CN115584659A - 一种高阻隔性保鲜材料及其制备方法 - Google Patents
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Abstract
本发明提供一种高阻隔性保鲜材料，高阻隔性保鲜材料由以植物纤维为主要原料的复合材料制成，至少包括纸基层和涂布层；涂布层由阻隔涂层和保鲜涂层复合而成或混合而成。本发明还提供一种高阻隔性保鲜材料的制备方法。本发明在纸张原纸表面涂布阻隔涂层和保鲜涂层，工艺简单，操作方便，能有效降低保鲜盒内氧气含量，降低果蔬有氧呼吸的消耗量，提高果蔬保鲜效果。同时，不影响保鲜盒内的湿度。此外，所用的涂层溶液均为可生物降解高分子物质，对环境有益，不产生污染问题。
Description
技术领域
本发明涉及果蔬保鲜膜的制备技术领域，具体涉及一种高阻隔性保鲜材料及其制备方法。
背景技术
新鲜水果蔬菜是人体必须的活性维生素、矿物质和膳食纤维的重要来源，具有独特的形、色、味，是保障人体机能和健康的重要食品。采收后的果蔬仍是鲜活有机体，还会进行休眠、水分蒸发、呼吸作用等复杂的生命活动，这些活动都会降低果蔬新鲜程度，提高营养流失率。因此，依靠先进的科学技术，延长果蔬保鲜期，并保证其营养质量，是果蔬保存的目标。
空气中氧含量的降低将明显提高果蔬的保鲜度。较低的氧浓度可以抑制叶绿素的降解、减少抗坏血酸的损失、降低不溶性果胶物质的减少速度、增大食品脆硬度。此外，较低的氧含量将抑制乙烯的生成，从而降低乙烯对果蔬的催熟作用，延缓果蔬衰老，延长食品保鲜期，提高食品的保存质量。若能在冰箱冷藏室保鲜盒内添加一种高阻隔性材料，合理调控冰箱储藏环境内空气各组分的组成比例，适当降低氧气含量，就能延缓果蔬呼吸作用，抑制微生物生长以及抑制果蔬成分的氧化和褐变，提高果蔬保鲜度。
目前，常用的提高纸张阻隔性能的方法包括阻隔性涂布、热塑性树脂表面层合以及胶乳浸渍等方式。其中，热塑性树脂表面层合及胶乳浸渍可提高纸和纸板的阻隔效果，但这两种方式会使纸产品的回用变得困难且不环保。阻隔性涂布是通过涂布的方式在纸张表面形成一层阻隔涂层从而达到阻隔效果，此方法工艺简单、易于实现。工业上常用的阻隔性优异材料主要有乙烯-乙烯醇共聚物(EVOH)、尼龙(PA)、聚偏二氯乙烯(PDVC)、铝箔等，但这些材料虽然阻隔性优异，但透湿性较差、不能生物降解，不符合冰箱果蔬保鲜的要求，且使用后几乎无法回收利用，对环境污染严重。
为解决以上发明存在的问题，本发明专利的目的是通过制备一种操作简单、成本低廉的冰箱用高阻隔性完全生物降解的复合材料来降低保鲜冰箱的氧气浓度，从而提高新鲜果蔬保鲜度。这种阻隔材料除了需要具有优异的阻隔氧气通过的能力外，还需要具有一定的透湿性，便于果蔬中水分保持在一定的范围内，使果蔬水分处在一种动态平衡状态，不至于因为环境湿度太大而腐坏，也不至于因为环境湿度太小而脱水。
发明内容
为解决现有技术存在的技术缺陷和不足，本发明提供一种高阻隔性保鲜材料及其制备方法。
一种高阻隔性保鲜材料，高阻隔性保鲜材料由以植物纤维为主要原料的复合材料制成，至少包括纸基层和涂布层；涂布层由阻隔涂层和保鲜涂层复合而成或混合而成；其中，阻隔涂层为水溶性聚合物涂层，包括聚乙烯醇(PVA)、微纤化纤维素(MFC)、纳米纤维素(NCC)中的一种或几种，溶液质量浓度为2％-15％；保鲜涂层为水溶性吸湿材料，包括壳聚糖、壳聚糖季铵盐、海藻酸钠、羧甲基纤维素、羟甲基纤维素、羟乙基纤维素中的一种或几种，溶液质量浓度为0.5％-5％。
与现有技术相比，本发明的技术效果为：本发明在纸张原纸表面涂布阻隔涂层和保鲜涂层，工艺简单，操作方便，能有效降低保鲜盒内氧气含量，降低果蔬有氧呼吸的消耗量，提高果蔬保鲜效果；同时，不影响保鲜盒内的湿度，3天内湿度负载的失水率和结露量达到保鲜冰箱的要求。此外，所用的涂层溶液均为可生物降解高分子物质，对环境有益，不产生污染问题。所选涂布方式将具有阻隔性的涂层涂在基纸上，形成具有不同结构、不同层次、高阻隔性能和一定透湿性能的复合材料。这种加工方式减少了复合的加工工序，避免了因复合引起的溶剂残留等问题。
可选地，纸基层利用中高打浆度的漂白化学木浆、高吸水性纤维等配抄，浆内添加湿强剂、干强剂等制成原纸，采用湿法抄纸设备抄造而成，纸基层定量为40-80g/m2，纵向干抗张力≥40N。
可选地，湿强剂为聚酰胺环氧氯丙烷(PAE)、三聚氰胺甲醛树脂中的一种或几种，湿强剂的质量为绝干纤维质量的0.1-1.0％；干强剂为阴离子聚丙烯酰胺、改性淀粉中的一种或几种，干强剂用量为绝干纤维质量的0.1％-0.4％。
本发明还提供一种高阻隔性保鲜材料的制备方法，包括如下步骤：(1)生产纸基层，(2)对纸基层进行涂布处理，形成涂布层，在步骤(2)中，将纸基层放置在涂布液中进行涂布处理，涂布量2-30g/m2，干燥温度90-120℃，涂布液包括阻隔涂层涂布液和保鲜涂层涂布液。
阻隔涂层涂布液为水溶性聚合物涂布液，包括聚乙烯醇(PVA)、微纤化纤维素(MFC)、纳米纤维素(NCC)中的一种或几种，溶液质量浓度为2％-15％；保鲜涂层涂布液为水溶性吸湿材料，包括壳聚糖、壳聚糖季铵盐、海藻酸钠、羧甲基纤维素、羟甲基纤维素、羟乙基纤维素中的一种或几种，溶液质量浓度为0.5％-5％。
根据本发明的一个实施例，涂布层由阻隔涂层和保鲜涂层叠加复合而成，涂布方式包括双面单涂或LBL层层自组装方式中的一种。
根据本发明的另一个实施例，涂布液由所述阻隔涂层涂布液和所述保鲜涂层涂布液混合而成，阻隔涂层涂布液和保鲜涂层涂布液混合比例为2∶1-5∶1，混合液的质量浓度为1.5％-15％，涂布方式包括单面双涂、双面单涂、双面双涂中的一种。
附图说明
附图1是根据本发明一个实施例提供的高阻隔性保鲜材料的结构示意图；
附图2是根据本发明又一个实施例提供的高阻隔性保鲜材料的结构示意图；
附图3是根据本发明一个实施例提供的涂布层的结构示意图；
附图4是根据本发明又一个实施例提供的涂布层的结构示意图；
附图5是根据本发明一个实施例提供的高阻隔性保鲜材料制备方法的流程图。
其中，附图标记表示如下：
1高阻隔性保鲜材料；2纸基层；3涂布层；4阻隔涂层；5保鲜涂层。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图对本发明的具体实施方式做详细的说明。在下面的描述中阐述了很多具体细节以便于充分理解本发明。但是本发明能够以很多不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似改进，因此本发明不受下面公开的具体实施例的限制。
为使本发明专利应用的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚完整的描述。
本发明提供一种高阻隔性保鲜材料及其制备方法。附图1和附图2示出了本发明的一种高阻隔性保鲜材料的结构示意图。参考附图1-2，该高阻隔性保鲜材料1由以植物纤维为主要原料的复合材料制成，至少包括纸基层2和涂布层3。参考附图3-4，涂布层3由阻隔涂层4和保鲜涂层5复合而成或混合而成。其中，阻隔涂层4为水溶性聚合物涂层，赋予纸张高阻隔性；所选材料为生物可降解型高分子类聚合物，包括聚乙烯醇(PVA)、微纤化纤维素(MFC)、纳米纤维素(NCC)中的一种或几种，溶液质量浓度为2％-15％。保鲜涂层5为水溶性吸湿材料，赋予纸张吸湿性；所选材料为壳聚糖、壳聚糖季铵盐、海藻酸钠、羧甲基纤维素、羟甲基纤维素、羟乙基纤维素中的一种或几种，质量浓度为0.5％-5％。
在本发明的又一个实施例中，纸基层2利用中高打浆度的漂白化学木浆、高吸水性纤维等配抄，浆内添加湿强剂、干强剂等制成原纸，采用湿法抄纸设备抄造而成。纸基层2定量为40-80g/m2，纵向干抗张力≥40N。
其中，湿强剂为聚酰胺环氧氯丙烷(PAE)、三聚氰胺甲醛树脂中的一种或几种，湿强剂的质量为绝干纤维质量的0.1-1.0％。干强剂为阴离子聚丙烯酰胺、改性淀粉中的一种或几种，干强剂用量为绝干纤维质量的0.1％-0.4％。
附图5示出了一种高阻隔性保鲜材料的制备方法的流程示意图。参考图5，根据本发明提供的一种高阻隔性保鲜材料的制备方法包括如下步骤：(1)生产纸基层2，(2)对纸基层2进行涂布处理，形成涂布层3；在步骤(2)中，将纸基层2放置在涂布液中进行涂布处理，涂布量2-30g/m2，干燥温度90-120℃，涂布液包括由阻隔涂层涂布液和由保鲜涂层涂布液，由此制得具有高阻氧性、透湿性的冰箱用保鲜材料。
阻隔涂层涂布液为水溶性聚合物涂布液，赋予纸张高阻隔性；所选材料为生物可降解型高分子类聚合物，包括聚乙烯醇(PVA)、微纤化纤维素(MFC)、纳米纤维素(NCC)中的一种或几种，溶液质量浓度为2％-15％。保鲜涂层涂布液为水溶性吸湿材料，赋予纸张吸湿性；所选材料为壳聚糖、壳聚糖季铵盐、海藻酸钠、羧甲基纤维素、羟甲基纤维素、羟乙基纤维素中的一种或几种，质量浓度为0.5％-5％。
其中，涂布层3由阻隔涂层4和保鲜涂层5叠加复合而成，涂布方式包括双面单涂或LBL层层自组装方式中的一种。
在本发明的另一个实施例中，涂布液由阻隔涂层涂布液和保鲜涂层涂布液混合而成，阻隔涂层涂布液和保鲜涂层涂布液混合比例为2∶1-5∶1，混合液的质量浓度为1.5％-15％，涂布方式包括单面双涂、双面单涂、双面双涂中的一种。
与现有技术相比，本发明的优势在于，本发明在纸张原纸表面涂布阻隔涂层和保鲜涂层，工艺简单，操作方便，能有效降低保鲜盒内氧气含量，降低果蔬有氧呼吸的消耗量，提高果蔬保鲜效果。同时，不影响保鲜盒内的湿度，3天内湿度负载的失水率和结露量达到保鲜冰箱的要求。此外，所用的涂层溶液均为可生物降解高分子物质，对环境有益，不产生污染问题。所选涂布方式将具有阻隔性的涂层涂在基纸上，形成具有不同结构、不同层次、高阻隔性能和一定透湿性能的复合材料。这种加工方式减少了复合的加工工序，避免了因复合引起的溶剂残留等问题。
本发明提供的高阻隔性保鲜材料纵向抗张力≥40N，氧气透过率≤100cm3/(m2·24h·0.1MPa)，水蒸气透过率在230±50g/(m2·24h)范围内，搭载冰箱保鲜盒后，3天失水率≤4％，结露量≤4g，平均湿度≥90％，达到冰箱保鲜要求。
本发明还提供了上述高阻隔性保鲜材料在冰箱中的应用，将制备的高阻隔性保鲜材料搭载冰箱保鲜盒，测试保鲜盒内相对湿度、结露量及湿度负载的失水率，具体方法为：将制成的高阻隔性保鲜材料安装在具有密封性能9升的冰箱保鲜盒顶盖上，保鲜盒内放置均匀吸附300g蒸馏水的海绵(模拟湿度负载)，在保鲜盒中放置温湿度测试仪。将保鲜盒放在风冷冰箱的冷藏室中进行试验，测试3天中保鲜盒中的平均相对湿度、氧气透过率和水蒸气透过率；试验达3天后，测量保鲜盒中盒壁和顶盖的结露量，并称海绵的失水率。
实施例1
纸基层：30％漂白硫酸盐针叶木浆：70％漂白硫酸盐阔叶木浆，PAE0.8％，针叶木浆打浆度70°SR，阔叶木浆打浆度70°SR，纸基层厚度0.15mm；抄纸设备：长网纸机；阻隔涂层：在纸基层表面涂布6.0％PVA溶液；保鲜涂层：在纸基层、阻隔涂层的基础上涂布2％壳聚糖溶液；涂布方式：采用双面单涂涂布方式，105℃下烘干得到高阻隔性保鲜材料，涂布量15g/m2。高阻隔性保鲜材料的检测结果见表1。
实施例2
纸基层：40％漂白硫酸盐针叶木浆：60％漂白硫酸盐阔叶木浆，PAE1.0％，针叶木浆打浆度65°SR，阔叶木浆打浆度65°SR，纸基层厚度0.15mm；抄纸设备：长网纸机；阻隔涂层：在纸基层表面涂布5.0％PVA溶液；保鲜涂层：在纸基层、阻隔涂层的基础上涂布2％壳聚糖季铵盐溶液；涂布方式：采用双面单涂涂布方式，105℃下烘干得到高阻隔性保鲜材料，涂布量15g/m2。高阻隔性保鲜材料的检测结果见表1。
实施例3
纸基层：50％漂白硫酸盐针叶木浆：50％漂白硫酸盐阔叶木浆，PAE1.0％，针叶木浆打浆度65°SR，阔叶木浆打浆度75°SR，纸基层厚度0.15mm；抄纸设备：长网纸机；涂布层：选取6％PVA溶液与3％海藻酸钠溶液，以2∶1混合，涂布在纸基层表面；涂布方式：采用双面双涂方式，涂布量10g/m2，105℃下烘干得到高阻隔性保鲜材料。高阻隔性保鲜材料的检测结果见表1。
实施例4
纸基层：40％漂白硫酸盐针叶木浆：60％漂白硫酸盐阔叶木浆，PAE1.0％，针叶木浆打浆度70°SR，阔叶木浆打浆度60°SR，纸基层厚度0.15mm；抄纸设备：长网纸机；涂布层：选取8.0％PVA溶液与6％羧甲基纤维素钠溶液，以3∶1混合，涂布在纸基层表面；涂布方式：采用双面双涂方式，涂布量16g/m2，105℃下烘干得到高阻隔性保鲜材料。阻隔膜的检测结果见表1。
表1实施例的检测结果与目标值的比较
由表1可见，上述各实施例所制成的高阻隔性保鲜材料的主要性能指标满足目标值要求。在搭载冰箱保鲜盒后，维持较高平均湿度的情况下，湿度负载失水率小，结露量少，说明采用本发明所研制的阻隔保鲜材料阻气效果优良，能达到高保湿保鲜效果，且能有效降低果蔬盒的结露量。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (7)
1.一种高阻隔性保鲜材料，其特征在于，所述高阻隔性保鲜材料由以植物纤维为主要原料的复合材料制成，至少包括纸基层和涂布层；所述涂布层由阻隔涂层和保鲜涂层复合而成或混合而成；
其中，所述阻隔涂层为水溶性聚合物涂层，包括聚乙烯醇(PVA)、微纤化纤维素(MFC)、纳米纤维素(NCC)中的一种或几种，溶液质量浓度为2％-15％；
所述保鲜涂层为水溶性吸湿材料，包括壳聚糖、壳聚糖季铵盐、海藻酸钠、羧甲基纤维素、羟甲基纤维素、羟乙基纤维素中的一种或几种，溶液质量浓度为0.5％-5％。
2.根据权利要求1所述的高阻隔性保鲜材料，其特征在于，所述纸基层利用中高打浆度的漂白化学木浆、高吸水性纤维等配抄，浆内添加湿强剂、干强剂等制成原纸，采用湿法抄纸设备抄造而成，所述纸基层定量为40-80g/m2，纵向干抗张力≥40N。
3.根据权利要求2所述的高阻隔性保鲜材料，其特征在于，所述湿强剂为聚酰胺环氧氯丙烷(PAE)、三聚氰胺甲醛树脂中的一种或几种，所述湿强剂的质量为绝干纤维质量的0.1-1.0％；所述干强剂为阴离子聚丙烯酰胺、改性淀粉中的一种或几种，所述干强剂用量为绝干纤维质量的0.1％-0.4％。
4.一种高阻隔性保鲜材料的制备方法，包括如下步骤：(1)生产纸基层，(2)对纸基层进行涂布处理，形成涂布层，其特征在于，在步骤(2)中，将所述纸基层放置在涂布液中进行涂布处理，涂布量2-30g/m2，干燥温度90-120°C，所述涂布液包括阻隔涂层涂布液和保鲜涂层涂布液。
5.根据权利要求4所述的制备方法，其特征在于，所述阻隔涂层涂布液为水溶性聚合物涂布液，包括聚乙烯醇(PVA)、微纤化纤维素(MFC)、纳米纤维素(NCC)中的一种或几种，溶液质量浓度为2％-15％；
所述保鲜涂层涂布液为水溶性吸湿材料，包括壳聚糖、壳聚糖季铵盐、海藻酸钠、羧甲基纤维素、羟甲基纤维素、羟乙基纤维素中的一种或几种，溶液质量浓度为0.5％-5％。
6.根据权利要求5所述的制备方法，其特征在于，所述涂布层由阻隔涂层和保鲜涂层叠加复合而成，涂布方式包括双面单涂或LBL层层自组装方式中的一种。
7.根据权利要求5所述的制备方法，其特征在于，所述涂布液由所述阻隔涂层涂布液和所述保鲜涂层涂布液混合而成，所述阻隔涂层涂布液和保鲜涂层涂布液混合比例为2∶1-5∶1，混合液的质量浓度为1.5％-15％，涂布方式包括单面双涂、双面单涂、双面双涂中的一种。
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