CN106436304B - 一种丝胶有机酸整理液及其对棉织物的亲肤整理方法 - Google Patents
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Abstract
本发明公开了一种丝胶有机酸整理液及其对棉织物的亲肤整理方法，涉及纺织技术领域。采用有机酸如柠檬酸、丁烷四羧酸等对蚕丝进行脱胶，得到有机酸脱胶液，所得的脱胶液不需处理，直接用于纺织品的抗皱整理。通过加入复合催化剂乙二胺四乙酸钠和纳米TiO2催化有机酸与棉织物、丝胶的交联反应，催化剂的用量大幅减少，大大降低了环境污染，成本低。通过有机酸和丝胶蛋白共同整理棉织物，不仅可解决棉织物抗皱和防缩性能差的关键问题，同时可赋予棉织物蛋白质化的亲肤属性。
Description
技术领域
本发明涉及纺织领域，特别涉及丝胶有机酸整理液及其对棉织物的亲肤整理方法。
背景技术
棉织物具有柔软、透气、吸湿等优点，广泛应用于服装面料、装饰织物和产业用织物等。然而，由于棉织物在洗涤或穿着过程中经受外力作用时，纤维素分子沿着外力的方向发生一定的形变，基本结构单元相对滑移，羟基在新的位置又会产生重新建立起新的氢键，这种不可逆形变导致棉织物产生大量折皱。为改善棉织物的易折皱性能，常采用交联法对棉织物进行抗皱整理，交联剂与纤维中相邻分子链上的羟基发生反应形成桥联共价结合，从而实现棉织物的抗皱目的。
现有技术中使用含有离子液体、丙烯酰琥珀酸的整理液整理棉织物，其原料价格昂贵，生产成本高；以多元酸整理棉织物，多采用各种有机化合物、表面活性剂及含磷催化剂，对环境有污染；专利CN201410784081.9采用浓度为17-68g/L的乙二胺四乙酸钠盐为无磷催化剂对棉织物进行多元羧酸抗皱整理。单独使用乙二胺四乙酸钠盐作为催化剂，其催化剂用量较大，催化效率较低。
发明内容
针对现有技术中存在的问题，本发明提供一种丝胶有机酸整理液及其对棉织物的亲肤整理方法。通过有机酸和丝胶蛋白共同整理棉织物，解决了现有棉织物改性技术中的环保性、亲肤等舒适功能差的技术难题，极大改善和提高了棉织物的抗皱、防缩性能，赋予棉织物蛋白质化的亲肤属性。
本发明具体的技术方案如下：
一种丝胶有机酸整理液，所述整理液主要由乙二胺四乙酸钠、纳米TiO2和有机酸蚕丝脱胶液组成，其中，乙二胺四乙酸钠的浓度为5～20g/L，进一步为10～15g/L；纳米TiO2的浓度为0.2～1.0g/L，进一步为0.4～0.8g/L。
其中，纳米TiO2的粒径为10～100nm，优选为20～50nm。
优选的，所述有机酸蚕丝脱胶液为将蚕丝或蚕丝织物进行有机酸脱胶处理得到。本发明的蚕丝脱胶液可采用现有技术中的常规步骤进行制备。作为优选的一种实施方式，蚕丝脱胶步骤中添加有机酸的浓度为10～60g/L，优选为30～50g/L；进一步优选的，还可添加适当渗透剂以提高蚕丝脱胶的效果。优选添加渗透剂为脂肪醇聚氧乙烯醚(JFC)，其浓度为2～5g/L，进一步优选为3～4g/L；
在本发明中，所述脱胶的温度为90～98℃；所述脱胶的时间为15～60min，优选为20～40min；
在本发明中，所述脱胶的浴比为1:10～40，优选为1:10～20。
进一步的，本发明所述有机酸优选为柠檬酸、丁烷四羧酸和马来酸酐中的一种或多种的任意比例。
上述丝胶有机酸整理液的制备方法为：将以上有机酸蚕丝脱胶液与乙二胺四乙酸钠盐、纳米TiO2混合，制备得到含有5～20g/L乙二胺四乙酸钠、0.2-1.0g/L纳米TiO2的丝胶有机酸整理液。
本发明还提供一种上述丝胶有机酸整理液对棉织物的亲肤整理方法，包括以下步骤：将棉织物浸入丝胶有机整理液中，二浸二轧，高温焙烘后，水洗烘干。
所述二浸二轧步骤中，压力为0.5～1.5kg/cm2，优选为0.8～1.2kg/cm2，进一步为0.9kg/cm2；带液率为70～90％，优选为75～85％。
所述高温焙烘的具体步骤为，先进行预烘，预烘温度为70～90℃，优选为80℃。预烘时间为3～10min，进一步为4～7min。所述预烘后停滞至少1min后，再在160～165℃下焙烘2～5min。
将高温焙烘后的棉织物水洗至中性后，烘干，烘干温度为25～30℃。
本发明还包括上述整理方法得到的亲肤棉织物，所述棉织物的纤维表面具有丝胶蛋白和有机酸的交联物质。优选的，所述有机酸为柠檬酸、丁烷四羧酸和马来酸酐中的一种或多种。
本发明技术方案的原理是：棉织物的羟基、丝胶蛋白的氨基、羧基和羟基，在乙二胺四乙酸四钠和纳米TiO2复合催化下，可与有机酸发生交联反应。有机酸与棉纤维大分子间产生交联作用，提高棉织物的抗皱防缩性能；有机酸与丝胶蛋白交联，固着在棉织物表面，增强棉纤维的抗皱性的同时，还能赋予棉织物蛋白质化的亲肤功能。纳米TiO2具有表面积大，表面活性中心多，吸附性强，具有高效催化性，与乙二胺四乙酸四钠催化剂一起使用具有协同作用，可促使整理剂和纤维素大分子交联，减少催化剂的使用量，提高催化效率。
与现有技术相比，本发明的优势在于：
1、将有机酸脱胶的丝胶蛋白脱胶液用于棉织物的整理，其丝胶蛋白脱胶液中的丝胶蛋白和有机酸，无需提取可直接用于棉织物的整理，其来源丰富，成本较低，制备工艺简单、易实现，因此，该方法具有可工业化生产和应用附加价值高的特点。
2、通过将无磷催化剂乙二胺四乙酸四钠与纳米TiO2复配作为催化剂，不仅可以将绿色交联剂柠檬酸、丁烷四羧酸、马来酸酐与棉纤维通过交联反应联结起来，而且通过纳米TiO2的协同作用，可显著减少乙二胺四乙酸四钠的用量，有利于环保。与单独使用纳米TiO2催化剂相比，乙二胺四乙酸四钠和纳米TiO2复合催化，提高棉织物抗皱防缩性能的同时，更能提高其强力保留率。同时制得丝胶有机酸整理液体系为环保生态型，不含甲醛等有毒有害物质。
3、通过将丝胶蛋白与有机酸的交联作用，使丝胶交联固着在棉纤维上，增强棉纤维的抗皱性的同时，还能赋予棉织物蛋白质化的亲肤功能。
具体实施方式
下面将结合本发明中的实施例，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做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
一、蚕丝有机酸脱胶：将桑(柞)蚕丝或其织物进行丁烷四羧酸脱胶处理，脱胶用有机酸10g/L，JFC 5g/L，脱胶温度98℃，时间60min，浴比1:10，获得蚕丝脱胶液。
二、整理液制备：将以上蚕丝脱胶液中加入乙二胺四乙酸钠盐、纳米TiO2，制备得到浓度为5g/L乙二胺四乙酸钠和0.2g/L纳米TiO2的丝胶有机酸整理液。
三、棉织物整理：将棉织物浸入步骤二中的丝胶有机酸整理液中，二浸二轧，压力为0.5kg/cm2，带液率为90％，在温度为70℃的鼓风烘箱中预烘10min，停滞1min，然后在温度为160℃下焙烘2min，水洗至中性后，在温度为25℃的低温下烘干后即得本发明亲肤棉织物。
实施例2：
一、蚕丝有机酸脱胶：将桑(柞)蚕丝或其织物进行马来酸酐脱胶处理，脱胶用有机酸40g/L，JFC 3g/L，脱胶温度95℃，时间30min，浴比1:40，获得蚕丝脱胶液。
二、整理液制备：将以上蚕丝脱胶液中加入乙二胺四乙酸钠盐、纳米TiO2，制备得到浓度为10g/L乙二胺四乙酸钠和0.5g/L纳米TiO2的丝胶有机酸整理液。
三、棉织物整理：将棉织物浸入步骤二中的丝胶有机酸整理液中，二浸二轧，压力为0.9kg/cm2，带液率为80％，在温度为85℃的鼓风烘箱中预烘5min，停滞1min，然后在温度为165℃下焙烘4min，水洗至中性后，在温度为25℃的低温下烘干后即得本发明亲肤棉织物。
实施例3：
一、蚕丝有机酸脱胶：将桑(柞)蚕丝或其织物进行柠檬酸脱胶处理，脱胶用有机酸60g/L，JFC 2g/L，脱胶温度90℃，时间15min，浴比1:20，获得蚕丝脱胶液。
二、整理液制备：将以上蚕丝脱胶液中加入乙二胺四乙酸钠盐、纳米TiO2，制备得到浓度为20g/L乙二胺四乙酸钠和1.0g/L纳米TiO2的丝胶有机酸整理液。
三、棉织物整理：将棉织物浸入步骤二中的丝胶有机酸整理液中，二浸二轧，压力为1.5kg/cm2，带液率为70％，在温度为75℃的鼓风烘箱中预烘5min，停滞1min，然后在温度为165℃下焙烘5min，水洗至中性后，在温度为30℃的低温下烘干后即得本发明亲肤棉织物。
对比例1：
一、蚕丝有机酸脱胶：将桑(柞)蚕丝或其织物进行柠檬酸脱胶处理，脱胶用有机酸60g/L，JFC 2g/L，脱胶温度90℃，时间15min，浴比1:20，获得蚕丝脱胶液。
二、整理液制备：将以上蚕丝脱胶液中加入乙二胺四乙酸钠盐，制备得到浓度为20g/L乙二胺四乙酸钠的丝胶有机酸整理液。
三、棉织物整理：将棉织物浸入步骤二中的丝胶有机酸整理液中，二浸二轧，压力为1.5kg/cm2，带液率为70％，在温度为75℃的鼓风烘箱中预烘5min，停滞1min，然后在温度为165℃下焙烘5min，水洗至中性后，在温度为30℃的低温下烘干后即得本发明亲肤棉织物。
对比例2：
一、蚕丝有机酸脱胶：将桑(柞)蚕丝或其织物进行柠檬酸脱胶处理，脱胶用有机酸60g/L，JFC 2g/L，脱胶温度90℃，时间15min，浴比1:20，获得蚕丝脱胶液。
二、整理液制备：将以上蚕丝脱胶液中加入纳米TiO2，制备得到浓度为1.0g/L的纳米TiO2丝胶有机酸整理液。
三、棉织物整理：将棉织物浸入步骤二中的丝胶有机酸整理液中，二浸二轧，压力为1.5kg/cm2，带液率为70％，在温度为75℃的鼓风烘箱中预烘5min，停滞1min，然后在温度为165℃下焙烘5min，水洗至中性后，在温度为30℃的低温下烘干后即得本发明亲肤棉织物。
取桑蚕丝柠檬酸脱胶液，脱胶液中丝胶蛋白浓度为3.0g/L,按照上述实施例进行棉织物丝胶有机酸整理，将整理前后的棉织物试样在标准状况下进行调湿平衡,结果如表1所示：
表1桑蚕丝脱胶液整理棉织物的性能
注：水洗尺寸变化率测定：参照GB/T 8630--2002(纺织品洗涤和干燥后尺寸变化的测定)标准测定；
经向水洗尺寸变化率＝(最终长度-初始长度)/初始长度×100％；
纬向水洗尺寸变化率＝(最终宽度一初始宽度)/初始宽度×100％。
白度测定：将样品折叠8层，在白度计上测量3次，取平均值。
取柞蚕丝柠檬酸脱胶液，脱胶液中丝胶蛋白浓度为3.2g/L,按照上述实施例进行棉织物丝胶有机酸整理，结果如表2所示：
表2柞蚕丝脱胶液整理棉织物的性能
由表1和表2可以看出，本发明采用有机酸如柠檬酸、丁烷四羧酸等对蚕丝进行脱胶，得到有机酸脱胶液，所得的脱胶液不需处理，直接用于纺织品的抗皱整理。通过加入复合催化剂乙二胺四乙酸钠和纳米TiO2催化有机酸与棉织物、丝胶的交联反应，催化剂的用量大幅减少，大大降低了环境污染，成本低。通过有机酸和丝胶蛋白共同整理棉织物，不仅可解决棉织物抗皱和防缩性能差的关键问题，同时可赋予棉织物蛋白质化的亲肤属性，强力保留率高。
上述实施方式旨在举例说明本发明可为本领域专业技术人员实现或使用，对上述实施方式进行修改对本领域的专业技术人员来说将是显而易见的，故本发明包括但不限于上述实施方式，任何符合本权利要求书或说明书描述，符合与本文所公开的原理和新颖性、创造性特点的方法、工艺、产品，均落入本发明的保护范围之内。
Claims (4)
1.一种丝胶有机酸整理液，其特征在于，所述整理液由乙二胺四乙酸钠、纳米TiO2 和有机酸蚕丝脱胶液组成，其中，乙二胺四乙酸钠的浓度为5～20g/L，纳米TiO2 的浓度为0.2～1.0g/L；
所述有机酸蚕丝脱胶液为将蚕丝或蚕丝织物进行有机酸脱胶处理制备得到；其中，脱胶用有机酸的浓度为10～60g/L，脱胶用脂肪醇聚氧乙烯醚浓度为2～5g/L，脱胶温度为90～98℃，时间为15～60min；脱胶浴比为1:10～40；
所述有机酸为柠檬酸、丁烷四羧酸和马来酸酐中的一种或多种任意比例的混合物。
2.采用权利要求1所述丝胶有机酸整理液对棉织物的亲肤整理方法，其特征在于，包括以下步骤：
将棉织物浸入所述丝胶有机酸整理液中，二浸二轧，压力为0.5～1.5kg/cm2 ，带液率为70～90％，高温焙烘后，水洗烘干。
3.根据权利要求2所述的亲肤整理方法，其特征在于，所述高温焙烘具体为，先在70～90℃下预烘3～10min，停滞至少1min后，在160～165℃下焙烘2～5min。
4.如权利要求2或3所述整理方法得到的亲肤棉织物，其特征在于，所述棉织物的纤维表面具有丝胶蛋白和有机酸的交联物质。
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