CN109054145B - 一种抗菌聚乙烯食品包装膜及其制备方法 - Google Patents
一种抗菌聚乙烯食品包装膜及其制备方法 Download PDFInfo
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- CN109054145B CN109054145B CN201810582802.6A CN201810582802A CN109054145B CN 109054145 B CN109054145 B CN 109054145B CN 201810582802 A CN201810582802 A CN 201810582802A CN 109054145 B CN109054145 B CN 109054145B
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- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 59
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- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 34
- CRGOPMLUWCMMCK-UHFFFAOYSA-M benzyl-dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)CC1=CC=CC=C1 CRGOPMLUWCMMCK-UHFFFAOYSA-M 0.000 claims abstract description 15
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 13
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- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明公开了一种抗菌聚乙烯食品包装膜,包括至少一层抗菌膜层,按重量份数计,聚乙烯抗菌膜层的原料组成包括:基材聚乙烯85~97.1份、纳米级无机抗菌剂0.05~0.3份、增容剂0.5~3.5份、季铵盐抗菌剂接枝纳晶纤维素2~5份;季铵盐抗菌剂接枝纳晶纤维素为季铵盐单体甲基丙烯酰氧乙基‑苄基‑二甲基氯化铵与纳晶纤维素辐照接枝制得。本发明采用无机抗菌剂与有机抗菌剂组合而成的复配抗菌剂,且有机抗菌剂以接枝纳晶纤维素的形式固定在膜层中,可减少无机抗菌剂在聚乙烯薄膜中的使用量;所得聚乙烯膜适用于较长货架期的食品包装。
Description
技术领域
本发明属于食品包装薄膜技术领域,具体涉及一种抗菌聚乙烯食品包装膜及其制备方法。
背景技术
抗菌薄膜是指将抗菌材料添加到成膜材料中支承的薄膜,由于受抗菌剂种类的限定,用于食品包装的抗菌塑料的制备技术具有与以往其它用途的抗菌塑料的生产技术有很大区别。目前,用于食品包装的抗菌剂主要为有机天然类、有机合成类和无机类。有机天然类抗菌剂包括壳聚糖及其衍生物、魔芋葡甘聚糖、纤维素及其衍生物、淀粉及衍生物、海藻酸盐、茶多酚、花青素以及具有抗菌作用的香精等,其有限在于安全性高,缺点在于寿命较短、耐热性差;有机合成类抗菌剂如季铵盐类、杂环吡啶咪唑噻吩类、有机金属类等,其优点在于杀菌速度快、抗菌范围广,缺点在于易迁移和水解,使用寿命较短;无机抗菌剂包括纳米银、纳米氧化锌、银沸石等,有点在于安全性高、耐热性好、有效期长、抗菌范围广,缺点在于易使包装薄膜变色,而且价格较高。
以季铵盐类抗菌剂为例,其抗菌机理为带负电荷的细菌会被抗菌材料上的阳离子(如有机季铵盐基团)所吸引,束缚细菌的活动,抑制其呼吸机能,即发生“接触死亡”;在电场引力的作用下,细胞壁和细胞膜上的负电荷分布不均匀造成变形,细胞的内脏物如水、蛋白质等渗出体外,发生“溶菌”观象而死亡。因此添加小分子的季铵盐的薄膜初始抗菌效果优良,但是对于货架期较长的食品而言,季铵盐类抗菌剂特别是小分子季铵盐类抗菌剂不能保证长期抗菌要求。
发明内容
本发明的目的之一在于克服现有技术中存在的缺陷,提供一种抗菌聚乙烯食品包装膜,在聚乙烯基槽中加入季铵盐抗菌剂接枝纳晶纤维素,利用纳晶纤维素固定季铵盐抗菌剂,达到缓释的效果,满足较长货架期食品包装抗菌的要求。
实现上述技术效果,本发明的技术方案为:一种抗菌聚乙烯食品包装膜,其特征在于,包括至少一层抗菌膜层,按重量份数计,聚乙烯抗菌膜层的原料组成包括:基材聚乙烯85~97.1份、纳米级无机抗菌剂0.05~0.3份、增容剂0.5~3.5份、季铵盐抗菌剂接枝纳晶纤维素2~5份,季铵盐抗菌剂接枝纳晶纤维素为季铵盐单体甲基丙烯酰氧乙基-苄基-二甲基氯化铵与纳晶纤维素辐照接枝制得。
上述抗菌膜层中的抗菌剂采用有机抗菌剂和无机抗菌剂复配而成,其中有机抗菌剂接枝在纳晶纤维素(纳米级微晶纤维素,NCC)表面,薄膜中的纳晶纤维素将季铵盐抗菌单体甲基丙烯酰氧乙基-苄基-二甲基氯化铵固定在其表面,增容剂的作用在于改善季铵盐抗菌剂接枝纳晶纤维素以及纳米级无机抗菌剂与基材聚乙烯的相容性。
优选的技术方案为,纳米级无机抗菌剂为纳米二氧化钛和/或纳米氧化锌。进一步的,该纳米二氧化钛为锐钛矿晶相纳米二氧化钛。二氧化钛与上述的缓释甲基丙烯酰氧乙基-苄基-二甲基氯化铵具有协同抗菌效果。
优选的技术方案为,抗菌聚乙烯食品包装膜为复合膜,复合膜的层叠结构由外之内依次包括聚乙烯表膜层、阻隔芯层和聚乙烯热封膜层,聚乙烯表膜层和/或聚乙烯热封膜层为抗菌膜层。
为了使聚乙烯膜层维持聚乙烯材料原有的力学性能,主要表现为混合接枝纳晶纤维素的聚乙烯薄膜具有良好的拉伸强度,优选的技术方案为,所述增容剂为LDPE-g-MAH,接枝率为1.2~1.6%,熔融指数MI为2.5~10g/10min。该熔融指数的测试条件为190℃×2.16kg。进一步的,聚乙烯为低密度聚乙烯和线性低密度聚乙烯中的一种或它们的组合物,其熔体流动速率在190℃×2.16kg的测试条件下为8~35g/10min。
优选的技术方案为,抗菌膜层的原料组成还包括分散剂,所述分散剂为选自聚乙烯蜡、硬脂酸和硬脂酸锌中的至少一种。
本发明的目的之二在于提供一种抗菌聚乙烯食品包装膜及其制备方法,包括配置原料、混合、共挤吹膜、冷却步骤,其特征在于,还包括季铵盐抗菌剂接枝纳晶纤维素的制备步骤:
S1:微晶纤维素加入过硫酸铵溶液中,超声反应后离心洗涤至中性,加入有机酸溶液继续超声反应,再次高速离心洗涤至中性,透析干燥,得到纳晶纤维素;
S2:将纳晶纤维素和甲基丙烯酰氧乙基-苄基-二甲基氯化铵分散于去离子水中,Co60γ射线辐照反应5~10min,用去离子水反复洗涤,真空干燥,得季铵盐抗菌剂接枝纳晶纤维素。
优选的技术方案为,S2中纳晶纤维素的浓度为5~15mg/ml,甲基丙烯酰氧乙基-苄基-二甲基氯化铵的浓度为0.1~2mg/ml。季铵盐单体的浓度过大,有助于季铵盐单体之间的均聚反应,不利于接枝反应的进行。
优选的技术方案为,辐照接枝在常温下进行,S2辐照接枝的辐射剂量为25~100kGy。辐照剂量增加,接枝反应中接枝活性中心数量增加,但是季铵盐抗菌剂单体之间的均聚物也相应增多。
优选的技术方案为,过硫酸铵溶液的浓度为1.5~2mol/L。
优选的技术方案为,有机酸为柠檬酸和/或酒石酸,有机酸的浓度为0.7~1mol/L。
本发明的优点和有益效果在于:
本发明抗菌阻隔聚乙烯包装膜采用无机抗菌剂与有机抗菌剂组合而成的复配抗菌剂,且有机抗菌剂以接枝纳晶纤维素的形式固定在膜层中,有机抗菌剂的迁移速率得到改善,采用上述复配的抗菌组合,可减少无机抗菌剂在聚乙烯薄膜中的使用量,所得聚乙烯膜适用于较长货架期的食品包装;
与直接加入抗菌剂的薄膜相比,由于纳晶纤维素在聚乙烯基材中的异相成核作用,所得聚乙烯抗菌膜层的拉伸强度和阻隔性能得到提高,
纳晶纤维素来源广泛,相较而言,薄膜中使用季铵盐类抗菌剂成本较低,适于工业化生产。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
纳米级无机抗菌剂
纳米级无机抗菌剂的可选范围包括:纳米二氧化钛、纳米氧化锌、纳米银、纳米载银沸石,还包括载银羚基磷灰石、磷酸脂钠银、载银沸石、硅硼酸钠银、二氧化钛二氧化硅银铜。
增容剂
增容剂除LDPE-g-MAH(马来酸酐接枝低密度聚乙烯),还可以为乙烯丙烯酸共聚物、乙烯甲基丙烯酸共聚物。
阻隔芯层
阻隔芯层可为单层的EVOH层或PA层,也可以为具有中阻隔效果的PA/TIE/PE/TIE/PA或高阻隔效果的PA/EVOH/PA复合膜。
实施例1-8
实施例1-8抗菌聚乙烯食品包装膜中抗菌膜层,的原料组成包括:基材聚乙烯、纳米级无机抗菌剂、增容剂、季铵盐抗菌剂接枝纳晶纤维素,季铵盐抗菌剂接枝纳晶纤维素为季铵盐单体甲基丙烯酰氧乙基-苄基-二甲基氯化铵与纳晶纤维素辐照接枝制得。实施例1-4原料组成重量份数见下表:
实施例1季铵盐抗菌剂接枝纳晶纤维素的制备步骤为:
S1:纳晶纤维素的制备采用CN105584165A中公开的方法:将MCC原料与60%的硫酸混合后,于50~60℃酸解120~150分钟;然后将产物用透析袋处理,直至产物的pH为中性,干燥得到棒状的纳晶纤维素;
S2:将纳晶纤维素和甲基丙烯酰氧乙基-苄基-二甲基氯化铵分散于去离子水中,Co60γ射线辐照反应2min,用去离子水反复洗涤,真空干燥,得季铵盐抗菌剂接枝纳晶纤维素。
S2中纳晶纤维素的浓度为4mg/ml,甲基丙烯酰氧乙基-苄基-二甲基氯化铵的浓度为3mg/ml。
辐照接枝在常温下进行,S2辐照接枝的辐射剂量为25kGy。
实施例2中季铵盐抗菌剂接枝纳晶纤维素的制备步骤与实施例1中的区别在于S1和工艺参数:微晶纤维素加入过硫酸铵溶液中,超声反应后离心洗涤至中性,加入有机酸溶液继续超声反应,再次高速离心洗涤至中性,透析干燥,得到纳晶纤维素;
S2中Co60γ射线辐照反应时间为5min;纳晶纤维素的浓度为15mg/ml,甲基丙烯酰氧乙基-苄基-二甲基氯化铵的浓度为2mg/ml;S2辐照接枝的辐射剂量为25kGy;过硫酸铵溶液的浓度为2mol/L;有机酸为柠檬酸,有机酸的浓度为0.7mol/L。
实施例3-8中季铵盐抗菌剂接枝纳晶纤维素的制备步骤与实施例2中的区别在于工艺参数:S2中Co60γ射线辐照反应时间为10min;纳晶纤维素的浓度为5mg/ml;甲基丙烯酰氧乙基-苄基-二甲基氯化铵的浓度为0.1mg/ml;S2辐照接枝的辐射剂量为100kGy;过硫酸铵溶液的浓度为1.5mol/L;有机酸为柠檬酸,有机酸的浓度为1mol/L。
实施例3中纳米级无机抗菌剂为纳米银,实施例4中纳米级无机抗菌剂为纳米二氧化钛,实施例5中纳米级无机抗菌剂为纳米氧化锌,实施例6中纳米级无机抗菌剂为纳米氧化锌和纳米二氧化钛以重量比1:1混合而成。
实施例1-5中增容剂为乙烯丙烯酸共聚物,实施例6增容剂为LDPE-g-MAH,接枝率为1.2%,熔融指数MI为2.5g/10min;实施例7-8中LDPE-g-MAH的接枝率为1.6%,熔融指数MI为10g/10min。
实施例7中分散剂为聚乙烯蜡,实施例8中分散剂为硬脂酸锌。对比例1
对比例1和2均基于实施例1,区别在于:对比例1中仅含有无机抗菌剂;对比例2中含有无机抗菌剂和季铵盐单体甲基丙烯酰氧乙基-苄基-二甲基氯化铵1份。
实施例中的聚乙烯选用燕山石化公司生产的LDPE,商品牌号为IF7B,所用的超细二氧化钛为杜邦公司DLS-210,纳米氧化锌为深圳晶材化工有限公司的平均粒径30nm、比表面积50m2/g的氧化锌;纳米银粉为购自上海茂果纳米科技有限公司的MG-Ag-50。
将实施例和对比例试样原料高速混合器中干混15分钟;将混合均匀的原料加入双螺杆挤出机中,经熔融挤出,冷却造粒得到聚乙烯复合材料,其工艺为:一区160~170℃,二区17~180℃,三区180~190℃,四区175~185℃;整个挤出过程的停留时间1.5~2分钟,压力为15~18MPa;最后将制备的聚乙烯复合材料置于吹塑成型机中吹制得到聚乙烯薄膜,其中料筒温度为165~175℃。
性能评价方式及实行标准:
1、聚乙烯薄膜的综合力学性能通过测试拉伸强度进行评判。拉伸强度按GB/T1040-2006方法测试;
2、气体阻隔性测试:按照GB/T1038-2000方法测试;
3、抗菌性能参照QB/T 2591-2003《抗菌塑料-抗菌性能试验方法和抗菌效果》(贴膜法)测试,检测菌种:大肠杆菌和金黄色葡萄球菌,薄膜样品置于室温静置10d后清洗干燥再进行测试。
实施例1-8以及对比例1-2的测试结果见下表:
对比例1和2与实施例形成对照,随着纳晶纤维素添加量的增加,聚乙烯膜拉伸强度和气体透过系数均有所增加,将抗菌剂单体负载到纳晶纤维素上能延长薄膜的抗菌效果,相应的延长了薄膜包装食品的货架期,对比例由于采用直接添加的方式,大肠杆菌抗菌率和金黄色葡萄球菌抗菌率主要取决于无机抗菌剂。
抗菌聚乙烯食品包装膜为复合膜,复合膜的层叠结构由外之内依次包括聚乙烯表膜层、阻隔芯层和聚乙烯热封膜层,聚乙烯表膜层和/或聚乙烯热封膜层为抗菌膜层。由于对比例中抗菌剂的迁移,实施对比例2的抗菌效果仅略优于对比例1。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种抗菌聚乙烯食品包装膜,其特征在于,包括至少一层抗菌膜层,按重量份数计,聚乙烯抗菌膜层的原料组成包括:基材聚乙烯85~97.1份、纳米级无机抗菌剂0.05~0.3份、增容剂0.5~3.5份、季铵盐抗菌剂接枝纳晶纤维素2~5份;季铵盐抗菌剂接枝纳晶纤维素为季铵盐单体甲基丙烯酰氧乙基-苄基-二甲基氯化铵与纳晶纤维素辐照接枝制得。
2.根据权利要求1所述的抗菌聚乙烯食品包装膜,其特征在于,纳米级无机抗菌剂为纳米二氧化钛和/或纳米氧化锌。
3.根据权利要求1所述的抗菌聚乙烯食品包装膜,其特征在于,抗菌聚乙烯食品包装膜为复合膜,复合膜的层叠结构由外之内依次包括聚乙烯表膜层、阻隔芯层和聚乙烯热封膜层,聚乙烯表膜层和/或聚乙烯热封膜层为抗菌膜层。
4.根据权利要求1所述的抗菌聚乙烯食品包装膜,其特征在于,所述增容剂为LDPE-g-MAH,接枝率为1.2~1.6%,熔融指数MI为2.5~10g/ 10min。
5.根据权利要求1所述的抗菌聚乙烯食品包装膜,其特征在于,抗菌膜层的原料组成还包括分散剂,所述分散剂为选自聚乙烯蜡、硬脂酸和硬脂酸锌中的至少一种。
6.一种抗菌聚乙烯食品包装膜的制备方法,所述抗菌聚乙烯食品包装膜为权利要求1至5中任意一项所述的抗菌聚乙烯食品包装膜,包括配置原料、混合、共挤吹膜、冷却步骤,其特征在于,还包括季铵盐抗菌剂接枝纳晶纤维素的制备步骤:
S1:微晶纤维素加入过硫酸铵溶液中,超声反应后离心洗涤至中性,加入有机酸溶液继续超声反应,再次高速离心洗涤至中性,透析干燥,得到纳晶纤维素;
S2:将纳晶纤维素和甲基丙烯酰氧乙基-苄基-二甲基氯化铵分散于去离子水中,Co60γ射线辐照反应5~10min,用去离子水反复洗涤,真空干燥,得季铵盐抗菌剂接枝纳晶纤维素。
7.根据权利要求6所述的抗菌聚乙烯食品包装膜的制备方法,其特征在于,S2中纳晶纤维素的浓度为5~15mg/ml, 甲基丙烯酰氧乙基-苄基-二甲基氯化铵的浓度为0.1~2mg/ml。
8.根据权利要求6所述的抗菌聚乙烯食品包装膜的制备方法,其特征在于,辐照接枝在常温下进行,S2辐照接枝的辐射剂量为25~100kGy。
9.根据权利要求6所述的抗菌聚乙烯食品包装膜的制备方法,其特征在于,过硫酸铵溶液的浓度为1.5~2mol/L。
10.根据权利要求6所述的抗菌聚乙烯食品包装膜的制备方法,其特征在于,有机酸为柠檬酸和/或酒石酸,有机酸的浓度为0.7~1mol/L。
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