CN109054222A - 一种清洁生态可降解pvc装饰人造革 - Google Patents
一种清洁生态可降解pvc装饰人造革 Download PDFInfo
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Abstract
本发明公开了一种清洁生态可降解装饰PVC人造革的制备方法,该人造革利用生态PVC浆料制成;所述生态浆料由以下成分制成:PVC树脂粉、氯醋树脂、二乙酰环氧大豆油酸甘油酯、聚己内酯基聚氨酯弹性体、发泡剂、环氧大豆油、有机改性黏土、润滑剂、硅酮母粒、稳定剂。本发明处理工艺制得的人造革有无毒环保、耐低温、耐磨耐刮、柔软度佳、极易保养、可部分生物降解、有质感、色泽饱满,吸湿透气、滑爽舒适、抗菌除臭、抗迁移性好。
Description
技术领域
本发明属于人造革制造领域,具体涉及一种清洁生态可降解PVC装饰人造革。
背景技术
生态人造合成革的理念包括以下四个方面:一是在生产制造过程中不给环境带来污;二是将其加工成革制品过程中无害;三是使用过程中对人体无害,对环境不产生污染;四是可生物降解,且降解产物不会对环境造成新的污染。目前,我们提到生态合成革,人们强调的是产品在使用过程中对人体无害,对环境不产生污染,这仅仅是生态合成革的一个方面,如果考虑其他三要素:生产制造过程中绿色化、革制品加工绿色化、废弃物再生化或可生物降解,可以说,我们还没有真正意识上的生态合成革。目前,合成革企业大多采用溶剂型浆料,材料非环境友好,制造过程非绿色化。生态人造合成革的开发必须采用清洁生产技术。低碳、低能耗、零排放或少排放、循环利用是清洁生产技术的核心内容。
发明内容
本发明的目的是针对现有的问题,提供了一种清洁生态可降解PVC装饰人造革。
一种清洁生态可降解PVC装饰人造革,由下列重量份数的原料制成:PVC树脂粉50~100份、氯醋树脂20~30份、二乙酰环氧大豆油酸甘油酯32~45份、聚己内酯基聚氨酯弹性体10~25份、发泡剂1~2份、环氧大豆油20~24份、有机改性黏土15~22份、润滑剂1~2份、硅酮母粒1~2份、稳定剂1~2份、颜料1~2份。
一种清洁生态可降解PVC装饰人造革的制备,其包括以下步骤:
(1)将经过称量的PVC树脂粉、氯醋树脂、聚己内酯基聚氨酯弹性体、润滑剂、硅酮母粒、稳定剂,投入到高速捏合机中,随后加入环氧大豆油,搅拌5~10min,再加入有二乙酰环氧大豆油酸甘油酯,再搅拌5~10min后,加入颜料,再搅拌3min,将有机改性黏土和发泡剂加入,并搅拌3~5min。当混合温度至90~100℃时,达到混合料握在手心中不湿润,柔软均匀,有弹性,即可放料,得初混料。
(2)将初混料放入密炼机中,放下浮压锤,密炼3.5~4min,待电流平稳、料团密炼至料团不带生粉,送入将物料送至炼塑机;
(3)炼塑在初炼塑机上打包翻卷几次送至终炼塑机,炼塑至料卷发糯、半透明无亮光时,切成直径为中10~15cm的料卷或开成料片,用传送带送至压延机,得到压延浆料;
(4)压延浆料贴合经预热开幅处理的布基,平整地引入中、下辊间,把经预热的面层膜在贴合部分和上述制得的半成品革再贴合后进入烘箱塑化,220℃下发泡,经冷却定型后,得到清洁生态可降解PVC装饰人造革。
进一步的,所述炼塑工艺条件为初炼辊温165~175℃,辊距5~7mm,终炼辊温170~180℃,辊距3~5mm,使中下辊间余料直径不超过中2~3cm。
进一步的,第1步所述的有机改性黏土为质量分数为20%的均匀黏土悬浮液,与表面活改性性剂溶解在反应水和乙醇的混合溶液,在温度为25~80℃,搅拌1h,后经过滤得到的有机改性黏土;所述的表面改性活性剂为二烷基咔唑鎓盐、氨丙基异丁基多面体低聚倍半硅氧烷、十六烷基氯化吡啶/a-环糊精、脱氧苯偶姻二甲基十六烷基季铵盐、季铵盐4-(4-金刚烷基苯氧基)-1丁基胺、溴化烷基咔唑鎓盐、二烷基咔唑鎓盐、喹啉鎓盐、多面体低聚倍半硅氧烷的一种过多种。
进一步的,所述聚己内酯基聚氨酯弹性体为NCO/OH摩尔比为1.05:1的二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯和聚己内酯二元醇在超声20kHz条件下加入总重0.01~0.08%分数的辛酸亚锡,在60℃下搅拌反应24h, 固化交联得到的聚合物弹性体。
进一步的,所述的发泡剂为4,4'-氧代双苯磺酰肼、二氯四氟乙烷、一氯三氟丙烯的一种或多种。
进一步的,所述氯醋树脂为氯乙烯-醋酸乙烯酯共聚物,醋酸乙烯酯含量为5%~14%。
进一步的,所述布基为克重155~175g/m2、厚度0.55~0.65mm、幅宽1.55~1.65m、经向拉伸负荷≥300N、纬向拉伸负荷≥300N、经向断裂伸长率≥10%、纬向断裂伸长率≥15%、经向撕裂负荷≥20N、纬向撕裂负荷≥20N、经向和纬向热收缩率≥3%的机织单面起绒斜纹布。
本发明的有益效果:
引入本身内增塑的氯醋树脂,增加人造革的强度,减少增塑剂的用量,避免了小分子的迁移,同时增加了人造革的韧性,光亮性。人造革溶解性能及配成的胶浆流动性能优良,人造革具有很好的韧性,耐久的饶曲性,极好的抗撕特性和对所有漆膜显示出优异的粘合性,能增加有机改性黏土分子间作用力,降低成本,耐增塑剂迁移。
引入与聚氯乙烯相容性很好的聚己内酯基弹性体,具有形状记忆功能,人造革形状保持性能好,耐皱,耐折。聚己内酯基聚氨酯,有生物降解性,利用人造革的回收利用。而且是人造革具有优良的热性能、机械性能、形状记忆功能和生物性能。在室温下形状回复时间少,且无细胞毒性。
采用有机改性黏土对材料的耐热性能进行改善。用于有机改性黏土的表面活性剂,结构中通常含有脂肪族长链。脂肪链会根据它自身的尺寸及浓度,自动排列成单层、双层类三层或斜蜡状结构,并决定黏土的最终层间距。选择合适种类的表面改性剂,可提高聚合物和黏土间的相容性,并促进纳米黏土在合适制备条件下的插层。当黏土发生剥离、均匀分散在聚合物中时,在不影响力学性能的前提下,材料的耐热性能得到明显提高,还可以提高部分阻燃性。
本发明相比现有技术具有以下优点:
本发明提供的一种清洁生态可降解PVC装饰人造革,经过本发明对PVC树脂粉的共混改性,制备的人造革耐迁移性得到极大的加强,通过本发明各成分之间的协同配合作用,制成的人造革不仅具有较好的机械性能(如拉伸负荷、断裂伸长率、撕裂伸长率、撕裂负荷等),相较于普通人造革,本发明人造革拉伸负荷提高了20%左右,撕裂负荷提高了66%左右,还具有较佳的耐折牢度老化性能,该皮革通过了32000次耐折牢度实验,老化性能实验结果为不开裂。试验发现,本发明力学性能得到极大的提高,增加了阻燃可降解能力,增强了耐热性,并且吸湿透气、清洁滑爽舒适、抗菌除臭、抗迁移性好。
具体实施方式
下面用具体实施例说明本发明,但并不是对本发明的限制。
实施例1
一种清洁生态可降解PVC装饰人造革,由下列重量份数的原料制成:PVC树脂粉100份、氯醋树脂30份、二乙酰环氧大豆油酸甘油酯38份、聚己内酯基聚氨酯弹性体20份、发泡剂1份、环氧大豆油20份、有机改性黏土20份、润滑剂1份、硅酮母粒1份、稳定剂1份、颜料1份。
一种清洁生态可降解PVC装饰人造革的制备,其包括以下步骤:
(1)将经过称量的PVC树脂粉、氯醋树脂、聚己内酯基聚氨酯弹性体、润滑剂、硅酮母粒、稳定剂,投入到高速捏合机中,随后加入环氧大豆油,搅拌10min,再加入有二乙酰环氧大豆油酸甘油酯,再搅拌10min后,加入颜料,再搅拌3min,将有机改性黏土和发泡剂加入,并搅拌5min。当混合温度至100℃时,达到混合料握在手心中不湿润,柔软均匀,有弹性,即可放料,得初混料。
(2)将初混料放入密炼机中,放下浮压锤,密炼4min,待电流平稳,料团密炼至料团不带生粉,送入将物料送至炼塑机;
(3)炼塑在初炼塑机上打包翻卷几次送至终炼塑机,炼塑至料卷发糯、半透明无亮光时,切成直径为中10~15cm的料卷或开成料片,用传送带送至压延机,得到压延浆料;
(4)压延浆料贴合经预热开幅处理的布基,平整地引入中、下辊间,把经预热的面层膜在贴合部分和上述制得的半成品革再贴合后进入烘箱塑化,220℃下发泡,经冷却定型后,得到清洁生态可降解PVC装饰人造革。
进一步的,所述炼塑工艺条件为初炼辊温165~175℃,辊距5~7mm,终炼辊温170~180℃,辊距3~5mm,使中下辊间余料直径不超过中2~3cm。
进一步的,第1步所述的有机改性黏土为质量分数为20%的均匀黏土悬浮液,与表面活改性性剂溶解在反应水和乙醇的混合溶液,在温度为50℃,搅拌1h,后经过滤得到的有机改性黏土;所述的表面改性活性剂为二烷基咔唑鎓盐、氨丙基异丁基多面体低聚倍半硅氧烷、十六烷基氯化吡啶/a-环糊精、脱氧苯偶姻二甲基十六烷基季铵盐、季铵盐4-(4-金刚烷基苯氧基)-1丁基胺、溴化烷基咔唑鎓盐、二烷基咔唑鎓盐、喹啉鎓盐、多面体低聚倍半硅氧烷的一种过多种。
进一步的,所述聚己内酯基聚氨酯弹性体为NCO/OH摩尔比为1.05:1的二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯和聚己内酯二元醇在超声20kHz条件下加入总重0.08%分数的辛酸亚锡,在60℃下搅拌反应24h, 固化交联得到的聚合物弹性体。
进一步的,所述的发泡剂为4,4'-氧代双苯磺酰肼、二氯四氟乙烷、一氯三氟丙烯的一种或多种。
进一步的所述氯醋树脂为氯乙烯-醋酸乙烯酯共聚物,醋酸乙烯酯含量为10%。
进一步的,所述布基为克重155~175g/m2、厚度0.55~0.65mm、幅宽1.55~1.65m、经向拉伸负荷≥300N、纬向拉伸负荷≥300N、经向断裂伸长率≥10%、纬向断裂伸长率≥15%、经向撕裂负荷≥20N、纬向撕裂负荷≥20N、经向和纬向热收缩率≥3%的机织单面起绒斜纹布。
实施例2
一种清洁生态可降解PVC装饰人造革,由下列重量份数的原料制成:PVC树脂粉100份、氯醋树脂30份、二乙酰环氧大豆油酸甘油酯36份、聚己内酯基聚氨酯弹性体15份、发泡剂1份、环氧大豆油24份、有机改性黏土22份、润滑剂1份、硅酮母粒1份、稳定剂1份、颜料1份。
一种清洁生态可降解PVC装饰人造革的制备,其包括以下步骤:
(1)将经过称量的PVC树脂粉、氯醋树脂、聚己内酯基聚氨酯弹性体、润滑剂、硅酮母粒、稳定剂,投入到高速捏合机中,随后加入环氧大豆油,搅拌5~10min,再加入有二乙酰环氧大豆油酸甘油酯,再搅拌10min后,加入、润滑剂、颜料,再搅拌3min,将有机改性黏土和发泡剂加入,并搅拌5min。当混合温度至90~100℃时,达到混合料握在手心中不湿润,柔软均匀,有弹性,即可放料,得初混料;
(2)将初混料放入密炼机中,放下浮压锤,密炼4min,待电流平稳、料团密炼至,料团不带生粉,送入将物料送至炼塑机;
(3)炼塑在初炼塑机上打包翻卷几次送至终炼塑机,炼塑至料卷发糯、半透明无亮光时,切成直径为中10~15cm的料卷或开成料片,用传送带送至压延机,得到压延浆料;
(4)压延浆料贴合经预热开幅处理的布基,平整地引入中、下辊间,把经预热的面层膜在贴合部分和上述制得的半成品革再贴合后进入烘箱塑化,220℃下发泡,经冷却定型后,得到清洁生态可降解PVC装饰人造革。
进一步的,所述炼塑工艺条件为初炼辊温175℃,辊距5mm,终炼辊温180℃,辊距3mm,使中下辊间余料直径不超过中3cm。
进一步的,所述的有机改性黏土为质量分数为20%的均匀黏土悬浮液,与表面活改性剂溶解在反应水和乙醇的混合溶液,在温度为50℃,搅拌1h,后经过滤得到的有机改性黏土;所述的表面改性活性剂为二烷基咔唑鎓盐、氨丙基异丁基多面体低聚倍半硅氧烷、十六烷基氯化吡啶/a-环糊精、脱氧苯偶姻二甲基十六烷基季铵盐、季铵盐4-(4-金刚烷基苯氧基)-1丁基胺、溴化烷基咔唑鎓盐、二烷基咔唑鎓盐、喹啉鎓盐、多面体低聚倍半硅氧烷的一种过多种。
进一步的,所述聚己内酯基聚氨酯弹性体为NCO/OH摩尔比为1.05:1的二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯和聚己内酯二元醇在超声20kHz条件下加入总重0.08%分数的辛酸亚锡,在60℃下搅拌反应24h, 固化交联得到的聚合物弹性体。
进一步的,所述的发泡剂为4,4'-氧代双苯磺酰肼、二氯四氟乙烷、一氯三氟丙烯的一种或多种。
进一步的,所述布基为克重155~175g/m2、厚度0.55~0.65mm、幅宽1.55~1.65m、经向拉伸负荷≥300N、纬向拉伸负荷≥300N、经向断裂伸长率≥10%、纬向断裂伸长率≥15%、经向撕裂负荷≥20N、纬向撕裂负荷≥20N、经向和纬向热收缩率≥3%的机织单面起绒斜纹布。
进一步的,所述氯醋树脂为氯乙烯-醋酸乙烯酯共聚物,醋酸乙烯酯含量为14%。
对比例1
本对比例与实施例2相比,在原料称取步骤中,省去氯醋树脂成分,除此外的方法步骤均相同。
对比例2
本对比例与实施例2相比,在原料称取步骤中,省去聚己内酯基聚氨酯弹性体成分,除此外的方法步骤均相同。
对比例3
本对比例与实施例2相比,在原料称取步骤中,省去有机改性黏土成分,除此外的方法步骤均相同。
表1实施例和对比例的人造革性能对比
注:堆肥生物降解实验:将上述制得各组鱼网线按照GB/T 19277.2-2013进行堆肥降解实验,实验过程中要严格控制温度、水分,且试验时间为50天。
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 (8)
1.一种清洁生态可降解PVC装饰人造革,其特征在于,该人造革利用生态PVC浆料采用压延法制备而成,所述生态PVC浆料按重量份计由以下成分制成:PVC树脂粉50~100份、氯醋树脂20~30份、二乙酰环氧大豆油酸甘油酯32~45份、聚己内酯基聚氨酯弹性体10~25份、发泡剂1~2份、环氧大豆油20~24份、有机改性黏土15~22份、润滑剂1~2份、硅酮母粒1~2份、稳定剂1~2份、颜料1~2份。
2.一种权利要求1所述的一种清洁生态可降解PVC装饰人造革的制备方法,其特征在于,制备过程包括以下步骤:
(1)将经过称量的PVC树脂粉、氯醋树脂、聚己内酯基聚氨酯弹性体、润滑剂、硅酮母粒、稳定剂,投入到高速捏合机中,随后加入环氧大豆油,搅拌5~10min,再加入二乙酰环氧大豆油酸甘油酯,再搅拌5~10min后,加入颜料,再搅拌3min,将有机改性黏土和发泡剂加入,并搅拌3~5min。当混合温度至90~100℃时,达到混合料握在手心中不湿润,柔软均匀,有弹性,即可放料,得初混料。
(2)将初混料放入密炼机中,放下浮压锤,密炼3.5~4min,待电流平稳、料团密炼至料团不带生粉,送入将物料送至炼塑机;
(3)炼塑在初炼塑机上打包翻卷几次送至终炼塑机,炼塑至料卷发糯、半透明无亮光时,切成直径为中10~15cm的料卷或开成料片,用传送带送至压延机,得到压延浆料;
(4)压延浆料贴合经预热开幅处理的布基,平整地引入中、下辊间,把经预热的面层膜在贴合部分和上述制得的半成品革再贴合后进入烘箱塑化,220℃下发泡,经冷却定型后,得到清洁生态可降解PVC装饰人造革。
3.根据权利要求2所述的一种清洁生态可降解PVC装饰人造革的制备方法,其特征在于,所述炼塑工艺条件为初炼辊温165~175℃,辊距5~7mm,终炼辊温170~180℃,辊距3~5mm,使中下辊间余料直径不超过中2~3cm。
4.根据权利要求2所述的一种清洁生态可降解PVC装饰人造革的制备方法,其特征在于,第1步所述的有机改性黏土为质量分数为20%的均匀黏土悬浮液,与表面活改性性剂溶解在反应水和乙醇的混合溶液,在温度为25~80℃,搅拌1h,后经过滤得到的有机改性黏土;所述的表面改性活性剂为二烷基咔唑鎓盐、氨丙基异丁基多面体低聚倍半硅氧烷、十六烷基氯化吡啶/a-环糊精、脱氧苯偶姻二甲基十六烷基季铵盐、季铵盐4-(4-金刚烷基苯氧基)-1丁基胺、溴化烷基咔唑鎓盐、二烷基咔唑鎓盐、喹啉鎓盐、多面体低聚倍半硅氧烷的一种过多种。
5.根据权利要求2所述的一种清洁生态可降解PVC装饰人造革的制备方法,其特征在于,所述聚己内酯基聚氨酯弹性体为NCO/OH摩尔比为1.05:1的二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯和聚己内酯二元醇在超声20kHz条件下加入总重0.01~0.08%分数的辛酸亚锡,在60℃下搅拌反应24h,固化交联得到的聚合物弹性体。
6.根据权利要求2所述的一种清洁生态可降解PVC装饰人造革的制备方法,其特征在于,所述的发泡剂为4,4'-氧代双苯磺酰肼、二氯四氟乙烷、一氯三氟丙烯的一种或多种。
7.根据权利要求2所述的一种清洁生态可降解PVC装饰人造革的制备方法,其特征在于,所述氯醋树脂为氯乙烯-醋酸乙烯酯共聚物,醋酸乙烯酯含量为5%~14%。
8.根据权利要求2所述的一种清洁生态可降解PVC装饰人造革的制备方法,其特征在于,所述布基为克重155~175g/m2、厚度0.55~0.65mm、幅宽1.55~1.65m、经向拉伸负荷≥300N、纬向拉伸负荷≥300N、经向断裂伸长率≥10%、纬向断裂伸长率≥15%、经向撕裂负荷≥20N、纬向撕裂负荷≥20N、经向和纬向热收缩率≥3%的机织单面起绒斜纹布。
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