CN110589240B - 冷链专用防雾防霉保鲜包装盒 - Google Patents
冷链专用防雾防霉保鲜包装盒 Download PDFInfo
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Abstract
本发明涉及一种冷链专用防雾防霉保鲜包装盒,包括四面侧壁和一体制出的下底壁,上部为可密封盖装的上盖,所述侧壁、底壁以及上盖均为双层保鲜膜板密封组成的中空结构,保鲜膜板为从内到外依次由抗菌防霉层、气凝胶隔热层和防雾层采用粘接剂粘接而成,在双层保鲜膜板密封组成的中空结构设置支撑筋,在盒体内部的保鲜膜板内壁上均匀设置多段毛细管,毛细管材质为PE塑料层包裹铜管层。本包装盒体及盒盖均采用双层、三层或多层密封结构,层间距5~20mm,并有“工”字形或三角形龙骨支撑连接,每层中间为半真空状态,其余成分为惰性气体填充。既能起到隔热保冷的效果,实现缓慢升降温不结露、并保持果粉防腐烂,同时半真空状态可防止盒体挤压变形。
Description
技术领域
本发明属于保鲜技术领域,尤其是一种冷链专用防雾防霉保鲜包装盒。
背景技术
生鲜果蔬采后仍属于鲜活农产品,在冷链物流过程中基本采用泡沫箱、塑料箱或纸箱包装,只起到一个密封作用,防止食品间混气味和交叉污染及食品中水分的耗散,但运输期间的保鲜效果并不好,目前我国果蔬在流通环节的损耗率在 25%-30%左右,远高于发达国家的1%。
(1)常规保鲜包装盒隔热和保温性能差,当从低温冷链物流到冷柜货架、从货架冷藏到消费过程中,盒内外升降温梯度大,一方面位于包装盒内部的果蔬表面冷凝而结露,产生湿害或破坏自身果粉引发腐烂,降低保鲜效果;另一方面保鲜盒外侧由于空气中水蒸气遇冷盒体液化凝结而形成水珠,不仅严重影响包装透明度和美观,凝结水同样会使细菌霉菌等微生物繁殖加快,加速果蔬腐败。
(2)常规保鲜盒为实现隔热保温效果常采用双层结构中间抽真空操作,对材料强度要求高,如钢化玻璃等,但作为果蔬物流包装盒运输造价高;而普通 PE材料轻便、造价低,但抽真空易挤压变形。
(3)包装盒防止结雾一般是在透明基材表面涂敷一层防雾材料,但常规防雾剂耐久性差,其表面活性剂容易被擦除或溶解,导致防雾时效短。另外隔热、防雾、防霉等材料的添加会影响包装盒的透明度。
(4)传统保鲜盒冷源、气体成分等随重力作用下沉,易造成保鲜盒内上下位置温度、湿度、气体分布差异大不均匀,影响果蔬品质。
发明内容
本发明的目的在于克服现有技术的不足之处,提供一种保鲜性能好、结构新颖的冷链专用防雾防霉保鲜包装盒。
本发明解决其技术问题是采取以下技术方案实现的:
一种冷链专用防雾防霉保鲜包装盒,包括四面侧壁和一体制出的下底壁,上部为可密封盖装的上盖,所述侧壁、底壁以及上盖均为双层保鲜膜板密封组成的中空结构,保鲜膜板为从内到外依次由抗菌防霉层、气凝胶隔热层和防雾层采用粘接剂粘接而成。
而且,在双层保鲜膜板密封组成的中空结构设置支撑筋。
而且,双层保鲜膜板密封组成的中空结构中填充混合惰性气体,惰性气体配比N2为75%~90%,Ar为5%~10%,CO2为5%~15%。
所述抗菌防霉层材料的制备方法如下:
配方:PE或PP塑料基材100份,抗菌剂5~10份,碳酸钙母粒1~5份;
步骤:将上述PE或PP塑料基材、抗菌剂和碳酸钙母粒按比例添加到高速搅拌机中,在80~120r/min的转速下搅拌3~5min,混合均匀后加入挤出机中,设定温度180~260℃下物料熔融混合,经模口挤出后进入制片机,调节制片机辊筒间隙制得厚度为0.5~2.5mm的抗菌防霉片材;所述抗菌剂为纳米银、纳米氧化锌、纳米铜抗菌母粒中的一种;
所述气凝胶隔热层的制备方法如下:
①以中空二氧化硅纳米粒子作为气凝胶前驱体,将硅源、丙酮、无水乙醇、去离子水按照摩尔比为1:4:4:4的比例混合搅拌10~20min至均匀,先用稀盐酸调节溶胶pH至3~4,搅拌水解2~5h得到硅溶胶;随后缓慢加入稀氨水调节pH 至6~7,在室温静置使之成为硅凝胶,之后密封保温30~40℃充分老化2~3天;以上混合、反应均在超声和磁力搅拌条件下完成以保证凝胶的透明度,超声功率 150W,频率50kHz,磁力搅拌速度200-300r/min;
②上述所得老化后的凝胶用有机溶剂洗涤置换去除凝胶骨架中残留的去离子水,所用有机溶剂为正己烷,每隔12~18h更换一次有机溶剂,直到凝胶水含量降低到2%~3%;
③将②中所得置换完毕的凝胶进行表面折光疏水改性,具体操作为将凝胶完全浸入体积比为5:3:10:20~50的纳米石墨、紫外线吸收剂、三甲基氯硅烷和正己烷组成的均匀混合液中,密封反应2~3天,所述紫外线吸收剂为苯并三唑类紫外吸收剂,可有效吸收波长270~380nm的紫外线;
④密封后的凝胶采用丙酮清洗后自然挥发完全,置于55~65℃干燥3h即制得隔热折光疏水气凝胶,制得气凝胶隔热层。
而且,所述防雾层的制备方法如下:
配方:聚丙烯酸30~40份,聚乙烯醇60~70份,纳米二氧化硅10~20份;
步骤①:先将一定质量的聚乙烯醇加入蒸馏水中水浴2~3h,水浴温度 80~90℃,得到浓度为10%的聚乙烯醇溶液;再将一定质量聚丙烯酸加入常温蒸馏水中制成浓度为3%的溶液;然后将按上述配比将两种溶液混合,搅拌30min 至混合均匀,静置12~24h以脱除气泡,之后先在50~60℃条件下干燥4~6h,再进行热处理交联改性以提高膜的耐热水和亲水性能,热处理温度为150~180℃、时间5~10min,得到高分子量聚丙烯酸改性的聚乙烯醇薄膜;
步骤②:在上述得到的聚合物膜涂层上沉积一层粒径大小60~100nm的二氧化硅纳米颗粒,采用原位纳米压印技术将一定质量二氧化硅纳米颗粒压入聚合物膜涂层中,通过130~150℃热处理5~10min,促进聚合物交联,之后用蒸馏水冲洗涂层表面15次,清洗掉没有嵌入涂层的纳米颗粒,常温干燥后获得防雾层;
而且,所述粘接剂包括聚氨酯质量分数80%~90%的聚氨酯和10%~20%的硅烷偶联剂,均匀混合即可。
而且,在盒体内部的保鲜膜板内壁上均匀设置多段毛细管,毛细管材质为 PE塑料层包裹铜管层。
而且,所述毛细管的PE塑料层厚度为1~2mm、铜管层厚度为0.2~0.5mm,毛细管内径Φ0.3mm~Φ1.5mm。
本发明的优点和积极效果是:
1、本包装盒体及盒盖均采用双层、三层或多层密封结构,层间距5~20mm,并有“工”字形或三角形龙骨支撑连接,每层中间为半真空状态,其余成分为惰性气体填充。既能起到隔热保冷的效果,实现缓慢升降温不结露、并保持果粉防腐烂,同时半真空状态可防止盒体挤压变形。
2、本保鲜盒的盒体材料以PE、PP或PC塑料为基材,从内到外依次为抗菌防霉层、气凝胶隔热层和防雾层,并通过对功能助剂采取纳米级超细处理或物理化学改性保证盒体透明度,实现内侧防霉、中层隔热和外侧防雾的三重功效。
3、本保鲜盒内部针对不同果蔬品种调节特定适宜的气体成分,起到气调保鲜的效果。并且内层壁上均匀设置多段毛细管,利用毛细管的隧道效应和毛细引流效应使保鲜盒内温度、湿度、气体分布均匀,形成稳定的内循环,起到缓冲波动作用。
附图说明
图1为本申请包装盒结构示意图。
图2为倾斜支撑筋结构示意图。
具体实施方式
下面结合附图并通过具体实施例对本发明作进一步详述,以下实施例只是描述性的,不是限定性的,不能以此限定本发明的保护范围。
一种冷链专用防雾防霉保鲜包装盒,包括四面侧壁和一体制出的下底壁,上部为可密封盖装的上盖1,所述侧壁、底壁以及上盖均为双层保鲜膜板4密封组成的中空结构,保鲜膜板为从内到外依次由抗菌防霉层、气凝胶隔热层和防雾层粘接而成。
为了保证中空结构的稳定,在双层保鲜膜板密封组成的中空结构设置支撑筋 2,支撑筋为竖直、倾斜或者弧形设置。
双层保鲜膜板密封组成的中空结构中保持半真空+惰性气体填充,首先抽至-0.1MPa全真空状态后再充惰性气体至-0.5MPa半真空状态。其中惰性气体配比 N2为75%~90%,Ar为5%~10%,CO2为5%~15%,三种气体配比后传热系数范围在0.002~0.023W/(m·K),隔热保温效果强。
三种气体组份包含两种非极性分子N2和Ar、一种极性分子CO2,在低温下中性原子可依靠弥散力产生的瞬时电偶极矩作用发生关联结合成分子晶体,惰性气体晶体与CO2极性分子相互吸引碰撞发生能量转移,电偶极矩取向一致时系统能量最低。
氩气为无色无臭极经济的惰性气体,导热系数低同时可降低PE塑料的热对流。研究证明对果蔬有明显抑菌和保鲜作用,一方面氩气可通过改变微生物细胞的膜流特性从而影响其功能;另一方面氩原子大小类似O2,加之氩气密度大、溶解度高,可从果蔬细胞及活性酶的氧接收器中置换O2,达到抗氧化并减缓呼吸代谢。
上述保鲜膜板的组成材料从内到外依次为抗菌防霉层、气凝胶隔热层和防雾层,具体实施方式如下:
(1)抗菌防霉层材料的制备:
配方:PE或PP塑料基材100份,抗菌剂5~10份,碳酸钙母粒1~5份
步骤:将上述PE或PP塑料基材、抗菌剂和碳酸钙母粒按比例添加到高速搅拌机中,在80~120r/min的转速下搅拌3~5min,混合均匀后加入挤出机中,设定温度180~260℃下物料熔融混合,经模口挤出后进入制片机,调节制片机辊筒间隙制得厚度为0.5~2.5mm的抗菌防霉片材。
所述抗菌剂为纳米银、纳米氧化锌、纳米铜抗菌母粒中的一种。采用纳米材料分散技术,不仅保证了制品的透明度,还增加了抗菌防霉性能。
纳米抗菌母粒主要成分为带有活性基团的氯苯咪唑类高分子化合物,带有的抗菌基团通过干扰病菌细胞膜的通透性和阻碍病菌蛋白质的合成实现持久抗真菌和霉菌的效果,抗菌寿命和制品寿命同步。
加入的碳酸钙母粒可增强制品的刚性和热稳定性,独特的微孔结构可使果蔬进行O2、CO2和乙烯等气体的自发调节,实现防霉保鲜效果。
(2)气凝胶隔热层的制备:
①以中空二氧化硅纳米粒子作为气凝胶前驱体,将硅源、丙酮、无水乙醇、去离子水按照摩尔比为1:4:4:4的比例混合搅拌10~20min至均匀,先用稀盐酸调节溶胶pH至3~4,搅拌水解2~5h得到硅溶胶;随后缓慢加入稀氨水调节pH 至6~7,在室温静置使之成为硅凝胶,之后密封保温30~40℃充分老化2~3天。以上混合、反应均在超声和磁力搅拌条件下完成以保证凝胶的透明度,超声功率 150W,频率50kHz,磁力搅拌速度200-300r/min。
②上述所得老化后的凝胶用有机溶剂洗涤置换去除凝胶骨架中残留的去离子水,所用有机溶剂为正己烷,每隔12~18h更换一次有机溶剂,直到凝胶水含量降低到2%~3%,可最大程度降低凝胶表面张力保持完整性。
③将②中所得置换完毕的凝胶进行表面折光疏水改性,具体操作为将凝胶完全浸入体积比为5:3:10:20~50的纳米石墨、紫外线吸收剂、三甲基氯硅烷和正己烷组成的均匀混合液中,密封反应2~3天。所述紫外线吸收剂为苯并三唑类紫外吸收剂,可有效吸收波长270~380nm的紫外线。
④密封后的凝胶采用丙酮清洗后自然挥发完全,置于55~65℃干燥3h即制得隔热折光疏水气凝胶。最终制得气凝胶层具有三维网络结构,孔洞尺寸为 10~50nm,导热率为0.012W/(m·K)。
(3)防雾层的制备:
配方:聚丙烯酸30~40份,聚乙烯醇60~70份,纳米二氧化硅10~20份。
步骤①:先将一定质量的聚乙烯醇加入蒸馏水中水浴2~3h,水浴温度 80~90℃,得到浓度为10%的聚乙烯醇溶液;再将一定质量聚丙烯酸加入常温蒸馏水中制成浓度为3%的溶液。然后将按上述配比将两种溶液混合,搅拌30min 至混合均匀,静置12~24h以脱除气泡,之后先在50~60℃条件下干燥4~6h,再进行热处理交联改性以提高膜的耐热水和亲水性能,热处理温度为150~180℃、时间5~10min,得到高分子量聚丙烯酸改性的聚乙烯醇薄膜。
步骤②:在上述得到的聚合物膜涂层上沉积一层粒径大小60~100nm的二氧化硅纳米颗粒,采用原位纳米压印技术将一定质量二氧化硅纳米颗粒压入聚合物膜涂层中,通过130~150℃热处理5~10min,促进聚合物交联,之后用蒸馏水冲洗涂层表面15次,清洗掉没有嵌入涂层的纳米颗粒,常温干燥后获得防雾性能好、机械性较强的防雾层。
说明:在聚乙烯醇链的流动与表面羟基的协同作用下,防雾涂层刮痕处的自由羟基会与表面的羟基重新形成氢键,从而使得刮痕很快愈合。进一步沉积一层空心二氧化硅纳米颗粒,凝结在空心硅纳米颗粒表面的小水珠会通过空心球层的空洞、空隙、裂缝进入聚合物层与其羟基基团相互作用,阻止雾的形成,从而消除由于表面小水珠带来的散射。
(4)上述(1)中抗菌防霉层、(2)中气凝胶隔热层与(3)中防雾层依次采用粘接剂连接得到所述盒体材料,然后进入预设温度为250~350℃的热成型机,通过不同形状模具造型制成冷链专用防雾防霉保鲜盒用的保鲜膜板。
所述粘接剂包括聚氨酯质量分数80%~90%的聚氨酯和10%~20%的硅烷偶联剂,均匀混合即可。
说明:硅烷偶联剂本身有两种基团,一种可以和被粘的骨架材料结合,另一种可以与高分子材料或粘接剂结合,从而在粘接界面形成高强力的化学键,促进界面融合,改善粘接强度。
(5)本申请还推荐一种结构,在盒体内部的保鲜膜板内壁上均匀设置多段毛细管3,毛细管材质为PE塑料层包裹铜管层,其中PE塑料层厚度为1~2mm、铜管层厚度为0.2~0.5mm,毛细管内径Φ0.3mm~Φ1.5mm,毛细管长度占盒体内壁高度1/3~1/2,毛细管排列间距为毛细管外径的3~20倍,可实现流体、介质、气体和其他物质通过所述毛细管传输。
保鲜盒内部针对不同果蔬设定不同气调保鲜参数,通过果蔬自发调控盒体内气体微环境达到冷链运输保鲜目标。常见果蔬(列举10种常见水果)保鲜按以下气体配比设定:
品种 | O<sub>2</sub> | CO<sub>2</sub> | N<sub>2</sub> |
苹果 | 1%~2% | 0.5%~5% | 93%~98.5% |
梨 | 5%~10% | <1% | 89%~94% |
山楂 | 3%~5% | 4%~5% | 90%~93% |
桃 | 3%~5% | 3%~5% | 90%~94% |
鲜枣 | 7%~8% | <1% | 91%~92% |
樱桃 | 3%~5% | 10%~20% | 75%~87% |
草莓 | 10% | 5%~10% | 80%~85% |
柿子 | 2%~5% | 3%~8% | 87%~95% |
石榴 | 2%~4% | 1%~2% | 94%~97% |
柑橘/柚子 | 5%~10% | 0~5% | 85%~95% |
说明:毛细管选用PE塑料层包裹铜层,既可以实现里层铜管所具有的良好导热性能,使保鲜盒内上下位置温度均匀分布,又可以利用PE塑料层惰性且致密的功能保护铜层免受潮湿空气及腐蚀性气体的腐蚀。
本发明最终制得保鲜盒符合国家食用标准,可重复使用。保鲜包装箱规格 0.3~125L,可用于单果包装也可用于成箱包装,适用于易腐水果、蔬菜、生鲜食品等,尤其是鲜切果蔬的冷链保鲜包装。
以苹果为例,从冷链温度4℃到室温25℃,传统塑料保鲜盒内外温度平衡时间为1~2h,本发明冷链专用防雾防霉保鲜盒内外温度平衡时间长达6~8h,温度回升延缓4~7h,保鲜盒内温度缓慢上升从而不结露,另外保鲜盒内气体、湿度分布均匀,贮运损伤少、货架期延长,实现果蔬有机防腐效果。
Claims (1)
1.一种冷链专用防雾防霉保鲜包装盒,包括四面侧壁和一体制出的下底壁,上部为可密封盖装的上盖,其特征在于:所述侧壁、底壁以及上盖均为双层保鲜膜板密封组成的中空结构,保鲜膜板为从内到外依次由抗菌防霉层、气凝胶隔热层和防雾层采用粘接剂粘接而成;
在双层保鲜膜板密封组成的中空结构设置支撑筋;
双层保鲜膜板密封组成的中空结构中填充混合惰性气体,惰性气体配比N2为75%~90%,Ar为5%~10%,CO2为5%~15%;
所述抗菌防霉层材料的制备方法如下:
配方:PE或PP塑料基材100份,抗菌剂5~10份,碳酸钙母粒1~5份;
步骤:将上述PE或PP塑料基材、抗菌剂和碳酸钙母粒按比例添加到高速搅拌机中,在80~120r/min的转速下搅拌3~5min,混合均匀后加入挤出机中,设定温度180~260℃下物料熔融混合,经模口挤出后进入制片机,调节制片机辊筒间隙制得厚度为0.5~2.5mm的抗菌防霉片材;所述抗菌剂为纳米银、纳米氧化锌、纳米铜抗菌母粒中的一种;
所述气凝胶隔热层的制备方法如下:
①以中空二氧化硅纳米粒子作为气凝胶前驱体,将硅源、丙酮、无水乙醇、去离子水按照摩尔比为1:4:4:4的比例混合搅拌10~20min至均匀,先用稀盐酸调节溶胶pH至3~4,搅拌水解2~5h得到硅溶胶;随后缓慢加入稀氨水调节pH至6~7,在室温静置使之成为硅凝胶,之后密封保温30~40℃充分老化2~3天;以上混合、反应均在超声和磁力搅拌条件下完成以保证凝胶的透明度,超声功率150W,频率50kHz,磁力搅拌速度200-300r/min;
②上述所得老化后的凝胶用有机溶剂洗涤置换去除凝胶骨架中残留的去离子水,所用有机溶剂为正己烷,每隔12~18h更换一次有机溶剂,直到凝胶水含量降低到2%~3%;
③将②中所得置换完毕的凝胶进行表面折光疏水改性,具体操作为将凝胶完全浸入体积比为5:3:10:20~50的纳米石墨、紫外线吸收剂、三甲基氯硅烷和正己烷组成的均匀混合液中,密封反应2~3天,所述紫外线吸收剂为苯并三唑类紫外吸收剂,可有效吸收波长270~380nm的紫外线;
④密封反应后的凝胶采用丙酮清洗后自然挥发完全,置于55~65℃干燥3h即制得隔热折光疏水气凝胶,制得气凝胶隔热层;
所述防雾层的制备方法如下:
配方:聚丙烯酸30~40份,聚乙烯醇60~70份,纳米二氧化硅10~20份;
步骤①:先将一定质量的聚乙烯醇加入蒸馏水中水浴2~3h,水浴温度80~90℃,得到浓度为10%的聚乙烯醇溶液;再将一定质量聚丙烯酸加入常温蒸馏水中制成浓度为3%的溶液;然后将按上述配比将两种溶液混合,搅拌30min至混合均匀,静置12~24h以脱除气泡,之后先在50~60℃条件下干燥4~6h,再进行热处理交联改性以提高膜的耐热水和亲水性能,热处理温度为150~180℃、时间5~10min,得到高分子量聚丙烯酸改性的聚乙烯醇薄膜;
步骤②:在上述得到的聚合物膜涂层上沉积一层粒径大小60~100nm的二氧化硅纳米颗粒,采用原位纳米压印技术将一定质量二氧化硅纳米颗粒压入聚合物膜涂层中,通过130~150℃热处理5~10min,促进聚合物交联,之后用蒸馏水冲洗涂层表面15次,清洗掉没有嵌入涂层的纳米颗粒,常温干燥后获得防雾层;
所述粘接剂包括聚氨酯质量分数80%~90%的聚氨酯和10%~20%的硅烷偶联剂,均匀混合即可;
在盒体内部的保鲜膜板内壁上均匀设置多段毛细管,毛细管材质为PE塑料层包裹铜管层;
所述毛细管的PE塑料层厚度为1~2mm、铜管层厚度为0.2~0.5mm,毛细管内径Φ0.3mm~Φ1.5mm。
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