CN107254270B - 一种高附着力水性复膜胶及其制备方法 - Google Patents

一种高附着力水性复膜胶及其制备方法 Download PDF

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CN107254270B
CN107254270B CN201710424722.3A CN201710424722A CN107254270B CN 107254270 B CN107254270 B CN 107254270B CN 201710424722 A CN201710424722 A CN 201710424722A CN 107254270 B CN107254270 B CN 107254270B
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张宵
宋昊
孙冬
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Abstract

本发明公开了一种高附着力水性复膜胶及其制备方法,属于胶黏剂制备技术领域。本发明先将去离子水、乳化剂OP‑10、油酸三乙醇胺等搅拌形成乳化液,以甲基丙烯酸甲酯、丙烯酸乙酯等作为原料,反应获得聚丙烯酰胺,再以甲苯二异氰酸酯、乙二酸等搅拌反应,以过硫酸铵作为引发剂,乙烯基三乙氧基硅烷作为交联剂,在生成聚氨酯的同时对聚丙烯酰胺进行包裹,形成核壳状混合物,提高附着力及耐热稳定性能,最后与硅藻土、马来酸酐、壳聚糖搅拌,引入抗菌物质,增加抗菌性能,同时提高耐热性能,从而获得高附着力水性复膜胶,本发明复膜胶具有剥离强度高、耐热稳定性好、持粘性能好、安全无毒、抗菌防霉性能好的优点,是一种绿色环保的水性复膜胶产品。

Description

一种高附着力水性复膜胶及其制备方法
技术领域
本发明公开了一种高附着力水性复膜胶及其制备方法,属于胶黏剂制备技术领域。
背景技术
纸塑复合是利用胶黏剂将双向拉伸聚丙烯或涤纶薄膜与纸张印刷品复合在一起,复合后的印刷品不仅美观,而且更能耐光、耐热和耐水,从而大大改进了印刷品的应用性和外观。纸塑复合产品可广泛应用于装饰建材、包装材料、精装书籍、产品宣传广告等。
能将PP薄膜粘贴到纸产品上的胶黏剂称为纸塑复合胶黏剂,简称复膜胶。目前纸塑复合胶黏剂主要有3类:热熔型、有机溶剂型和水基乳液型。热熔型复膜胶采用预涂膜的方式,使用不方便、粘结力低、不易后续加工,因而较少采用;有机溶剂型复膜胶由于大量使用甲苯、汽油、醋酸乙酯等有机溶剂,因而物料成本高、劳动条件差、生产及使用不安全、危害身体健康并且严重污染环境。随着消费者对绿色健康需求的重视及国家环保法规的日益严苛,发展环保化、无毒化、性能多元化的水性复膜胶势在必行。
现有的水性复膜胶主要包括聚乙烯醇及其缩醛、聚醋酸乙烯酯、乙烯基聚氨酯双组分、氯丁胶胶乳、复合乳液和聚丙烯酸酯类水性复膜胶等。然而,水性复膜胶虽然具有无毒、无味、无污染、易涂布、干燥快、成本低等优点,但也存在许多不足,主要是现有技术制备的水性复膜胶剥离强度较低,尤其在塑料薄膜上的附着力较差,且复膜胶耐热稳定性不佳,抗菌性较差,长时间放置易发霉,导致其使用受限。因此,开发一种剥离强度高、附着力强,且耐热稳定性及抗菌防霉效果较好的水性复膜胶产品具有重要的现实意义。
发明内容
本发明主要解决的技术问题:针对现有技术制备的复膜胶剥离强度较低,在塑料薄膜上的附着力较差,且复膜胶耐热稳定性不佳,抗菌性较差的缺陷,提供了一种高附着力水性复膜胶及其制备方法。
为了解决上述技术问题,本发明所采用的技术方案是:
一种高附着力水性复膜胶,其特征在于,按重量份数计,包括如下组份:70~80份基料、10~12份硅藻土、4~6份马来酸酐及1~2份壳聚糖。
所述基料按重量份数计,包括70~90份去离子水、12~14份甲基丙烯酸甲酯、9~11份乙二酸、5~8份丙烯酸乙酯、5~8份甲苯二异氰酸酯、3~6份丙烯酸异辛酯、3~5份丙三醇、0.7~0.9份乳化剂OP-10、0.4~0.7份过硫酸铵、0.4~0.6份油酸三乙醇胺、0.2~0.4份三乙烯二胺。
所述的基料中还含有0.13~0.16份乙烯基三乙氧基硅烷及0.06~0.09份乙二胺四乙酸二钠。
所述基料的制备,包括以下步骤:
(1)按照配比,将去离子水、碳酸氢钠、乳化剂OP-10及油酸三乙醇胺,放入容器中,对容器进行加热,设定温度为77~79℃,搅拌30~35min;
(2)向容器中加入甲基丙烯酸甲酯、丙烯酸乙酯,使用氮气保护,将过硫酸铵总质量二分之一的量加入容器中,保温40~50min,升温至82~86℃,分别加入甲苯二异氰酸酯、乙二酸、丙三醇、丙烯酸异辛酯及三乙烯二胺,搅拌反应10~15min;
(3)待搅拌反应结束后,将剩余过硫酸铵加入容器中,保温3~4h后,降温至65~70℃,加入乙烯基三乙氧基硅烷及乙二胺四乙酸二钠,搅拌10~15min后,使用氢氧化钠溶液调节容器中物质pH至7.5~8.0,静置1~2h;
(4)在静置结束后,将容器中的物质倒入蒸馏装置中,设定温度为95~98℃,进行蒸馏,收集蒸馏剩余物,得基料。
一种高附着力水性复膜胶的制备方法,包括如下步骤:
(1)按照配比取料;
(2)将基料、硅藻土、马来酸酐及壳聚糖放入在50~55℃下,搅拌30~40min,收集搅拌混合物,即可得高附着力水性复膜胶。
本发明的有益效果是:
(1)本发明先将去离子水、乳化剂OP-10、油酸三乙醇胺等搅拌形成乳化液,以甲基丙烯酸甲酯、丙烯酸乙酯等作为原料,反应获得聚丙烯酰胺,再以甲苯二异氰酸酯、乙二酸等搅拌反应,以过硫酸铵作为引发剂,在生成聚氨酯的同时对聚丙烯酰胺进行包裹,形成核壳状混合物,提高附着力及耐热稳定性能;
(2)本发明通过添加乙烯基三乙氧基硅烷作为交联剂,使生成聚氨酯对聚丙烯酰胺进行包裹时进行交联,增加强度,进而增加复膜胶剥离强度,同时通过乙烯基三乙氧基硅烷提高在塑料薄膜上的附着力;
(3)本发明利用乙二胺四乙酸二钠作为螯合剂,将基料与硅藻土中金属进行螯合,增加两者的结合度,增加强度;
(4)本发明通过壳聚糖引入抗菌物质,增加抗菌性能,同时利用马来酸酐对壳聚糖进行酰化处理,提高与其他物质的相容性。
具体实施方式
基料的原料:按重量份数计,包括70~90份去离子水、12~14份甲基丙烯酸甲酯、9~11份乙二酸、5~8份丙烯酸乙酯、5~8份甲苯二异氰酸酯、3~6份丙烯酸异辛酯、3~5份丙三醇、0.7~0.9份乳化剂OP-10、0.4~0.7份过硫酸铵、0.4~0.6份油酸三乙醇胺、0.2~0.4份三乙烯二胺。
在基料的原料中还可以加入0.13~0.16份乙烯基三乙氧基硅烷及0.06~0.09份乙二胺四乙酸二钠。
基料的制备:
(1)将去离子水、碳酸氢钠、乳化剂OP-10及油酸三乙醇胺,放入带有搅拌器、滴液漏斗、温度计及冷凝管的容器中,并将容器置于水浴锅中,设定温度为77~79℃,以150r/min搅拌30~35min;
(2)向容器中加入甲基丙烯酸甲酯、丙烯酸乙酯,使用氮气保护,将过硫酸铵总质量二分之一的量加入容器中,保温40~50min,再升温至82~86℃,分别向容器中加入甲苯二异氰酸酯、乙二酸、丙三醇、丙烯酸异辛酯及三乙烯二胺,以120r/min搅拌反应10~15min;
(3)待搅拌反应结束后,将剩余过硫酸铵加入容器中,保温3~4h后,降温至65~70℃,向容器中加入乙烯基三乙氧基硅烷及乙二胺四乙酸二钠,搅拌10~15min后,使用氢氧化钠溶液调节容器中物质pH至7.5~8.0,静置1~2h;
(4)在静置结束后,将容器中的物质倒入蒸馏装置中,设定温度为95~98℃,蒸馏,收集蒸馏剩余物,得基料。
高附着力水性复膜胶,按重量份数计,包括如下组份:70~80份基料、10~12份硅藻土、4~6份马来酸酐及1~2份壳聚糖。
高附着力水性复膜胶的制备方法,包括如下步骤:
(1)按照配比取料,取70~80份基料、10~12份硅藻土、4~6份马来酸酐及1~2份壳聚糖;
(2)将原料放入搅拌机中,在温度为50~55℃下,以200r/min搅拌30~40min,收集搅拌混合物,即可得高附着力水性复膜胶。
实例1
基料的原料:按重量份数计,包括70份去离子水、12份甲基丙烯酸甲酯、9份乙二酸、5份丙烯酸乙酯、5份甲苯二异氰酸酯、3份丙烯酸异辛酯、3份丙三醇、0.7份乳化剂OP-10、0.4份过硫酸铵、0.4份油酸三乙醇胺、0.2份三乙烯二胺。
基料的制备:
(1)将去离子水、碳酸氢钠、乳化剂OP-10及油酸三乙醇胺,放入带有搅拌器、滴液漏斗、温度计及冷凝管的容器中,并将容器置于水浴锅中,设定温度为77℃,以150r/min搅拌30min;
(2)向容器中加入甲基丙烯酸甲酯、丙烯酸乙酯,使用氮气保护,将过硫酸铵总质量二分之一的量加入容器中,保温40min,再升温至82℃,分别向容器中加入甲苯二异氰酸酯、乙二酸、丙三醇、丙烯酸异辛酯及三乙烯二胺,以120r/min搅拌反应10min;
(3)待搅拌反应结束后,将剩余过硫酸铵加入容器中,保温3h后,降温至65℃,使用氢氧化钠溶液调节容器中物质pH至7.5,静置1h;
(4)在静置结束后,将容器中的物质倒入蒸馏装置中,设定温度为95℃,蒸馏,收集蒸馏剩余物,得基料。
高附着力水性复膜胶,按重量份数计,包括如下组份:70份基料、10份硅藻土、4份马来酸酐及1份壳聚糖。
高附着力水性复膜胶的制备方法,包括如下步骤:
(1)按照配比取料,取70份基料、10份硅藻土、4份马来酸酐及1份壳聚糖;
(2)将原料放入搅拌机中,在温度为50℃下,以200r/min搅拌30min,收集搅拌混合物,即可得高附着力水性复膜胶。
实例2
基料的原料:按重量份数计,包括70份去离子水、12份甲基丙烯酸甲酯、9份乙二酸、5份丙烯酸乙酯、5份甲苯二异氰酸酯、3份丙烯酸异辛酯、3份丙三醇、0.7份乳化剂OP-10、0.4份过硫酸铵、0.4份油酸三乙醇胺、0.2份三乙烯二胺。
在基料的原料中还可以加入0.13份乙烯基三乙氧基硅烷及0.06份乙二胺四乙酸二钠。
基料的制备:
(1)将去离子水、碳酸氢钠、乳化剂OP-10及油酸三乙醇胺,放入带有搅拌器、滴液漏斗、温度计及冷凝管的容器中,并将容器置于水浴锅中,设定温度为77℃,以150r/min搅拌30min;
(2)向容器中加入甲基丙烯酸甲酯、丙烯酸乙酯,使用氮气保护,将过硫酸铵总质量二分之一的量加入容器中,保温40min,再升温至82℃,分别向容器中加入甲苯二异氰酸酯、乙二酸、丙三醇、丙烯酸异辛酯及三乙烯二胺,以120r/min搅拌反应10min;
(3)待搅拌反应结束后,将剩余过硫酸铵加入容器中,保温3h后,降温至65℃,使用氢氧化钠溶液调节容器中物质pH至7.5,静置1h;
(4)在静置结束后,将容器中的物质倒入蒸馏装置中,设定温度为95℃,蒸馏,收集蒸馏剩余物,得基料。
高附着力水性复膜胶,按重量份数计,包括如下组份:70份基料、10份硅藻土、4份马来酸酐及1份壳聚糖。
高附着力水性复膜胶的制备方法,包括如下步骤:
(1)按照配比取料,取70份基料、10份硅藻土、4份马来酸酐及1份壳聚糖;
(2)将原料放入搅拌机中,在温度为50℃下,以200r/min搅拌30min,收集搅拌混合物,即可得高附着力水性复膜胶
实例3
基料的原料:按重量份数计,包括70份去离子水、12份甲基丙烯酸甲酯、9份乙二酸、5份丙烯酸乙酯、5份甲苯二异氰酸酯、3份丙烯酸异辛酯、3份丙三醇、0.7份乳化剂OP-10、0.4份过硫酸铵、0.4份油酸三乙醇胺、0.2份三乙烯二胺。
在基料的原料中还可以加入0.16份乙烯基三乙氧基硅烷及0.09份乙二胺四乙酸二钠。
基料的制备:
(1)将去离子水、碳酸氢钠、乳化剂OP-10及油酸三乙醇胺,放入带有搅拌器、滴液漏斗、温度计及冷凝管的容器中,并将容器置于水浴锅中,设定温度为77℃,以150r/min搅拌30min;
(2)向容器中加入甲基丙烯酸甲酯、丙烯酸乙酯,使用氮气保护,将过硫酸铵总质量二分之一的量加入容器中,保温40min,再升温至82℃,分别向容器中加入甲苯二异氰酸酯、乙二酸、丙三醇、丙烯酸异辛酯及三乙烯二胺,以120r/min搅拌反应10min;
(3)待搅拌反应结束后,将剩余过硫酸铵加入容器中,保温3h后,降温至65℃,使用氢氧化钠溶液调节容器中物质pH至7.5,静置1h;
(4)在静置结束后,将容器中的物质倒入蒸馏装置中,设定温度为95℃,蒸馏,收集蒸馏剩余物,得基料。
高附着力水性复膜胶,按重量份数计,包括如下组份:70份基料、10份硅藻土、4份马来酸酐及1份壳聚糖。
高附着力水性复膜胶的制备方法,包括如下步骤:
(1)按照配比取料,取70份基料、10份硅藻土、4份马来酸酐及1份壳聚糖;
(2)将原料放入搅拌机中,在温度为50℃下,以200r/min搅拌30min,收集搅拌混合物,即可得高附着力水性复膜胶。
对实例1~3制得的高附着力水性复膜胶和聚醋酸乙烯酯类水性复膜胶(对比例)进行性能检测,其检测结果如表1:
表1不同水性复膜胶性能
分别将实例1~3制得的高附着力水性复膜胶和聚醋酸乙烯酯类水性复膜胶(对比例)涂布在PE薄膜基材上,控制复膜胶涂布量为8g/m2,待复膜胶在PE薄膜基材上固化后,再将PE薄膜基材与铜版纸基材一同放入压膜机中热压制成纸塑复合材料,随后对制得的纸塑复合材料进行性能检测,其检测结果如表2:
表2不同复膜胶制成的纸塑复合材料性能
检测项目 对比例 实例1 实例2 实例3 检验方法
粘接强度(N/25mm) 3.82 3.95 3.93 4.06 粘接强度检测仪检测
180°剥离强度(kN/m) 0.32 0.45 0.39 0.48 拉力试验机检测/按GB/T2970-1995测定
耐热稳定性(kN/m) 0.12 0.36 0.38 0.41 100℃沸水中蒸煮3h后180°剥离强度变化<±0.15kN/m
综上所述,本发明制得的高附着力水性复膜胶具有粘接性能好、剥离强度高、耐热稳定性优异的特点,且高附着力水性复膜胶抗菌防霉能力较好,能有效预防纸塑成品发霉现象,延长复膜胶存储周期。

Claims (2)

1.一种高附着力水性复膜胶,其特征在于,按重量份数计,包括如下组份:70~80份基料、10~12份硅藻土、4~6份马来酸酐及1~2份壳聚糖;所述基料按重量份数计,包括70~90份去离子水、12~14份甲基丙烯酸甲酯、9~11份乙二酸、5~8份丙烯酸乙酯、5~8份甲苯二异氰酸酯、3~6份丙烯酸异辛酯、3~5份丙三醇、0.7~0.9份乳化剂OP-10、0.4~0.7份过硫酸铵、0.4~0.6份油酸三乙醇胺、0.2~0.4份三乙烯二胺;所述的基料中还含有0.13~0.16份乙烯基三乙氧基硅烷及0.06~0.09份乙二胺四乙酸二钠;所述基料的制备,包括以下步骤:
(1)按照配比,将去离子水、碳酸氢钠、乳化剂OP-10及油酸三乙醇胺,放入容器中,对容器进行加热,设定温度为77~79℃,搅拌30~35min;
(2)向容器中加入甲基丙烯酸甲酯、丙烯酸乙酯,使用氮气保护,将过硫酸铵总质量二分之一的量加入容器中,保温40~50min,升温至82~86℃,分别加入甲苯二异氰酸酯、乙二酸、丙三醇、丙烯酸异辛酯及三乙烯二胺,搅拌反应10~15min;
(3)待搅拌反应结束后,将剩余过硫酸铵加入容器中,保温3~4h后,降温至65~70℃,加入乙烯基三乙氧基硅烷及乙二胺四乙酸二钠,搅拌10~15min后,使用氢氧化钠溶液调节容器中物质pH至7.5~8.0,静置1~2h;
(4)在静置结束后,将四口烧瓶中的物质倒入蒸馏装置中,设定温度为95~98℃,蒸馏1~2h,收集蒸馏剩余物,得基料。
2.一种如权利要求1所述的高附着力水性复膜胶的制备方法,包括如下步骤:
(1)按照配比取料;
(2)将基料、硅藻土、马来酸酐及壳聚糖放入在50~55℃下,搅拌30~40min,收集搅拌混合物,即可得高附着力水性复膜胶。
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