CN100482463C - 在基材上涂覆支化聚酰胺层的方法 - Google Patents
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Abstract
一种制造叠层的方法,其至少包括在基材上涂覆一层聚酰胺,优选地通过挤压涂覆,主要使用支化聚酰胺作为该聚酰胺,其至少由衍生自以下物质的单元组成:a.AB单体,其被理解为表示具有羧酸基团(A)和胺基团(B)的单体,b.至少一种化合物I,其是官能度ν≥2的羧酸(Aν)或官能度ω≥2的胺(Bω),c.至少一种化合物II,其是官能度ν≥3的羧酸(Aν)或官能度ω≥3的胺(Bω),如果化合物I是胺,那么化合物II是羧酸,或者如果化合物I是羧酸,那么化合物II是胺。基材优选地为(金属化的)纸或纸板,使得形成非常适合于制造食物包装的叠层。
Description
本发明涉及叠层的制造方法,该方法至少包括在基材(substrate)上涂覆聚酰胺层。
这类方法例如从WO 01/40055中已知。在该文献中,纸板基材通过挤压涂覆(extrusion coating)而被涂覆有尼龙层、粘结层和聚乙烯层(从纸板向外看)。
该已知方法的缺点在于下述事实:在高生产速度下,膜状挤出物易于变得不稳定,以致基材的涂覆厚度不均匀。该不稳定性表现在下述事实中:仍然熔融的挤出物没有保持平坦,而是开始显示出不规则的波浪图样,以致形成局部的厚度差异。通常,波的幅度在基材边缘处最大,因此,经常必须在涂覆之后切除不能用的某一宽度部分。如果数层被同时挤压,那么该效应会发生到甚至更大的程度。
本发明的目标为提供一种方法,通过该方法可以在高速下用至少一层聚酰胺涂覆基材。
此目标可以根据本发明实现,其中,使用的聚酰胺主要为支化聚酰胺,其至少由衍生自下列物质的单元组成:
a.AB单体,其被理解为表示具有羧酸基(A)和胺基(B)的单体,
b.至少一种化合物I,其为官能度v≥2的羧酸(Av)或官能度ω≥2的胺(Bω),
c.至少一种化合物II,其是官能度v≥3的羧酸(Av)或官能度ω≥3的胺(Bω),如果化合物I是胺,那么化合物II是羧酸,或者如果化合物I是羧酸,那么化合物II是胺,其中,聚酰胺中衍生自所有羧酸和胺的单元的数量满足式1
P<1/[(FA—1)·(FB—1)] (1)
其中:
P=[∑(ni·fi)]X/[∑(ni·fi)]Y (2)
其中,P≤1,并且或者X=A,Y=B,或者X=B,Y=A,且
分别地,对于所有羧酸(FA)和胺(FB)来说,其中,fi是羧酸的官能度(vi)或胺的官能度(ωi),ni是羧酸或胺的摩尔数,并且对聚酰胺中衍生自羧酸和胺的所有单元求和。
所指定的支化聚酰胺从WO 00/35992中获知,并且对上式中各部分给出的定义也适用于此。特别地,化合物I和化合物II也应理解为是具有相同官能度的几种羧酸的混合物或者具有相同官能度的几种胺的混合物。
这种材料选择看来可导致明显更稳定的挤出物,这意味着其实际上保持平坦,即使在高生产速度下,以及即使将数层同时涂覆到基材上也一样。结果,可以达到高出50%的生产速度。
这种选择还使聚酰胺层具有高度均匀的外观而没有由凝胶造成的不规则性。非常适合用于根据本发明的方法中的是支化聚酰胺,其中己内酰胺是最常出现的单体单元。
根据本发明的方法的另一个优点是以聚酰胺层切掉部分的形式或以涂覆具有不同厚度的聚酰胺层的基材形式的边缘废料的减少。结果,需要更少的起始材料来制造相同表面面积的叠层基材,并且需要回收或破坏的材料更少。
这里所指的叠层由整体平坦的固体基材组成,例如纸、纸板、金属箔或片或塑料膜。聚酰胺层被涂覆到基材上作为给予该叠层聚酰胺性质的功能层。在纸或纸板的情况下,这特别是提供对空气、氧气和芳族物质的阻挡。同样为了降低对湿气的可渗透性,通常在聚酰胺层和可选的其他功能层上涂覆至少一层高密度或低密度聚乙烯。还可能在基材上相对于聚酰胺层的背侧上涂覆功能层。不同材料层的适当组合本身是已知的,以用于所得叠层的各种预期应用。涂覆有数层的这种基材广泛应用于食物包装,例如用于牛奶或果汁的纸盒或金属罐。其中,聚酰胺层优选地直接毗接在基材上,如果需要可以设置一层金属箔。在给予叠层某些性质的相邻功能层之间可以涂覆粘结层。如果在支化聚酰胺层上涂覆聚乙烯层,那么粘结层的适当材料例如为改性聚烯烃,例如LDPE、LLDPE、茂金属PE、聚乙烯-乙烯基醇、聚乙烯-丙烯酸、聚乙烯-甲基丙烯酸和聚丙烯,其被接枝有选自由α,β-不饱和二元羧酸,例如马来酸、富马酸和衣康酸及其酸酐、酸性酯、酰亚胺和亚胺组成的组中的至少一种化合物。乙烯和所述二元羧酸的共聚物也可以以所示方式被改性后用作粘结层。
如果这些层彼此直接毗接,而没有单独的粘结层,那么毗接在聚酰胺层上的聚合物层优选地由所述聚合物和上述适合用作粘结层的材料的混合物组成,在聚乙烯的情况中是上述的改性聚烯烃,以促进相接层之间的粘合。也可能对相接层中的两者或其中之一改性以改进相互间的粘合。
该层或多层是利用公知且适用于此的技术而被涂覆到基材上,特别是利用挤压涂覆。挤压涂覆本身是已知的技术,用于将熔融塑料膜状层,例如聚酰胺、聚乙烯、聚丙烯、乙烯-乙烯醇和热塑性塑料,涂覆到固体基材上,例如纸、纸板、金属箔和塑料膜。基材本身也可以由数层组成,这些层例如是在一个或多个先前的工艺步骤中涂覆到彼此的。也可能将数层,例如聚酰胺层和用于将在后面涂覆的下一层的粘合层,通过共同挤出这些层而同时涂覆到基材上。
这些层的厚度可以根据期望的效果来选择。例如,具有增加厚度的聚酰胺层更好地形成对氧气和芳族物质的阻挡。在实践中,厚度可以在1到100克/平方米之间。非常合适的是在5到50克/平方米之间的厚度。前述的也可应用于任何其他的功能层,要注意的是,粘结层一般可以比由该粘结层彼此粘结的层要薄。在包装应用中,经常使用所述聚乙烯层通过热密封来密封包装,并且为此所需的层厚度是比由湿气阻挡性能所设定的要求更具决定性的因素。
所涂覆的聚酰胺主要由支化聚酰胺组成,这被理解为表示除了支化聚酰胺之外,还可以存在一定量的非支化聚酰胺。此量应该受限制,使得应用支化聚酰胺的有利效果不会丧失到无法接受的程度。优选地,聚酰胺层中至少50%的聚酰胺是支化聚酰胺,更优选地至少75%,甚至至少90%。在层中的所有聚酰胺都是支化聚酰胺时,支化聚酰胺存在的有利效果是最明显的。不同支化聚酰胺的混合物也可以用作支化聚酰胺。
聚酰胺还可以含有常用的添加剂,例如成核剂、润滑剂、抗静电剂、抗结块剂、着色剂和稳定剂。这同样适用于可选地涂覆的其他层。
本发明还涉及一种叠层,其包括基材和主要由如前文定义的支化聚酰胺组成的层,该叠层用于制造食物包装的应用和包括该叠层的食物包装。
Claims (6)
1.一种制造叠层的方法,其至少包括在基材上涂覆一层聚酰胺,其特征在于,主要使用支化聚酰胺作为该聚酰胺,其至少由衍生自以下物质的单元组成:
a.AB单体,其被理解为表示具有羧酸基(A)和胺基(B)的单体,
b.至少一种化合物I,其为官能度ν≥2的羧酸(Aν)或官能度ω≥2的胺(Bω),
c.至少一种化合物II,其是官能度ν≥3的羧酸(Aν)或官能度ω≥3的胺(Bω),如果化合物I是胺,那么化合物II是羧酸,或者如果化合物I是羧酸,那么化合物II是胺,其中,该聚酰胺中衍生自所有羧酸和胺的单元的数量满足式1
P<1/[(FA—1)·(FB—1)] (1)
其中:
P=[∑(ni·fi)]X/[∑(ni·fi)]Y (2)
其中,P≤1,并且或者X=A,Y=B,或者X=B,Y=A,且
分别地,对于所有羧酸(FA)和胺(FB)来说,其中,fi是羧酸的官能度(νi)或胺的官能度(ωi),ni是羧酸或胺的摩尔数,并且对该聚酰胺中衍生自羧酸和胺的所有单元求和。
2.根据权利要求1所述的方法,其中,所述聚酰胺层通过挤压涂覆而被涂覆。
3.根据权利要求1或2所述的方法,其中,所述基材是金属或纸。
4.根据权利要求1—3任一项所述的方法获得的叠层。
5.根据权利要求4的叠层在制造食物包装中的应用。
6.一种食物包装,包括根据权利要求4所述的叠层。
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US20040175466A1 (en) | 2003-03-07 | 2004-09-09 | Douglas Michael J. | Multilayer barrier structures, methods of making the same and packages made therefrom |
US20040175464A1 (en) | 2003-03-07 | 2004-09-09 | Blemberg Robert J. | Multilayer structures, packages, and methods of making multilayer structures |
US20100015423A1 (en) * | 2008-07-18 | 2010-01-21 | Schaefer Suzanne E | Polyamide structures for the packaging of moisture containing products |
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- 2003-07-04 CN CNB038163284A patent/CN100482463C/zh not_active Expired - Fee Related
- 2003-07-04 AT AT03762922T patent/ATE339307T1/de active
- 2003-07-04 DK DK03762922T patent/DK1519836T3/da active
- 2003-07-04 US US10/520,704 patent/US20060166021A1/en not_active Abandoned
- 2003-07-04 AU AU2003253496A patent/AU2003253496A1/en not_active Abandoned
- 2003-07-04 ES ES03762922T patent/ES2271647T3/es not_active Expired - Lifetime
- 2003-07-04 EP EP03762922A patent/EP1519836B1/en not_active Expired - Lifetime
- 2003-07-04 JP JP2004519363A patent/JP4317128B2/ja not_active Expired - Fee Related
- 2003-07-07 TW TW92118508A patent/TWI314118B/zh not_active IP Right Cessation
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KR20210012644A (ko) * | 2019-07-26 | 2021-02-03 | 한국과학기술연구원 | 화학사고 후 안정성동위원소 분석을 통한 토양내 화학물질 저감 양상 모니터링을 위한 모의 실험 시스템 |
KR102242839B1 (ko) | 2019-07-26 | 2021-04-21 | 한국과학기술연구원 | 화학사고 후 안정성동위원소 분석을 통한 토양내 화학물질 저감 양상 모니터링을 위한 모의 실험 시스템 |
Also Published As
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TWI314118B (en) | 2009-09-01 |
EP1519836B1 (en) | 2006-09-13 |
ATE339307T1 (de) | 2006-10-15 |
WO2004005026A1 (en) | 2004-01-15 |
DE60308376T2 (de) | 2007-09-20 |
CN1668464A (zh) | 2005-09-14 |
DE60308376D1 (de) | 2006-10-26 |
ES2271647T3 (es) | 2007-04-16 |
EP1519836A1 (en) | 2005-04-06 |
DK1519836T3 (da) | 2007-01-15 |
JP4317128B2 (ja) | 2009-08-19 |
JP2005532194A (ja) | 2005-10-27 |
TW200404708A (en) | 2004-04-01 |
US20060166021A1 (en) | 2006-07-27 |
AU2003253496A1 (en) | 2004-01-23 |
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