条件下(25±5℃)可生物降解,其中,至少一层B和第二层基材使用聚氨酯分散体胶粘剂A粘合,并且
其中,至少一种基材是在家庭堆肥条件下可生物降解的高分子膜,其中,至少60wt%的聚氨酯由以下成分组成:
(a)至少一种二异氰酸酯
(b)至少一种聚酯二醇,和
(c)至少一种双官能羧酸,所述羧酸选自由以下项组成的组:二羟基羧酸和二氨基羧酸;
其中,聚氨酯的玻璃化转变温度低于20℃,熔点不高于20℃,或熔点高于20℃的同时熔化焓低于10J/g,并且
其中,优选地,在家庭堆肥条件下,聚氨酯胶粘剂层A在360天内超过90wt%分解为CO2和水;其中,优选地,聚氨酯胶粘剂层A可用于家庭堆肥,以及
其中,优选地,如果在25±5℃的条件下,经过最多180天的有氧堆肥处理后,在大于2mm的筛分物中,材料原始干重的至多10%存在于筛分物中,则由此制成的层压膜A/B在家庭堆肥条件下是生物可降解的。
优选地,由聚氨酯胶粘剂、层B和/或基材和/或复合膜组成的薄膜可家庭堆肥。
巴斯夫公司以Eco商标名销售的聚氨酯分散体尤其适用。
根据本发明的层B具有5μm至150μm的层厚度,包含脂肪族聚酯和/或脂肪族-芳香族聚酯,其中,脂肪族-芳香族聚酯的成分组成如下:
b1-i)以成分b1-i和b1-ii为基础,30mol%至70mol%的C6-C18二羧酸;
b1-ii)以成分b1-i和b1-ii为基础,30mol%至70mol%的对苯二甲酸;
b1-iii)以成分b1-i和b1-ii为基础,98mol%至100mol%的1,3-丙二醇或1,4-丁二醇;
b1-iv)以成分b1-i和b1-iii为基础,0mol%至2mol%的扩链剂和/或支化剂
例如,脂肪族聚酯应理解为如WO 2010/034711中更详细描述的聚酯,该聚酯在此明确引用。
一般地,WO 2010/034711(i)的聚酯构成如下:
i-a)以成分i-a至i-b为基础,80mol%至100mol%的丁二酸;
i-b)以成分i-a至i-b为基础,0mol%至20mol%的一种或多种C6-C20二羧酸;
i-c)以成分i-a至i-b为基础,99mol%至102mol%、优选99mol%至100mol%的1,3-丙二醇或1,4-丁二醇;
i-d)以成分i-a至i-c为基础,0wt%至1wt%的扩链剂和/或支化剂;
WO 2010/034711中的聚酯i优选通过各组分的直接缩聚反应合成。二羧酸衍生物与二元醇在酯交换催化剂存在下直接反应,形成高分子量的缩聚物。另一方面,在二元醇存在下,聚丁二酸丁二醇酯(PBS)与C6-C20二羧酸发生酯交换反应,也可以得到共聚多酯。通常使用锌催化剂、铝催化剂,特别是钛催化剂作为催化剂。钛催化剂,如钛酸四异丙酯,特别是钛酸四丁酯(TBOT),与文献中常用的锡催化剂、锑催化剂、钴催化剂和铅催化剂(如辛酸锡)相比,其优点是产品中残留的催化剂或催化剂副产物的毒性较低。这对于可生物降解的聚酯尤为重要,因为这些催化剂会直接释放到环境中。
此外,上述聚酯也可按照JP 2008-45117和EP-A 488 617中所述的方法制备。已证明有利的是,首先使组份a至c转化形成VZ值为50mL/g至100mL/g、优选60mL/g至80mL/g的预聚酯,然后与扩链剂i-d发生扩链反应,例如与二异氰酸酯或含环氧化物的聚甲基丙烯酸酯发生扩链反应,转化形成VZ值为100mL/g至450mL/g、优选150mL/g至300mL/g的聚酯i。
使用的酸组分i-a是80mol%至100mol%、优选90mol%至99mol%、特别优选92mol%至98mol%(基于酸组分a和b)的丁二酸。丁二酸可以通过石油化工手段获得,优选来自可再生原料,例如EPA 2185682中所述。EPA 2185682公开了一种利用巴氏杆菌纲(Pasteurellaceae)微生物从不同碳水化合物中制备丁二酸和1,4-丁二醇的生物技术方法。
以酸组分i-a和i-b为基础,酸组分i-b的使用量为0mol%至20mol%,优选为1mol%至10mol%,特别优选为2mol%至8mol%。
尤其地,C6-C20二羧酸i-b应理解为己二酸、辛二酸、壬二酸、癸二酸、十三烷二酸和/或C18二羧酸。优选辛二酸、壬二酸、癸二酸和/或十三烷二酸。上述酸类可从可再生原料中获得。例如,可从蓖麻油中获得癸二酸。这种聚具有优异的生物降解性能[文献:聚合物的降解性和稳定性2004,85,855-863]。
使用二羧酸i-a和i-b既可以是游离酸的形式,也可以是形成酯的衍生物的形式。形成酯的衍生物特别是二C1-C6烷基酯,如二甲基、二乙基、二正丙基、二异丙基、二正丁基、二异丁基、二叔丁基、二正戊基、二异戊基或二正己基酯,可作为酯形成衍生物。也可以使用二羧酸的酸酐。二羧酸或其他形成酯的衍生物可以单独使用,也可以混合使用。
二元醇1,3-丙二醇和1,4-丁二醇也可以从可再生原料中获得。也可以使用这两种二元醇的混合物。由于1,4-丁二醇的熔化温度更高,形成的共聚物结晶性更好,因此是优选二元醇。
一般地,二元醇(组分i-c)在聚合开始时加入酸(组分i-a和i-b)中,二元醇与二元酸的比例为1.0:1至2.5:1,优选为1.3:1至2.2:1。过量的二元醇在聚合过程中被除去,以便在聚合结束时达到近似等摩尔量的比例。所谓近似等摩尔量,是指二元酸/二元醇的比例为0.98至1.00。
在一个实施方式中,使用0wt%至1wt%、优选0.1wt%至0.9wt%、特别优选0.1wt%至0.8wt%(以成分i-a至i-b为基础)的支化剂i-d和/或扩链剂i-d',其选自由以下项组成的组:多官能异氰酸酯、异氰脲酸酯、噁唑啉、羧酸酐(如马来酸酐)、环氧化物(特别是含环氧化物的聚(甲基)丙烯酸酯)、至少三官能的醇或至少三官能的羧酸。通常不使用支化剂,只使用扩链剂。
合适的双官能扩链剂包括甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、2,2'-二苯基甲烷二异氰酸酯、2,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯或苯二甲基二异氰酸酯、1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或亚甲基双(4-异氰酸环己烷)。特别优选异佛尔酮二异氰酸酯,尤其是1,6-六亚甲基二异氰酸酯。
尤其地,脂肪族聚酯i指聚丁二酸丁二醇酯(PBS)、聚丁二酸-己二酸丁二醇酯(PBSA)、聚丁二酸-癸二酸丁二醇酯(PBSSe)、聚丁二酸-壬二酸丁二醇酯酯(PBSAz)或聚丁二酸-十三烷二酸丁二醇酯(PBSBr)。脂肪族聚酯PBS和PBSA例如由三菱公司以名称在市场上销售。WO 2010/034711中描述了更多最新进展。
一般地,聚酯i的数均分子量(Mn)在5000至100000之间、特别是10000g/mol至75000g/mol之间、优选15000g/mol至50000g/mol之间,重均分子量(Mw)在30000至300000之间,优选60000g/mol至200000g/mol之间,且Mw/Mn比例为1至6、优选2至4。粘度值在30g/mL至450g/mL之间、优选100g/mL至400g/mL之间(在邻二氯苯/苯酚(重量比为50/50)中测量计算)。熔点在85℃至130℃之间,优选95℃至120℃之间。根据DIN EN 1133-1标准,MVR的范围为8cm3/10min至50cm3/10min,特别是15cm3/10min至40cm3/10min(190℃,2.16kg)。
层B的脂肪族聚酯还可以使用聚羟基烷酸酯,如聚己内酯(PCL)、聚-3-羟基丁酸酯(PHB)、聚-3-羟基丁酸酯-co-3-羟基戊酸酯(P(3HB)-co-P(3HV))、聚-3-羟基丁酸酯-co-4-羟基丁酸酯(P(3HB)-co-P(4HB))和聚-3-羟基丁酸酯-co-3-羟基己酸酯(P(3HB)-co-P(3HH)),特别是聚乳酸(PLA)。
优选使用具有以下特性的聚乳酸b2:
熔体体积流动速率(根据ISO 1133-1DE标准,在190℃且2.16kg下,MVR)为0.5cm3/10min至100cm3/10min,特别是5cm3/10min至50cm3/10min
熔点低于240℃;
玻璃化温度(Tg)高于55℃;
含水量低于1000ppm
残余单体含量(丙交酯)低于0.3%
分子量大于80000道尔顿。
优选的聚乳酸是自然工坊公司(NatureWorks)的结晶型聚乳酸,如6201D、6202 D、6251 D、3051 D和3251 D,特别是4043 D和4044D,以及道达尔-科碧恩公司(Total Corbion)的聚乳酸,如/>L175和LX175 Corbion,以及海正药业(Hisun)的聚乳酸,如/>190或110。不过,无定形聚乳酸类型也可以适用,如自然工坊公司的4060D。
层B中的脂肪族-芳香族聚酯b1是指线型、扩链型聚酯,以及可选的支链型、扩链型聚酯,如WO 96/15173至15176或WO 98/12242中所述,在此明确引用。也可以考虑使用不同的部分芳香族聚酯的混合物。有趣的最新进展基于可再生原料(参见WO 2010/034689)。尤其地,聚酯b1是指(巴斯夫公司)等产品。
优选的聚酯b1是指包括以下基本成分的聚酯:
b1-i)基于成分b1-i)和b1-ii),30mol%至70mol%、优选40mol%至60mol%,特别优选50mol%至60mol%的脂肪族二羧酸或其混合物,优选如下:己二酸,特别是壬二酸、癸二酸和十三烷二酸,
b1-ii)基于成分b1-i)和b1-ii),30mol%至70mol%、优选40mol%至50mol%,特别优选40mol%至60mol%的芳香族二羧酸或其混合物,优选如下:对苯二甲酸,
b1-iii)以成分b1-i和b1-ii为基础,98mol%至100mol%的1,4-丁二醇或1,3-丙二醇;和
b1-iv)以成分b1-i至b1-iii为基础,0wt%至2wt%、优选0.1wt%至1wt%的扩链剂,特别是双官能的或多官能的异氰酸酯,优选六亚甲基二异氰酸酯,以及可选的支化剂,优选:三羟甲基丙烷、季戊四醇,特别是甘油。
脂肪族二元酸和相应的衍生物b1-i通常具有6至18个碳原子,优选9至14个碳原子。它们可以是线性的,也可以是分支的。
示例性地包括:己二酸、壬二酸、癸二酸和十三烷二酸和辛二酸(软木酸)。二羧酸或其酯形成衍生物可以单独使用,也可以作为由两种或两种以上的上述物质组成的混合物使用。
优选使用己二酸、壬二酸、癸二酸、十三烷二酸或其相应的酯形成衍生物或其混合物。特别优选使用壬二酸或癸二酸或其相应的酯形成衍生物或其混合物。
特别优选以下脂肪族-芳香族聚酯:聚己二酸-对苯二甲酸丁二醇酯(PBAT)、聚己二酸-壬二酸对苯二甲酸丁二醇酯(PBAAzT)、聚己二酸-癸二酸对苯二甲酸丁二醇酯(PBASeT)、聚壬二酸-对苯二甲酸丁二醇酯(PBAzT)和聚癸二酸-对苯二甲酸丁二醇酯(PBSeT),以及这些聚酯的混合物。
由于根据澳大利亚标准AS 5810-2010和ISO 14855-1(2012)标准具有更好的家庭可堆肥性,特别优选聚己二酸-壬二酸对苯二甲酸丁二醇酯(PBAAzT)、聚己二酸-癸二酸对苯二甲酸丁二醇酯(PBASeT)、聚壬二酸-对苯二甲酸丁二醇酯和聚癸二酸-对苯二甲酸丁二醇酯(PBSeT)以及聚己二酸-对苯二甲酸丁二醇酯(PBAT)与聚己二酸-壬二酸对苯二甲酸丁二醇酯(PBAzT)和聚己二酸-癸二酸对苯二甲酸丁二醇酯(PBSeT)的混合物。
芳香族二羧酸或其酯形成衍生物b1-ii可以单独使,也可以作为由两种或两种以上的上述物质组成的混合物使用。特别优选对苯二甲酸或其酯形成衍生物,如对苯二甲酸二甲酯。
二元醇b1-iii--1,4-丁二醇和1,3-丙二醇--可作为可再生原料获得。也可以使用这些二元醇的混合物。
通常使用0wt%至1wt%、优选0.1wt%至1wt%、特别优选0.1wt%至0.3wt%(以聚酯总重量为基础)的支化剂和/或0wt%至1wt%、优选0.1wt%至1wt%(以聚酯总重量为基础)的扩链剂(b1-vi)。优选使用双官能或多官能的异氰酸酯(优选六亚甲基二异氰酸酯)作为扩链剂,并使用多元醇(例如优选三羟甲基丙烷、季戊四醇,特别是甘油)作为支化剂。
一般地,聚酯b1的数均分子量(Mn)在5000g/mol至100000g/mol之间、特别是10000g/mol至75000g/mol之间、优选15000g/mol至38000g/mol之间,重均分子量(Mw)在30000g/mol至300000g/mol之间,优选60000g/mol至200000g/mol之间,且Mw/Mn比例为1至6、优选2至4。粘度值在50g/mL至450g/mL之间、优选80g/mL至250g/mL之间(在邻二氯苯/苯酚(重量比为50/50)中测量计算)。熔点在85℃至150℃之间,优选地在95℃至140℃之间。
根据EN ISO 1133-1DE标准(190℃,2.16kg重量),聚酯b1的MVR(熔体体积流动率)一般为0.5cm3/10min至20cm3/10min、优选为5cm3/10min至15cm3/10min。根据DIN EN 12634标准,酸数一般为0.01mg KOH/g至1.2mg KOH/g、优选为0.01mg KOH/g至1.0mg KOH/g、特别优选为0.01mg KOH/g至0.7mg KOH/g。
通常地,0wt%至25wt%、特别是3wt%至20wt%(以层B总重量为基础)的至少一种矿物填料b3选自由以下项组成的组:白垩、石墨、石膏、导电炭黑、氧化铁、硫酸钙、白云石、高岭土、二氧化硅(石英)、碳酸钠、碳酸钙、二氧化钛、硅酸盐、硅灰石、云母、蒙脱石和滑石。优选的矿物填料是二氧化硅、高岭土和硫酸钙,特别优选的是:碳酸钙和滑石。
层B的一个优选实施方式包含:
b1)60wt%至100wt%、优选60wt%至99.95wt%的脂肪族-芳香族聚酯,所述脂肪族-芳香族聚酯选自由以下项组成的组:聚己二酸-对苯二甲酸丁二醇酯、聚壬二酸-对苯二甲酸丁二醇酯和聚癸二酸-对苯二甲酸丁二醇酯;
b2)0wt%至15wt%、优选3wt%至12wt%的聚羟基烷酸酯、优选聚乳酸;
b3)0wt%至25wt%、优选3wt%至20wt%的矿物填料。
特别优选地,层B还包含
b4)0.05wt%至0.3wt%的润滑剂,所述润滑剂选自芥酸酰胺和硬脂酸酰胺。
在一个实施方式中,层B不包含润滑剂或脱模剂。在层厚度达到150μm的情况下,这种实施方式与层A的相容性非常好,因此层压膜与基材(尤其是纸或纸板)的粘附性非常好。当试图将膜从纸或纸板上剥离时,纤维撕裂的现象就证明了这一点。
在另一个实施方式中,层B含有0.05wt%至0.3wt%(以层B总重量为基础)的润滑剂或脱模剂,如芥酸酰胺或优选硬脂酸酰胺。尤其地,润滑剂或脱模剂与防粘连剂结合使用,可防止聚酯膜在开卷过程中发生粘连,聚酯膜可在下一步骤中用于层压。这种含有聚酯层的层压塑料可以进行后续的、可选地紧随进行的变形。在层厚度达到50μm、甚至层厚度达到80μm(对于硬脂酸酰胺)的情况下,这种实施方式与层A的相容性非常好,因此层压膜与基材(尤其是纸或纸板)的粘附性非常好。当试图将膜从纸或纸板上剥离时,纤维撕裂的现象就证明了这一点。另一方面,如果润滑剂或脱模剂(如山嵛酸酰胺、芥酸酰胺或硬脂酸酰胺)在层B中的使用浓度高于0.3wt%,则会观察到与层A的相容性变差。如果层B含有硬脂酸酰胺,则层B的厚度优选为5μm至50μm、优选为10μm至50μm。如果层B含有芥酸酰胺,则层厚度优选在5μm至80μm之间、更优选在5μm至50μm之间、特别优选在10μm至50μm之间。
此外,根据本发明的成分i至v的化合物还可以含有技术人员已知的其他添加剂。例如,塑料技术中常用的添加剂,如稳定剂;成核剂,如上述矿物填料b3或结晶型聚乳酸;脱模剂,如硬脂酸盐(特别是硬脂酸钙);增塑剂,如柠檬酸酯(特别是乙酰柠檬酸三丁酯)、甘油酸酯(如三乙酰甘油或乙二醇衍生物)、表面活性剂(如聚山梨醇酯、棕榈酸酯或月桂酸酯);抗静电剂、紫外线吸收剂;紫外线稳定剂;防雾剂、颜料或优选巴斯夫公司的生物可降解染料使用添加剂的浓度为0wt%至2wt%,特别是0.1wt%至2wt%(以层B为基础)。根据本发明的层B中可包含增塑剂,其浓度为0.1wt%至10wt%。
对于食品工业中的软包装,对氧气阻隔性或香味阻隔性的要求很高。在这里,带有附加阻隔层C的层结构已被证明是有利的。例如,合适的层结构是A/B/C/B,其中层A和层B具有上述含义,层C是由聚乙醇酸(PGA)、乙烯-乙烯醇(EVOH)或优选聚乙烯醇(PVOH)组成的阻隔层。
氧气阻隔层C的层厚度通常为2μm至10μm,优选地由聚乙烯醇组成。合适的PVOH例如是三菱化学公司的G聚合物、特别是G聚合物BVE8049。由于PVOH不能充分附着在生物聚合物层B上,因此阻隔层优选由C'/C/C'层组成,其中层C'为增附剂层。例如,三菱化学公司的共聚物BTR-8002P适合用作增附剂。增附剂层的厚度通常为2μm至6μm。在这种情况下,层压膜例如具有整体层结构A/B/C'/C/C'/B或B'。
另一种合适的层结构是A/B/C/B',其中层A、B和C具有上述含义,层B'的层厚度为10μm至100μm,除了层B所提及的成分外,还含有0.1wt%至0.5wt%/优选0.2wt%至0.5wt%(以层B'总重量为基础)的芥酸酰胺、硬脂酸酰胺或优选山嵛酸酰胺作为润滑剂或脱模剂。
根据本发明的层压膜用于基材的复合膜胶合的用途,所述基材选自由以下项组成的组:生物可降解的膜、金属膜、金属化膜、玻璃纸或优选纸制品。
在本发明中,术语“纸制品”包括所有类型的纸和纸板。
适用于制造上述纸制品的纤维包括所有常用类型,例如机械纸浆、漂白和未漂白纸浆、源自所有一年生植物的纸浆以及废纸(包括涂布或未涂布的破损纸张)。上述纤维既可以单独使用,也可以以任何混合物的形式用于生产纸浆,纸制品用这些纸浆制成。木纸浆包括磨木浆、热机械浆(TMP)、化学热机械浆(CTMP)、加压磨木浆、半化学浆、高产化学浆和磨浆机械浆(RMP)。例如,适用的化学浆包括硫酸盐浆、亚硫酸盐浆和碳酸钠浆。适合制造纸浆的一年生植物的示例有大米、小麦、甘蔗和槿麻。
通常在纸浆中加入0.01wt%至3wt%、优选0.05wt%至1wt%(分别以纸浆干物质的固体含量为基础)的胶合剂,胶合剂的用量取决于纸张成品所需的胶合度。此外,纸中还可以含有其他物质,如淀粉、颜料、染料、光学增白剂、生物杀灭剂、纸张增强剂、固着剂、消泡剂、助留剂和/或脱水助剂。
优选地,制成的复合膜具有以下结构:
i)单位面积重量为30g/m2至600g/m2、优选为40g/m2至400g/m2、特别优选为50g/m2至150g/m2的纸,
ii)总厚度为5.5μm至300μm、优选为10μm至150μm、特别优选为15μm至100μm的根据本发明的层压膜。
纸层可以使用多种材料,例如白色或棕色牛皮纸、纸浆、废纸、瓦楞纸板或栅渣(Rechengut)。
纸膜复合材料的总厚度通常在31g/m2至1000g/m2之间。优选地,通过层压法生产80-500μm的纸膜复合材料,特别是通过挤压涂布法生产50-300μm的纸膜复合材料。
用本发明的层压膜和基材制造复合膜优选地分多个步骤进行:首先优选地,i)层B的表面通过电晕处理活化;ii)涂上并干燥聚氨酯胶粘剂的水性分散体;iii)通过适当的滚压将权利要求1至7所述的获得的层压膜的面A压在所述基材上。
在涂覆聚合物分散体A之前,对层B进行表面处理并非绝对必要。但是,如果在涂覆工艺之前对层B的表面进行改性,则可以获得更好的效果。在这里,可以使用传统的表面处理方法(如电晕处理)来增强粘合效果。电晕处理或其他表面处理的程度应满足涂层化合物充分润湿的要求。通常情况下,每平方米每分钟约10瓦的电晕处理就足够了。替代性地或附加地,也可以在层B和胶粘剂涂层A之间使用底漆或中间层。如前所述,复合膜、特别是层压膜还可以有其他附加功能层,如阻隔层、印刷层、涂层或漆层或保护层。功能层的位置优选在外侧,即在层B远离胶粘剂涂层的一侧。
在本发明的复合膜内,基材(如纸)可防止矿物油和其他类型的油以及油脂和湿气的侵害,因为复合膜具有相应的阻隔效果。另一方面,当将复合膜用于食品包装时,由于复合膜具有这种阻隔效果,食品可免受废纸中的矿物油和矿物质的影响。由于复合膜既可以与自身焊接,也可以与纸、纸板、玻璃纸和金属焊接,因此可用于制造咖啡杯、饮料纸盒或冷冻产品纸盒等。
这种复合膜尤其适用于生产干食品(如咖啡、茶、汤粉、酱粉)纸袋;液体(如化妆品、清洁剂、饮料)纸袋;管状层压材料;冰淇淋、糖果(如巧克力和麦棒)纸袋、纸层压材料膜和共挤膜以及纸胶带;纸杯、酸奶罐;即食餐盘;包装纸板箱纸(罐、桶),用于外包装的湿强度纸盒(酒瓶、食品);涂布纸板制成的水果箱;快餐盘;保鲜盘;饮料纸盒和液体纸盒,如洗涤剂和清洁剂,冷冻产品纸盒,冰淇淋包装(如冰淇淋桶、包装材料)(如冰淇淋桶、锥形冰淇淋威化饼的包装材料);纸标签;花盆和植物盆。
有利地,使用挤出涂覆工艺将层压膜涂覆到基材上。涂覆上述水性复膜胶制剂(聚合物分散体A)作为中间层。在挤压涂覆工艺中使用复膜胶制剂的优点是可以降低挤压温度。所使用的温和条件可节省能源,并防止生物可降解的或优选可家庭堆肥的聚合物分解。
分散体涂料在使用前不需要加热。就片状涂料而言,其涂覆技术可与热熔胶粘剂的相媲美。卷筒速度非常高:最高可达3000m/min。因此,分散涂覆工艺也可以在造纸机上在线进行。
对于薄层,也可以采用热熔胶粘剂的形式涂覆层A,这在某种程度上是挤压涂覆工艺或分散涂覆工艺的一种特殊情况。Ullmann,TSE Troller涂层一书中介绍了这种工艺。热熔胶粘剂(Hotmelt)从预热的储存容器中以约150℃至200℃的温度泵入喷嘴,通过喷嘴将材料涂覆到表面。
根据本发明制造的复合膜特别适用于制造软包装,尤其是食品包装。
因此,本发明提供了使用本发明所述层压膜来制造生物可降解的或优选在家庭堆肥条件下生物可降解的复合膜的方法,其中,复合膜是家庭可堆肥的软包装的一部分。
本发明的优点在于,根据本发明使用的层压膜可以在不同材料(如基材和层B)之间实现良好的粘合,从而使粘合后的复合膜具有较高的强度。此外,根据本发明制造的复合膜还具有良好的生物可降解性,特别是家庭可堆肥性。
在本发明中,根据DIN EN 13432标准,如果一种物质或物质混合物在180天后的生物降解度达到至少90%,即符合“生物可降解”的特性。
一般地,生物可降解性是指聚酯(混合物)在合理且可检测的时间内分解。降解可通过酶、水解、氧化和/或电磁辐射(如紫外线辐射)的作用进行,通常主要通过微生物(如细菌、酵母菌、真菌和藻类)的作用进行。生物可降解性可以通过将聚酯与堆肥混合并存放一段时间来量化。例如,根据DIN EN 13432标准(参照ISO 14855标准),在堆肥过程中,让不含CO2的空气流过成熟的堆肥,并将其置于规定的温度程序中。在这里,生物可降解性是指样品的CO2净释放量(扣除不含样品的堆肥释放的CO2后)与样品的最大CO2释放量(根据样品的碳含量计算)之比作为生物降解程度的百分比。生物可降解聚酯(混合物)一般在堆肥几天后就会出现明显的降解迹象,如真菌生长、开裂和孔洞形成。
例如,ASTM D 5338和ASTM D 6400-4中描述了测定生物可降解性的其他方法。
优选地,本发明提供了在家庭堆肥条件(25±5℃)下生物可降解的层压膜或包含该层压膜的复合膜。家庭堆肥条件是指在360天内,层压膜或复合膜超过90wt%降解成CO2和水。
家庭可堆肥性根据澳大利亚标准AS 5810-2010或法国标准NF T 51-800或ISO14855-1(2012)标准“受控堆肥条件下塑料最终需氧生物分解能力的测定--采用分析测定释放的二氧化碳的方法”在环境温度(28±2℃)下进行测试,以模拟并非ISO 14855-1(2012)标准中所述的58℃的家庭堆肥条件。
特征:
玻璃化转变温度采用差示扫描量热法(ASTM D 3418-08,第二条加热曲线的“中点温度”,加热速度20K/m)测定。
熔点和熔化焓是根据DIN 53765(1994)标准(熔点=峰值温度)测定的,方法是将聚氨酯膜加热到120℃后,以20K/min的速度加热,再以20K/min的速度冷却到23℃,然后退火20小时。
起始材料
层A)的成分
a-1)巴斯夫公司的Eco 3702,水性聚氨酯分散体(参见PCT/EP2021/054570)
a-2)巴斯夫公司的P 100eco,水性聚氨酯分散体(参见WO 2010/034712)
层B)的成分
成分b1):
b1-1)聚己二酸-对苯二甲酸丁二醇酯:巴斯夫公司的F C1200(MVR为2.5-4.5cm3/10min(190℃,2.16kg))
b1-2)聚癸二酸-对苯二甲酸丁二醇酯:巴斯夫公司的FSC2200(MVR为3-5cm3/10min(190℃,5kg))
成分b2):
b2-1)聚乳酸:自然工坊公司的(PLA)4044D(MVR 1.5-3.5cm3/10min(190℃,2.16kg))
成分b3):
b3-1)海明斯公司的Plustalc H05C
b3-2)欧米亚公司的碳酸钙
成分b4):
b4-1)芥酸酰胺:克罗达国际有限公司的CrodamideTMER
b4-2)硬脂酸酰胺:克罗达公司的Crodamide SRV
b4-3)山嵛酸酰胺:克罗达公司的Crodamide BR
成分b5):
b5-1)巴斯夫公司的ADR 4468,甲基丙烯酸缩水甘油酯
层C的成分)
c-1(C‘)三菱化学公司的BTR-8002P增附剂
c-2三菱化学公司的G聚合物BVE8049聚乙烯醇
层B的复合
表1所列化合物是在Coperion MC 40挤出机上制成的。出口处的温度设定为250℃。然后将挤出物在水中造粒。造粒后,颗粒在60℃下干燥。
用于膜制造的吹膜设备的描述:
吹膜设备包括直径为30mm、长度为25D的单螺杆挤出机,直径为80mm、喷嘴缝隙为0.8mm的熔体螺旋分配器。吹塑比通常为3.5,膜管平面宽度约为440mm。
多层薄膜是通过共挤出法制造的。
表1:层B的组成成分
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V在表1和表2中表示对比例
表2:层压膜的组成成分
*层压膜与基材(纸)的粘合度如下进行确定:
将基膜B固定在实验室涂布台上,经过电晕处理的一面朝上,然后用刮板将待测胶粘剂直接涂在基膜上。用热风机将胶粘剂A吹干2分钟,然后用手辊将层压膜涂覆,并在辊式层压工位上在70℃下以5m/min的辊速、6.5巴的层压压力压在厚度为50gsm至130gsm纸上。然后使用切割模板将层压塑料切割成15mm宽的条状,并使其经过不同的存放周期。存放后,在拉伸试验机上将层压塑料条拉开,并记录所需的力。测试在拉伸试验机上进行,角度为90度,拉开速度为100mm/min。将试验板条的一侧切开,将其中一个松开的端头夹在拉伸试验机的上夹钳中,另一个夹在下夹钳中,然后开始试验。
表2最后一栏给出的等级(+)表示:纤维撕裂力大于0.6N/15mm
最后一栏给出的等级(-)表示:在作用力大于0.6N/15mm时纤维撕裂
表2中所列测试表明,层中不含脱模剂b4的、总层厚达到约为150μm的层压膜与纸基材的粘附性非常好。如果使用浓度达到0.3wt%的芥酸酰胺b4-1或硬脂酸酰胺b4-2作为脱模剂,则总厚度达到约为50-60μm的层压膜与纸基材的粘附性非常好。另一方面,如果使用浓度为0.2wt%至0.3wt%的山嵛酸酰胺b4-3或浓度为0.4wt%的硬脂酸作为脱模剂,则在层压膜厚度为10μm或17μm时,纸的附着力已经不足。
家庭堆肥试验
家庭可堆肥性根据法国标准NF T 51-800或ISO 14855-1(2012)标准“受控堆肥条件下塑料最终需氧生物分解能力的测定--采用分析测定释放的二氧化碳的方法”在环境温度(28±2℃)下进行测试,以模拟非所述的58℃的家庭堆肥条件。
在上述条件下,对实例4和实例12中厚度约为60μm的层压膜的家庭可堆肥性进行了测试,分别在116天和157天后观察到膜完全降解(>90%)。因此,根据澳大利亚标准AS5810-2010和ISO 14855-1(2012)标准,这些膜符合家庭可堆肥性标准。因此可以认为,具有层结构为A/B和层B成分的较薄的膜:I、V至XI(见表1)也是家庭可堆肥的。
Claims (9)
1.一种具有层结构A/B的生物可降解的层压膜,其中,0.5μm至7μm厚的层A包含聚氨酯胶粘剂或丙烯酸酯胶粘剂;层B包含脂肪族聚酯和/或脂肪族-芳香族聚酯以及0.05wt%至0.3wt%的润滑剂,所述润滑剂选自芥酸酰胺和硬脂酸酰胺,其中,所述脂肪族-芳香族聚酯的组成成分如下:
b1-i)以成分b1-i和b1-ii为基础,30mol%至70mol%的脂肪族C6-C18二羧酸;
b1-ii)以成分b1-i和b1-ii为基础,30mol%至70mol%的芳香族二羧酸;
b1-iii)以成分b1-i和b1-ii为基础,98mol%至100mol%的1,3-丙二醇或1,4-丁二醇;
b1-iv)以成分b1-i至b1-iii为基础,0mol%至2mol%的扩链剂和/或支化剂,
其中,含芥酸酰胺的层B的层厚度为5μm至80μm,
含硬脂酸酰胺的层B的层厚度为5μm至50μm。
2.根据权利要求1所述的层压膜,其中,层B由以下成分组成:
b1)60wt%至99.95wt%的脂肪族-芳香族聚酯,所述脂肪族-芳香族聚酯选自由以下项组成的组:聚己二酸-对苯二甲酸丁二醇酯、聚壬二酸-对苯二甲酸丁二醇酯和聚癸二酸-对苯二甲酸丁二醇酯;b2)0wt%至15wt%、优选3wt%至12wt%的聚羟基烷酸酯、优选聚乳酸;
b3)0wt%至25wt%、优选3wt%至20wt%的矿物填料;
b4)0.05wt%至0.3wt%的润滑剂,所述润滑剂选自芥酸酰胺和硬脂酸酰胺。
3.根据权利要求1或2所述的层压膜,其中,层A由水性聚氨酯分散体构成,至少60wt%的聚氨酯由以下成分组成:
a1)至少一种二异氰酸酯;
a2)至少一种聚酯醇;
a3)至少一种双官能羧酸,所述羧酸选自由以下项组成的组:二羟基羧酸和二氨基羧酸;以及
其中,聚氨酯的玻璃化温度低于20℃,或聚氨酯的熔点不高于20℃,且熔化焓低于10J/G。
4.根据权利要求1至3中任一项所述的层压膜,其中,层B的层厚度为10μm至50μm,并且包含以层B的总重量为基础0.05wt%至0.3wt%的芥酸酰胺。
5.一种具有层结构A/B/C/B的生物可降解的层压膜,其中,所述层A和层B具有权利要求1至4所述的含义,层C是由聚乙醇酸、乙烯-乙烯醇或优选聚乙烯醇组成的氧气阻隔层或香味阻隔层。
6.根据权利要求5所述的层压膜,其中,所述阻隔层由各个单层C‘/C/C‘组成,层C由聚乙烯醇组成,C'为增附剂层。
7.一种具有层结构A/B/C/B'的生物可降解的层压膜,其中,所述层A、层B和层B'具有根据权利要求1至4所述的含义,层B'的层厚度为10μm至100μm,并含有以层B的总重量为基础0.2wt%至0.5wt%的芥酸酰胺、硬脂酸酰胺或优选山嵛酸酰胺。
8.根据权利要求1至7中任一项所述的层压膜用于基材的复合膜胶合的用途,所述基材选自由以下项组成的组:生物可降解的薄膜、金属薄膜、金属化薄膜、玻璃纸或优选纸或纸板。
9.一种复合膜的制造方法,其中,i)层B的表面通过电晕处理活化;ii)涂上并干燥聚氨酯胶粘剂的水性分散体;iii)通过适当的滚压将根据权利要求1至7所述的获得的层压膜的面A压在所述基材上。
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