CN109537305A - 一种具有抑菌功能的超细纤维绒面人工皮革及其制备方法 - Google Patents
一种具有抑菌功能的超细纤维绒面人工皮革及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种具有抑菌功能的超细纤维绒面人工皮革及其制备方法,本发明使用复合配方,以吡硫锌为主剂,配合使用纳米氧化锌助剂,大大降低了复合配方的MIC值,即使用较少的剂量即可达到较高的抑菌效果,使此项抑菌技术可以在超细纤维人工皮革中得到应用。
Description
(一)技术领域
本发明涉及人工皮革领域,具体涉及一种具有抑菌功能的超细纤维绒面人工皮革及其制备方法。
(二)背景技术
目前,人工皮革合成革正向功能化高端方向发展。产品品种多样,应用领域细分,满足客户要求更全面,使用性能更突出,这也是市场对人工皮革合成革企业提出的新标准。其中抑菌防霉功能化是行业发展前景相对较好的一个方向,相应抑菌剂的研究和应用将成为技术领域的研究热点,但是目前的抑菌防霉人工皮革技术落后,大多数的抑菌防霉处理是在制造工艺中添加的酚类、醛类等普通工业防霉剂,目的只是为了保证材料在较短时间内不长霉,即所谓“被动抑菌处理”;抑菌材料作为一种新兴功能材料,除了能保证材料本身不受有害微生物侵蚀,还能持久地抵御外来微生物的侵袭,保护使用者的人身安全,即所谓“主动抑菌处理”。
(三)发明内容
为实现主动抑菌的目标,研究人员进行了大量的实验,成功实现了保持原来抑菌防霉效果的同时提高了人工皮革的主动抑菌性能。
本发明的技术方案如下:
一种具有抑菌功能的超细纤维绒面人工皮革,按如下方法制备得到:
将超细纤维绒面人工皮革基布在含有纳米氧化锌、吡硫锌和粘合剂的处理液中进行含浸处理,之后经干热处理,即得具有抑菌功能的超细纤维人工皮革成品;
所述处理液中纳米氧化锌、吡硫锌、粘合剂的浓度分别为10-180g/L、10-20g/L、4-8g/L;
所述纳米氧化锌、吡硫锌、粘合剂可通过常规途径商购获得;
所述粘合剂为聚丙烯酸酯粘合剂;
所述吡硫锌的粒径在50-1000nm;
所述纳米氧化锌的粒径在20-500nm;
所述干热处理的温度为130℃(即上述粘合剂的交联温度),时间为1-5min。
本发明中,所述超细纤维绒面人工皮革基布的制备方法为:
(a)以海岛纤维为原料制备坯布;
所述海岛纤维可选用定岛型或不定岛型海岛纤维,所述海岛纤维的纤度为1D-3D,岛成分为涤纶或尼龙,海成分为涤纶;
所述坯布由海岛纤维经过开包、铺网、针刺/水刺固结的工艺制得,所得坯布的表观密度为200-500g/m2;
(b)将步骤(a)所得坯布进行热收缩工艺处理;
具体的,所述热收缩工艺处理的方法为:将坯布浸没于95℃热水中保持20min即完成热收缩工艺处理;
该步所得半成品的表观密度为240-700g/m2;
(c)将步骤(b)所得半成品进行聚氨酯含浸工艺处理;
所述聚氨酯含浸工艺处理包括第一含浸工艺和第二含浸工艺;
所述第一含浸工艺,浸液含有17-25wt.%的水溶性聚酯,干燥温度100-150℃;
所述第二含浸工艺,浸液含有10-30wt.%的水性聚氨酯,干燥温度100-150℃;
(d)对步骤(c)所得半成品依次进行水洗、开纤、染色、磨皮工艺处理,得到所述超细纤维绒面人工皮革基布;
具体的,所述水洗工艺,即用热水(70~95℃)洗涤去除水溶性聚酯,通常用热水冲洗5-30min即可;
所述开纤工艺,以2-20g/L氢氧化钠的水溶液为开纤液,开纤处理的温度为90-130℃,时间通常为15-45min,通过开纤可去除海岛纤维的海部分,留下岛部分的纤维束;
所述染色工艺具体例如液流染色工艺,根据纤维的种类不同可选用分散染料、酸性染料、直接染料等染料进行染色,染色处理在液流染色机中进行,染色的条件可按照原料的不同进行调整;
所述磨皮工艺在磨皮机上进行,使用80-600目的纸皮砂带,车速为2-10米/分钟。
本发明的有益效果在于:
本发明使用吡硫锌和氧化锌作为抑菌剂来实现人工皮革的抑菌功能。吡硫锌作为抑菌剂曾广泛的在日化用品中使用,但是由于其可能导致人类角质形成细胞和黑素细胞的热休克并引起DNA损伤,因此其使用量不能超过1.5%。氧化锌作为无机抑菌剂的代表也广泛的在涂料行业,建材行业得到广泛的利用。但是,上述的两种抑菌剂的MIC(最小发育阻止浓度)较高,所以在单独使用的情况下,其使用量较高,应用在超细纤维人工皮革的后处理时,会造成人工皮革的弹性变差,柔软度变差等情况。
本发明使用复合配方,以吡硫锌为主剂,配合使用纳米氧化锌助剂,大大降低了复合配方的MIC值(即使用较少的剂量即可达到较高的抑菌效果),使此项抑菌技术可以在超细纤维人工皮革中得到应用。
(四)具体实施方式
下面通过具体实施例对本发明作进一步说明,但本发明的保护范围并不仅限于此。
实施例1
涤纶超细纤维基布,使用纤维为2D 37岛定岛,海成分为涤纶,岛成分为涤纶,长度为51mm,海/岛比例为30/70。上述纤维经过铺网,针刺制备基布。基布的表观密度为300g/m2。此基布经过热予缩后的表观密度为350g/m2。提高表观密度后进行水性聚氨酯树脂的含浸处理,含浸处理分为两次含浸,第一次浸液为浓度在20%的水溶性聚酯,干燥温度130℃;第二次浸液为浓度在30%的水性树脂,干燥温度130℃,控制带液量使坯布的水性树脂的增重量在25%。之后经温水洗工艺去除第一次含浸的水溶性聚酯。之后经水洗工艺去除第一次含浸的水溶性聚酯后,使用NaOH水溶液进行开纤处理,开纤处理时的NaOH水溶液浓度为10g/L,开纤处理的温度为130度,时间为30min。经过开纤处理的基布经过染色处理(染色处方与条件:使用分散染料黄AM-2R,0.52%;红AM-SLR 0.092%;蓝AM-SLR 0.31%。染色浴比1∶15。染色条件,初始水温35度,依次将基布,助剂,染料添加入液流染色机中,以1度/min的速度升温至130度,保温30分钟后降温,降温至80度后添加还原清洗剂,经20mins还原清洗后排液,室温水洗后取出干燥),两次以上定量式磨皮处理(磨皮条件:初次粗磨采用80目纸皮砂带,二次细磨采用240目纸皮砂带,两次磨皮的车速均为4m/min)之后形成半成品基布。对此半成品基布进行抑菌后加工时,使用氧化锌10g/L,吡硫锌10g/L,粘合剂5g/L的混合溶液作为含浸液,基布在此含浸浴中处理后(含浸处理时,基布带液率大于40%),进行热干燥处理,热处理的温度为130度,处理时间为2分钟。
实施例2
涤纶超细纤维基布,使用纤维为2D 37岛定岛,海成分为涤纶,岛成分为涤纶,长度为51mm,海/岛比例为30/70。上述纤维经过铺网,针刺制备基布。基布的表观密度为300g/m2。此基布经过热予缩后的表观密度为350g/m2。提高表观密度后进行水性聚氨酯树脂的含浸处理,含浸处理分为两次含浸,第一次浸液为浓度在20%的水溶性聚酯,干燥温度130℃;第二次浸液为浓度在30%的水性树脂,干燥温度130℃,控制带液量使坯布的水性树脂的增重量在25%。之后经温水洗工艺去除第一次含浸的水溶性聚酯。之后经水洗工艺去除第一次含浸的水溶性聚酯后,使用NaOH水溶液进行开纤处理,开纤处理时的NaOH水溶液浓度为10g/L,开纤处理的温度为130度,时间为30min。经过开纤处理的基布经过染色处理(染色处方与条件:使用分散染料黄AM-2R,0.52%;红AM-SLR 0.092%;蓝AM-SLR 0.31%。染色浴比1∶15。染色条件,初始水温35度,依次将基布,助剂,染料添加入液流染色机中,以1度/min的速度升温至130度,保温30分钟后降温,降温至80度后添加还原清洗剂,经20mins还原清洗后排液,室温水洗后取出干燥),两次以上定量式磨皮处理(磨皮条件:初次粗磨采用100目纸皮砂带,二次细磨采用400目纸皮砂带,两次磨皮的车速均为2m/min)之后形成半成品基布。对此半成品基布进行抑菌后加工时,使用氧化锌50g/L,吡硫锌10g/L,粘合剂5g/L的混合溶液作为含浸液,基布在此含浸浴中处理后(含浸处理时,基布带液率大于40%),进行热干燥处理,热处理的温度为130度,处理时间为3分钟。
实施例3
尼龙超细纤维基布,使用纤维为3D 17岛定岛,海成分为涤纶,岛成分为尼龙,长度为51mm,海/岛比例为35/65。上述纤维经过铺网,针刺制备基布。基布的表观密度为400g/m2。此基布经过热予缩后的表观密度为470g/m2。提高表观密度后进行水性聚氨酯树脂的含浸处理,含浸处理分为两次含浸,第一次浸液为浓度在20%的水溶性聚酯,干燥温度150℃;第二次浸液为浓度在30%的水性树脂,干燥温度130℃,控制带液量使坯布的水性树脂的增重量在25%。之后经温水洗工艺去除第一次含浸的水溶性聚酯。之后经水洗工艺去除第一次含浸的水溶性聚酯后,使用NaOH水溶液进行开纤处理,开纤处理时的NaOH水溶液浓度为10g/L,开纤处理的温度为105度,时间为30min。经过开纤处理的基布经过染色处理(染色处方与条件:使用酸性染料黄N5G,0.3%;红NBR 0.1%;蓝NR 0.4%。染色浴比1:15。染色条件,初始水温35度,依次将基布,助剂,染料添加入液流染色机中,以1度/min的速度升温至130度,保温30分钟后降温,室温水洗后取出干燥),两次以上定量式磨皮处理(磨皮条件:初次粗磨采用100目纸皮砂带,二次细磨采用400目纸皮砂带,两次磨皮的车速均为5m/min)之后形成半成品基布。对此半成品基布进行抑菌后加工时,使用氧化锌150g/L,吡硫锌20g/L,粘合剂8g/L的混合溶液作为含浸液,基布在此含浸浴中处理后(含浸处理时,基布带液率大于40%),进行热干燥处理,热处理的温度为130度,处理时间为4分钟。
实施例4
尼龙超细纤维基布,使用纤维为3D 17岛定岛,海成分为涤纶,岛成分为尼龙,长度为51mm,海/岛比例为35/65。上述纤维经过铺网,针刺制备基布。基布的表观密度为400g/m2。此基布经过热予缩后的表观密度为470g/m2。提高表观密度后进行水性聚氨酯树脂的含浸处理,含浸处理分为两次含浸,第一次浸液为浓度在20%的水溶性聚酯,干燥温度150℃;第二次浸液为浓度在30%的水性树脂,干燥温度130℃,控制带液量使坯布的水性树脂的增重量在25%。之后经温水洗工艺去除第一次含浸的水溶性聚酯。之后经水洗工艺去除第一次含浸的水溶性聚酯后,使用NaOH水溶液进行开纤处理,开纤处理时的NaOH水溶液浓度为10g/L,开纤处理的温度为105度,时间为30min。经过开纤处理的基布经过染色处理(染色处方与条件:使用酸性染料黄N5G,0.3%;红NBR 0.1%;蓝NR 0.4%。染色浴比1:15。染色条件,初始水温35度,依次将基布,助剂,染料添加入液流染色机中,以1度/min的速度升温至130度,保温30分钟后降温,室温水洗后取出干燥),两次以上定量式磨皮处理(磨皮条件:初次粗磨采用100目纸皮砂带,二次细磨采用600目纸皮砂带,两次磨皮的车速均为3m/min)之后形成半成品基布。对此半成品基布进行抑菌后加工时,使用氧化锌150g/L,吡硫锌10g/L,粘合剂8g/L的混合溶液作为含浸液,基布在此含浸浴中处理后(含浸处理时,基布带液率大于40%),进行热干燥处理,热处理的温度为130度,处理时间为4分钟。
实施例5
尼龙超细纤维基布,使用纤维为3D 17岛定岛,海成分为涤纶,岛成分为尼龙,长度为51mm,海/岛比例为35/65。上述纤维经过铺网,针刺制备基布。基布的表观密度为200g/m2。此基布经过热予缩后的表观密度为230g/m2。提高表观密度后进行水性聚氨酯树脂的含浸处理,含浸处理分为两次含浸,第一次浸液为浓度在10%的水溶性聚酯,干燥温度100℃;第二次浸液为浓度在15%的水性树脂,干燥温度150℃,控制带液量使坯布的水性树脂的增重量在20%。之后经温水洗工艺去除第一次含浸的水溶性聚酯。之后经水洗工艺去除第一次含浸的水溶性聚酯后,使用NaOH水溶液进行开纤处理,开纤处理时的NaOH水溶液浓度为10g/L,开纤处理的温度为105度,时间为30min。经过开纤处理的基布经过染色处理(染色处方与条件:使用酸性染料黄N5G,0.3%;红NBR 0.1%;蓝NR 0.4%。染色浴比1:15。染色条件,初始水温35度,依次将基布,助剂,染料添加入液流染色机中,以1度/min的速度升温至130度,保温30分钟后降温,室温水洗后取出干燥),两次以上定量式磨皮处理(磨皮条件:初次粗磨采用80目纸皮砂带,二次细磨采用280目纸皮砂带,两次磨皮的车速均为5m/min)之后形成半成品基布。对此半成品基布进行抑菌后加工时,使用氧化锌10g/L,吡硫锌20g/L,粘合剂2g/L的混合溶液作为含浸液,基布在此含浸浴中处理后(含浸处理时,基布带液率大于40%),进行热干燥处理,热处理的温度为130度,处理时间为2分钟。
实施例6
尼龙超细纤维基布,使用纤维为1D 17岛定岛,海成分为涤纶,岛成分为尼龙,长度为51mm,海/岛比例为35/65。上述纤维经过铺网,针刺制备基布。基布的表观密度为300g/m2。此基布经过热予缩后的表观密度为350g/m2。提高表观密度后进行水性聚氨酯树脂的含浸处理,含浸处理分为两次含浸,第一次浸液为浓度在10%的水溶性聚酯,干燥温度100℃;第二次浸液为浓度在15%的水性树脂,干燥温度150℃,控制带液量使坯布的水性树脂的增重量在20%。之后经温水洗工艺去除第一次含浸的水溶性聚酯。之后经水洗工艺去除第一次含浸的水溶性聚酯后,使用NaOH水溶液进行开纤处理,开纤处理时的NaOH水溶液浓度为15g/L,开纤处理的温度为105度,时间为30min。经过开纤处理的基布经过染色处理(染色处方与条件:使用酸性染料黄N5G,0.3%;红NBR 0.1%;蓝NR 0.4%。染色浴比1:15。染色条件,初始水温35度,依次将基布,助剂,染料添加入液流染色机中,以1度/min的速度升温至130度,保温30分钟后降温,室温水洗后取出干燥),两次以上定量式磨皮处理(磨皮条件:初次粗磨采用80目纸皮砂带,二次细磨采用280目纸皮砂带,两次磨皮的车速均为5m/min)之后形成半成品基布。对此半成品基布进行抑菌后加工时,使用氧化锌100g/L,吡硫锌10g/L,粘合剂2g/L的混合溶液作为含浸液,基布在此含浸浴中处理后(含浸处理时,基布带液率大于40%),进行热干燥处理,热处理的温度为130度,处理时间为3分钟。
比较例1
涤纶超细纤维基布,使用纤维为2D 37岛定岛,海成分为涤纶,岛成分为涤纶,长度为51mm,海/岛比例为30/70。上述纤维经过铺网,针刺制备基布。基布的表观密度为300g/m2。此基布经过热予缩后的表观密度为350g/m2。提高表观密度后进行水性聚氨酯树脂的含浸处理,含浸处理分为两次含浸,第一次浸液为浓度在20%的水溶性聚酯,干燥温度130℃;第二次浸液为浓度在30%的水性树脂,干燥温度130℃,控制带液量使坯布的水性树脂的增重量在25%。之后经温水洗工艺去除第一次含浸的水溶性聚酯。之后经水洗工艺去除第一次含浸的水溶性聚酯后,使用NaOH水溶液进行开纤处理,开纤处理时的NaOH水溶液浓度为10g/L,开纤处理的温度为130度,时间为30min。经过开纤处理的基布经过染色处理(染色处方与条件:使用分散染料黄AM-2R,0.52%;红AM-SLR 0.092%;蓝AM-SLR 0.31%。染色浴比1:15。染色条件,初始水温35度,依次将基布,助剂,染料添加入液流染色机中,以1度/min的速度升温至130度,保温30分钟后降温,降温至80度后添加还原清洗剂,经20mins还原清洗后排液,室温水洗后取出干燥),两次以上定量式磨皮处理(磨皮条件:初次粗磨采用80目纸皮砂带,二次细磨采用240目纸皮砂带,两次磨皮的车速均为4m/min)之后形成半成品基布。对此半成品基布进行后加工时,使用粘合剂5g/L的溶液作为含浸液,基布在此含浸浴中处理后(含浸处理时,基布带液率大于40%),进行热干燥处理,热处理的温度为130度,处理时间为3分钟。
比较例2
涤纶超细纤维基布,使用纤维为2D 37岛定岛,海成分为涤纶,岛成分为涤纶,长度为51mm,海/岛比例为30/70。上述纤维经过铺网,针刺制备基布。基布的表观密度为300g/m2。此基布经过热予缩后的表观密度为350g/m2。提高表观密度后进行水性聚氨酯树脂的含浸处理,含浸处理分为两次含浸,第一次浸液为浓度在20%的水溶性聚酯,干燥温度130℃;第二次浸液为浓度在30%的水性树脂,干燥温度130℃,控制带液量使坯布的水性树脂的增重量在25%。之后经温水洗工艺去除第一次含浸的水溶性聚酯。之后经水洗工艺去除第一次含浸的水溶性聚酯后,使用NaOH水溶液进行开纤处理,开纤处理时的NaOH水溶液浓度为10g/L,开纤处理的温度为130度,时间为30min。经过开纤处理的基布经过染色处理(染色处方与条件:使用分散染料黄AM-2R,0.52%;红AM-SLR 0.092%;蓝AM-SLR 0.31%。染色浴比1:15。染色条件,初始水温35度,依次将基布,助剂,染料添加入液流染色机中,以1度/min的速度升温至130度,保温30分钟后降温,降温至80度后添加还原清洗剂,经20mins还原清洗后排液,室温水洗后取出干燥),两次以上定量式磨皮处理(磨皮条件:初次粗磨采用80目纸皮砂带,二次细磨采用240目纸皮砂带,两次磨皮的车速均为10m/min)之后形成半成品基布。对此半成品基布进行后加工时,使用氧化锌10g/L和粘合剂5g/L的溶液作为含浸液,基布在此含浸浴中处理后(含浸处理时,基布带液率大于40%),进行热干燥处理,热处理的温度为130度,处理时间为3分钟。
比较例3
涤纶超细纤维基布,使用纤维为2D 37岛定岛,海成分为涤纶,岛成分为涤纶,长度为51mm,海/岛比例为30/70。上述纤维经过铺网,针刺制备基布。基布的表观密度为300g/m2。此基布经过热予缩后的表观密度为350g/m2。提高表观密度后进行水性聚氨酯树脂的含浸处理,含浸处理分为两次含浸,第一次浸液为浓度在20%的水溶性聚酯,干燥温度130℃;第二次浸液为浓度在30%的水性树脂,干燥温度130℃,控制带液量使坯布的水性树脂的增重量在25%。之后经温水洗工艺去除第一次含浸的水溶性聚酯。之后经水洗工艺去除第一次含浸的水溶性聚酯后,使用NaOH水溶液进行开纤处理,开纤处理时的NaOH水溶液浓度为10g/L,开纤处理的温度为130度,时间为30min。经过开纤处理的基布经过染色处理(染色处方与条件:使用分散染料黄AM-2R,0.52%;红AM-SLR 0.092%;蓝AM-SLR 0.31%。染色浴比1:15。染色条件,初始水温35度,依次将基布,助剂,染料添加入液流染色机中,以1度/min的速度升温至130度,保温30分钟后降温,降温至80度后添加还原清洗剂,经20mins还原清洗后排液,室温水洗后取出干燥),两次以上定量式磨皮处理(磨皮条件:初次粗磨采用80目纸皮砂带,二次细磨采用240目纸皮砂带,两次磨皮的车速均为4m/min)之后形成半成品基布。对此半成品基布进行后加工时,使用吡硫锌10g/L和粘合剂5g/L的溶液作为含浸液,基布在此含浸浴中处理后(含浸处理时,基布带液率大于40%),进行热干燥处理,热处理的温度为130度,处理时间为3分钟。
经上述工艺制备的人工皮革的抑菌性测试依照GB/T20944.3-2008的标准进行检测,实验方法为震荡法。测试结果如表1所示
表1实施例1~6和比较例1~3的抑菌率结果
注1:根据GB/T20944.3-2008的标准合格标准为大肠杆菌抑菌率≧70%,金黄色葡萄球菌抑菌率≧70%,白色念珠菌抑菌率≧60%
Claims (10)
1.一种具有抑菌功能的超细纤维绒面人工皮革,其特征在于,按如下方法制备得到:
将超细纤维绒面人工皮革基布在含有纳米氧化锌、吡硫锌和粘合剂的处理液中进行含浸处理,之后经干热处理,即得具有抑菌功能的超细纤维人工皮革成品;
所述处理液中纳米氧化锌、吡硫锌、粘合剂的浓度分别为10-180g/L、10-20g/L、4-8g/L。
2.如权利要求1所述的具有抑菌功能的超细纤维绒面人工皮革,其特征在于,所述粘合剂为聚丙烯酸酯粘合剂。
3.如权利要求1所述的具有抑菌功能的超细纤维绒面人工皮革,其特征在于,所述超细纤维绒面人工皮革基布的制备方法为:
(a)以海岛纤维为原料制备坯布,所得坯布的表观密度为200-500g/m2;
(b)将步骤(a)所得坯布进行热收缩工艺处理,该步所得半成品的表观密度为240-700g/m2;
(c)将步骤(b)所得半成品进行聚氨酯含浸工艺处理;
所述聚氨酯含浸工艺处理包括第一含浸工艺和第二含浸工艺;
所述第一含浸工艺,浸液含有17-25wt.%的水溶性聚酯,干燥温度100-150℃;
所述第二含浸工艺,浸液含有10-30wt.%的水性聚氨酯,干燥温度100-150℃;
(d)对步骤(c)所得半成品依次进行水洗、开纤、染色、磨皮工艺处理,得到所述超细纤维绒面人工皮革基布。
4.如权利要求3所述的具有抑菌功能的超细纤维绒面人工皮革,其特征在于,步骤(a)中,所述海岛纤维选用定岛型或不定岛型海岛纤维,所述海岛纤维的纤度为1D-3D,岛成分为涤纶或尼龙,海成分为涤纶。
5.如权利要求3所述的具有抑菌功能的超细纤维绒面人工皮革,其特征在于,步骤(b)中,所述热收缩工艺处理的方法为:将坯布浸没于95℃热水中保持20min即完成热收缩工艺处理。
6.如权利要求3所述的具有抑菌功能的超细纤维绒面人工皮革,其特征在于,步骤(d)中,所述水洗工艺,即用70~95℃热水冲洗5-30min。
7.如权利要求3所述的具有抑菌功能的超细纤维绒面人工皮革,其特征在于,步骤(d)中,所述开纤工艺,以2-20g/L氢氧化钠的水溶液为开纤液,开纤处理的温度为90-130℃,时间为15-45min。
8.如权利要求3所述的具有抑菌功能的超细纤维绒面人工皮革,其特征在于,步骤(d)中,所述染色工艺为液流染色工艺,选用分散染料、酸性染料或直接染料进行染色。
9.如权利要求3所述的具有抑菌功能的超细纤维绒面人工皮革,其特征在于,步骤(d)中,所述磨皮工艺在磨皮机上进行,使用80-600目的纸皮砂带,车速为2-10米/分钟。
10.如权利要求1所述的具有抑菌功能的超细纤维绒面人工皮革,其特征在于,所述干热处理的温度为130℃,时间为1-5min。
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