CN115467191B - 环保型防霉变瓦楞纸张的研发 - Google Patents

环保型防霉变瓦楞纸张的研发 Download PDF

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CN115467191B
CN115467191B CN202211153068.4A CN202211153068A CN115467191B CN 115467191 B CN115467191 B CN 115467191B CN 202211153068 A CN202211153068 A CN 202211153068A CN 115467191 B CN115467191 B CN 115467191B
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corrugated paper
mildew
pulp
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slurry
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CN115467191A (zh
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黄宏悦
李海剑
姜义龙
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Zhuhai Zhengye Packaging Co ltd
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Abstract

本发明公开了防霉变瓦楞纸张及其制备方法，其涉及瓦楞纸制备技术领域。本发明。本申请包括如下重量份的原料：70‑80份回收纸浆纤维、4‑10份改性TiO2、15‑25份羧甲基纤维素钠。添加羧甲基纤维素钠具有提高纸张干强度、湿强度以及耐油性、吸墨性和抗水性的作用，纤维素表面引入阳离子基团，羧甲基纤维素钠与纤维素之间的交联状况得到改善，更为有效地改善瓦楞纸的物理强度性能。改性TiO2光激发产生的电子和空穴更容易达到光催化材料表面参加表面化学反应，有效提高材料抗菌防霉变的效果，本申请制备的瓦楞纸作为水果运输的外包装，有效改善水果储运的环境，调节水果保存的湿度，以及起到保鲜防霉变的效果。

Description

环保型防霉变瓦楞纸张的研发
技术领域
本发明涉及瓦楞纸制备技术领域，具体涉及环保型防霉变瓦楞纸张的研发。
背景技术
水果含有人体所需的多种营养物质，随着生活水平的提高，人们对于各种水果的需求也越来越多。伴随着互联网的快速发展，网络购物的需求逐渐旺盛。网购水果成为很多人的选择。但是由于水果生长的地域性、季节性和消费者的需求产生矛盾，新鲜的水果在采摘后，储存和运输不当，会出现失水萎蔫乃至腐烂变质等问题。快递运输过程中，经常使用的瓦楞纸箱是目前市场上最常见的的包装方式，瓦楞纸箱具有很好的抗压强度，是代替木材、塑料等包装的理想选择，并且具有轻便、牢固和保护商品的作用。
水果采摘后，水分供应被断绝，呼吸作用带走一部分水分，储藏环境中的水汽压低于水果表面的水汽压，水分从水汽压高的水果内部向外界水汽压低的环境扩散，水分大量向周围蒸散。细胞壁中的主要成分果胶是影响水果质地软、硬或者绵的重要因素，果胶物质以原果胶、果胶和果胶酸三种不同形态存在于水果组织中。在未成熟的水果中，果胶物质大部分是原果胶，随着水果的逐渐成熟，在果胶酶的作用下，原果胶与纤维素分离，分解成能溶于水的果胶，细胞进步一松散，水果随之变软、发绵。在水果的进一步储藏中，果胶又被分解成果胶酸，失去粘性，水果呈水烂状态。霉菌和细菌分泌可分解果胶物质的酶，破坏水果的组织，造成水果腐烂。因此，如何在储运的同时维持水果的鲜度成为水果运输的难题。
发明内容
本发明的目的在于提供环保型防霉变瓦楞纸张的研发，解决以下技术问题：
现有的瓦楞纸作为水果运输外包装，其对水果保存环境排湿、保鲜防霉变效果差的缺点。
本发明的目的可以通过以下技术方案实现：
环保型防霉变瓦楞纸张，包括如下重量份的原料：70-80份回收纸浆纤维、4-10份改性TiO2、15-25份羧甲基纤维素钠。
作为本发明进一步的方案：所述改性TiO2的制备方法包括如下步骤：
A1：将异丙醇钛、十二烷胺和去离子水加入反应瓶中,机械搅拌0.5-1h, 继续添加37wt％盐酸溶液，常温静置24h,烘箱陈化,过滤、滤渣烘干,得到 TiO2；
A2：取20g TiO2和40g甲苯2,6-二异氰酸酯、800mL无水甲苯加入反应瓶中,真空超声分散均匀，在氮气氛围中，升温至90-100℃下,保温反应6-12h,冷却、离心,洗涤、干燥，得到组分一；
A3：将组分一、甲苯加入反应釜中，加入十六烷基二乙醇胺，并滴加二月桂酸二丁基锡，升温至60-100℃，保温反应4-10h，得到组分二；
A4：将组分二、甲苯、碘甲烷加入反应瓶中，微波反应器功率300-500W，在80-140℃中反应5-12h，得到改性TiO2。
作为本发明进一步的方案：所述A1中异丙醇钛：十二烷胺：去离子水：37wt％盐酸溶液的添加比为20g：5-10g：500-800mL：0.5-1mL。
作为本发明进一步的方案：所述A3中组分一、甲苯、十六烷基二乙醇胺、二月桂酸二丁基锡的质量比为100:600-800:15-25:0.5-3。
作为本发明进一步的方案：所述A4中组分二：甲苯：碘甲烷的质量比为100:200-300:40-80。
作为本发明进一步的方案：所述回收纸浆纤维的制备方法包括如下步骤：
B1:将废旧瓦楞纸板撕成15×15mm2碎片,加水浸泡12h,调整浆料浓度为10％,碎浆机温控23℃以及270rpm的转速下碎解15min，取出碎解浆料拧干、平衡水分，得到废旧纸浆料；
B2:废旧纸浆料放入筛浆机料筒内筛浆,纸浆纤维从筛缝中漏下去,渣滓留在筛板上并通过排渣孔排出，收集筛缝漏下的纸浆纤维，即为回收纸浆纤维。
防霉变瓦楞纸张的制备方法，包括如下步骤：
C1:将10-20mL氯化亚砜、70-80g回收纸浆纤维加入反应釜中，继续加入400-600mLN,N-二甲基甲酰胺、4-10g改性TiO2，并滴加1-3g吡啶，在5-20℃中反应6-18h，得到组分三，将组分三和15-20g羧甲基纤维素钠混合、过滤、洗涤，得到浆样；
C2:浆样在水中浸泡并调整浆浓2％,浸泡24h，加重砣打浆，至所需打浆度时停止打浆；
C3:将浆料稀释后放入纤维标准解离器解离，加水稀释至浓度为0.35％, 用抄取器抄片,湿纸页在105℃下抽真空烘干，得到瓦楞纸张，纸页定量为(11+1)g/m2。
本发明的有益效果：
本申请添加羧甲基纤维素钠具有提高纸张干强度、湿强度以及耐油性、吸墨性和抗水性的作用，浆料纤维中具有负电荷特性，羧甲基纤维素钠更好的吸附在纤维表面，应该在纤维素表面引入阳离子基团，随着羧甲基纤维素钠表面吸附量的提高，纤维之间的交联状况得到改善，更为有效地改善瓦楞纸的物理强度性能。
改性TiO2具有颗粒大、晶粒尺寸小以及比表面积大等优点，大的比表面积使催化剂拥有更多的反应活性点，多孔有利于反应物向内部孔道的扩散、传质和在催化剂表面的吸附以及光催化降解产物从内表面脱附，另外，多孔孔道结构可以使光激发产生的电子和空穴更容易达到光催化材料表面参加表面化学反应，从而提高量子转换效率，有效提高材料抗菌防霉变的效果，本申请制备的瓦楞纸作为水果运输的外包装，有效改善水果储运的环境，调节水果保存的湿度，以及起到保鲜防霉变的效果。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
实施例1
改性TiO2的制备方法包括如下步骤：
A1：将20g异丙醇钛、5g十二烷胺和500mL去离子水加入反应瓶中, 机械搅拌0.5h,继续添加0.5mL 37wt％盐酸溶液，常温静置24h,烘箱陈化, 过滤、滤渣烘干,得到二氧化钛；
A2：取20g TiO2和40g甲苯2,6-二异氰酸酯、800mL无水甲苯加入反应瓶中,真空超声分散均匀，在氮气氛围中，升温至90℃下,保温反应6h, 冷却、离心,洗涤、干燥，得到组分一；
A3：将20g组分一、120g甲苯加入反应釜中，加入3g十六烷基二乙醇胺，并滴加0.1g二月桂酸二丁基锡，升温至60℃，保温反应4h，得到组分二；
A4：将20g组分二、40g甲苯、8g碘甲烷加入反应瓶中，微波反应器功率300W，在80℃中反应5h，得到改性TiO2。
实施例2
改性TiO2的制备方法包括如下步骤：
A1：将20g异丙醇钛、8g十二烷胺和700mL去离子水加入反应瓶中, 机械搅拌0.5h,继续添加0.8mL 37wt％盐酸溶液，常温静置24h,烘箱陈化, 过滤、滤渣烘干,得到二氧化钛；
A2：取20g TiO2和40g甲苯2,6-二异氰酸酯、800mL无水甲苯加入反应瓶中,真空超声分散均匀，在氮气氛围中，升温至95℃下,保温反应9h, 冷却、离心,洗涤、干燥，得到组分一；
A3：将20g组分一、140g甲苯加入反应釜中，加入4g十六烷基二乙醇胺，并滴加0.4g二月桂酸二丁基锡，升温至80℃，保温反应6h，得到组分二；
A4：将20g组分二、50g甲苯、12g碘甲烷加入反应瓶中，微波反应器功率400W，在100℃中反应9h，得到改性TiO2。
实施例3
改性TiO2的制备方法包括如下步骤：
A1：将20g异丙醇钛、10g十二烷胺和800mL去离子水加入反应瓶中, 机械搅拌1h,继续添加1mL 37wt％盐酸溶液，常温静置24h,烘箱陈化,过滤、滤渣烘干,得到二氧化钛；
A2：取20g TiO2和40g甲苯2,6-二异氰酸酯、800mL无水甲苯加入反应瓶中,真空超声分散均匀，在氮气氛围中，升温至100℃下,保温反应12h, 冷却、离心,洗涤、干燥，得到组分一；
A3：将20g组分一、160g甲苯加入反应釜中，加入5g十六烷基二乙醇胺，并滴加0.6g二月桂酸二丁基锡，升温至100℃，保温反应10h，得到组分二；
A4：将20g组分二、60g甲苯、16g碘甲烷加入反应瓶中，微波反应器功率500W，在140℃中反应12h，得到改性TiO2。
实施例4
B1:将废旧瓦楞纸板撕成15×15mm2碎片,加水浸泡12h,调整浆料浓度为10％,碎浆机温控23℃以及270rpm的转速下碎解15min，取出碎解浆料拧干、平衡水分，得到废旧纸浆料；
B2:废旧纸浆料放入筛浆机料筒内筛浆,纸浆纤维从筛缝中漏下去,渣滓留在筛板上并通过排渣孔排出，收集筛缝漏下的纸浆纤维，即为回收纸浆纤维。
实施例5
防霉变瓦楞纸张的制备方法，包括如下步骤：
C1:将10mL氯化亚砜、70g实施例4制备的回收纸浆纤维加入反应釜中，继续加入400mL N,N-二甲基甲酰胺、4g实施例1制备的改性TiO2，并滴加1g吡啶，在5℃中反应6h，得到组分三，将组分三和15g羧甲基纤维素钠混合、过滤、洗涤，得到浆样；
C2:浆样在水中浸泡并调整浆浓2％,浸泡24h，加重砣打浆，至31° SR，停止打浆；
C3:将浆料稀释后放入纤维标准解离器解离，加水稀释至浓度为0.35％, 用抄取器抄片,湿纸页在105℃下抽真空烘干，得到瓦楞纸张，纸页定量为(11+1)g/m2。
实施例6
防霉变瓦楞纸张的制备方法，包括如下步骤：
C1:将15mL氯化亚砜、75g实施例4制备的回收纸浆纤维加入反应釜中，继续加入500mL N,N-二甲基甲酰胺、6g实施例2制备的改性TiO2，并滴加2g吡啶，在10℃中反应12h，得到组分三，将组分三和17g羧甲基纤维素钠混合、过滤、洗涤，得到浆样；
C2:浆样在水中浸泡并调整浆浓2％,浸泡24h，加重砣打浆，至31°SR，停止打浆；
C3:将浆料稀释后放入纤维标准解离器解离，加水稀释至浓度为0.35％, 用抄取器抄片,湿纸页在105℃下抽真空烘干，得到瓦楞纸张，纸页定量为(11+1)g/m2。
实施例7
防霉变瓦楞纸张的制备方法，包括如下步骤：
C1:将20mL氯化亚砜、80g实施例4制备的回收纸浆纤维加入反应釜中，继续加入600mL N,N-二甲基甲酰胺、10g实施例3制备的改性TiO2，并滴加3g吡啶，在20℃中反应18h，得到组分三，将组分三和20g羧甲基纤维素钠混合、过滤、洗涤，得到浆样；
C2:浆样在水中浸泡并调整浆浓2％,浸泡24h，加重砣打浆，至31° SR时，停止打浆；
C3:将浆料稀释后放入纤维标准解离器解离，加水稀释至浓度为0.35％, 用抄取器抄片,湿纸页在105℃下抽真空烘干，得到瓦楞纸张，纸页定量为(11+1)g/m2。
对比例1
TiO2的制备方法包括如下步骤：
A1：将20g异丙醇钛、5g十二烷胺和500mL去离子水加入反应瓶中, 机械搅拌0.5h,继续添加0.5mL 37wt％盐酸溶液，常温静置24h,烘箱陈化, 过滤、滤渣烘干,得到二氧化钛。
对比例2
防霉变瓦楞纸张的制备方法，包括如下步骤：
C1:将10mL氯化亚砜、70g实施例4制备的回收纸浆纤维加入反应釜中，继续加入400mL N,N-二甲基甲酰胺、4g对比例1制备的改性TiO2，并滴加1g吡啶，在5℃中反应6h，得到组分三，将组分三和15g羧甲基纤维素钠混合、过滤、洗涤，得到浆样；
C2:浆样在水中浸泡并调整浆浓2％,浸泡24h，加重砣打浆，至31° SR，停止打浆；
C3:将浆料稀释后放入纤维标准解离器解离，加水稀释至浓度为0.35％, 用抄取器抄片,湿纸页在105℃下抽真空烘干，得到瓦楞纸张，纸页定量为(11+1)g/m2。
对比例3
防霉变瓦楞纸张的制备方法，包括如下步骤：
C1:将70g实施例4制备的回收纸浆纤维、15g羧甲基纤维素钠加入反应釜中混合、过滤、洗涤，得到浆样；
C2:浆样在水中浸泡并调整浆浓2％,浸泡24h，加重砣打浆，至31° SR，停止打浆；
C3:将浆料稀释后放入纤维标准解离器解离，加水稀释至浓度为0.35％, 用抄取器抄片,湿纸页在105℃下抽真空烘干，得到瓦楞纸张，纸页定量为(11+1)g/m2。
性能检测
(1)抗菌性能
将实施例5-7和对比例2-3制备的瓦楞纸，放入培养皿中，然后加入大肠杆菌悬菌液，悬菌液浓度为1×107CFU/mL，加入琼脂培养基，在恒温恒湿培养箱中培养24h，设置培养温度为37℃，按照平皿计数法检测菌落数以标准抗菌性。
(2)调湿性能
①吸湿率检测：将实施例5-7和对比例2-3制备的瓦楞纸在真空干燥器中干燥后,冷却至室温,放在小的培养皿(质量已称)上,准确称量其质量。将称好的试样置于已平衡好温湿度(25℃,80％RH)的恒温恒湿箱中,定期从恒温恒湿箱中去除实验盘并称重。此过程反复进行,直至约1h间隔的两次连续称重结果相差不超过0.1％；
②放湿率检测：将上述吸湿后的试样放入已平衡好的温湿度 (25℃,30％RH)的恒温恒湿箱中,定期从恒温恒湿箱中去除实验盘并称重。此过程反复进行,直至约Ih间隔的两次连续称重结果相差不超过0.1％。
表1：实施例5-7与对比例2-3性能检测
实施例5 实施例6 实施例7 对比例2 对比例3
抗菌性(％) 97.8 99.3 98.3 73.4 45.1
吸湿率(％) 10.2 10.7 10.4 31.2 29.8
放湿率(％) 89.1 92.3 90.7 67.3 53.2
由表1数据得知，本申请制备的瓦楞纸具有优良的抗菌性能，且具有优良的吸湿和放湿性能，能有效调控水果储放环境中的湿度，提升水果存放时间。
以上对本发明的一个实施例进行了详细说明，但所述内容仅为本发明的较佳实施例，不能被认为用于限定本发明的实施范围。凡依本发明申请范围所作的均等变化与改进等，均应仍归属于本发明的专利涵盖范围之内。

Claims (6)

1.环保型防霉变瓦楞纸张，其特征在于，包括如下重量份的原料：70-80份回收纸浆纤维、4-10份改性TiO2、15-25份羧甲基纤维素钠；
改性TiO2的制备方法包括如下步骤：
A1：将异丙醇钛、十二烷胺和去离子水加入反应瓶中,机械搅拌0.5-1h,继续添加37wt%盐酸溶液，常温静置24h,烘箱陈化,过滤、滤渣烘干,得到TiO2；
A2：取TiO2和甲苯2,6-二异氰酸酯、无水甲苯加入反应瓶中,真空超声分散均匀，在氮气氛围中，升温至90-100℃下,保温反应6-12h,冷却、离心,洗涤、干燥，得到组分一；
A3：将组分一、甲苯加入反应釜中，加入十六烷基二乙醇胺，并滴加二月桂酸二丁基锡，升温至60-100℃，保温反应4-10h，得到组分二；
A4：将组分二、甲苯、碘甲烷加入反应瓶中，微波反应器中微波反应，得到改性TiO2。
2.根据权利要求1所述的防霉变瓦楞纸张,其特征在于，所述A1中异丙醇钛：十二烷胺：去离子水：37wt%盐酸溶液的添加比为20g：5-10g：500-800mL：0.5-1mL。
3.根据权利要求1所述的防霉变瓦楞纸张,其特征在于，所述A3中组分一、甲苯、十六烷基二乙醇胺、二月桂酸二丁基锡的质量比为100:600-800:15-25:0.5-3。
4.根据权利要求1所述的防霉变瓦楞纸张,其特征在于，所述A4中组分二：甲苯：碘甲烷的质量比为100:200-300:40-80。
5.根据权利要求1所述的防霉变瓦楞纸张,其特征在于，所述回收纸浆纤维的制备方法包括如下步骤：
B1:将废旧瓦楞纸板撕成碎片,加水浸泡,调整浆料浓度为10%,碎浆机温控23℃以及270rpm的转速下碎解15min，取出碎解浆料拧干、平衡水分，得到废旧纸浆料；
B2:废旧纸浆料放入筛浆机料筒内筛浆,纸浆纤维从筛缝中漏下去,渣滓留在筛板上并通过排渣孔排出，收集筛缝漏下的纸浆纤维，即为回收纸浆纤维。
6.如权利要求1所述的防霉变瓦楞纸张的制备方法，其特征在于，包括如下步骤：
C1:将氯化亚砜、回收纸浆纤维加入反应釜中，继续加入N,N-二甲基甲酰胺、改性TiO2，并滴加吡啶，在5-20℃中反应6-18h，得到组分三，将组分三和羧甲基纤维素钠混合、过滤、洗涤，得到浆样；
C2:浆样在水中浸泡并调整浆浓2%,浸泡24h，加重砣打浆，至所需打浆度时停止打浆；
C3:将浆料稀释后放入纤维标准解离器解离，加水稀释至浓度为0.35%,用抄取器抄片,湿纸页在105℃下抽真空烘干，得到瓦楞纸张。
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