CN100449053C - 多功能纺织前处理剂 - Google Patents
多功能纺织前处理剂 Download PDFInfo
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Abstract
本发明涉及具有漂白、湿润和稳定作用并提供良好清洗和螯合效果的多功能纺织前处理剂。特别是两种不同的烷氧化物和羟基羧酸、磺酸酯以及膦酸酯的组合得到仅要求非常少量增溶剂(即便有)的一体化产品。
Description
本发明涉及具有漂白、湿润和稳定作用并提供良好清洗和螯合效果的多功能纺织前处理剂。
在纺织物料可以染色之前,需要进行适当的预处理,使用传统的例如退浆、脱脂/清洗和漂白操作。使用各种各样的化学品,例如湿润剂、洗涤剂、漂白剂、稳定剂、络合剂或消泡剂。这些前处理的工序常常联合为一个单独的操作,在这种情况下要使用一体化的产品。这些产品(通常为含水组合物)应该为前处理的纺织材料提供良好的可湿润性和为后来的染色提供良好的再湿润性同时泡沫很少,因为在分批喷射设备中泡沫会带来损害。
EP 1 092 804公开的用于纤维材料前处理的含水组合物包含磺酸盐或多元醇和乙氧基化/丙氧基化醇。然而,由于表面活性剂组合物,其缺点是必须使用大量的增溶剂(异丙苯磺酸钠或1,5-甲基戊二醇)。而且,尽管所公开的混合物不非常倾向于发泡,但在许多纺织整理机器中仍然产生太多泡沫。
因此本发明的目标是提供稳定、低粘度、一体化的纺织前处理剂,其具有少的增溶剂要求但仍然满足上面描述的要求。
令人惊奇的是某些烷氧化物或其磷酸酯和其他添加剂(例如螯合剂、稳定剂或消泡剂)的混合物具有所要求的性能。该混合物结合了所有所要求的需求,而任何其他市售产品达不到这一点。
因而本发明提供含水混合物,所述混合物包含:
A)至少一种式(I)的烷氧化物
R1-O-(CH2-CHR2-O)n-CH2-CH2-OH或其磷酸酯,
其中
R1是直链或支链C6-C19烷基,
R2是氢、甲基或乙基,和
n的平均值为3至11;
B)至少一种简单形式的羟基羧酸或低聚羟基羧酸(polyoligohydroxy carboxylic acid)或其盐、或聚丙烯酸酯、或膦酸酯或其盐,或其任何混合物,
C)芳族磺化物或亚磺化物或硫酸化物或其盐,
D)碱土金属盐,
和其他任选添加剂。
作为烷氧化物基础的醇也可由任何所要求的直链醇和支链醇的混合物组成。
在优选的混合物中
R1为直链或支链C8-C15烷基,
R2为氢或甲基,
n的平均值为5至9,
B为柠檬酸或葡萄糖酸钠或α-羟基聚丙烯酸酯或ATMP、HEDP、DTPMPA、EDTMPA或PBTC或这些膦酸酯的盐或其任何混合物,
C为异丙苯磺酸或萘磺酸或其碱金属/铵盐,和
D为氯化镁、硫酸镁、氯化钙或硫酸钙。
所提到的熟知缩写的膦酸酯为:
ATMP =氨基三(亚甲基膦酸),CAS No.6419-19-8;
HEDP =1-羟基亚乙基-1,1-二膦酸,CAS No.2809-21-4;
DTPMPA =二亚乙基三胺五(亚甲基膦酸),CAS No.15827-60-8;
EDTMPA =乙二胺四(亚甲基膦酸),CAS No.1429-50-1;
PBTC =2-膦酸基丁烷-1,24-三羧酸,CAS No.37971-36-1。
发现DTPMPA和ATMP为特别合适。
在同样非常适合的混合物中
R1为直链或支链C12-C15烷基,
R2为氢或甲基,
n的平均值为6或7,和
B为柠檬酸或葡萄糖酸钠或DTPMPA或其任何混合物,
C为异丙苯磺酸或其碱金属/铵盐,和
D为氯化镁或硫酸镁。
以上混合物特别优选
B为柠檬酸和葡萄糖酸钠的混合物,
C为异丙苯磺酸钠,和
D为氯化镁。
显示有利特性的混合物包含
A)两种不同的式(I)的烷氧化物,
A1)其中
R1为支链C6-C14烷基
R2为氢、甲基或乙基,和
n的平均值为3至11;
和
A2)其中
R1为直链或支链C8-C19烷基,
R2为氢、甲基或乙基,和
n的平均值为3至10,
和
B)至少一种简单形式的羟基羧酸或低聚羟基羧酸或其盐、或聚丙烯酸酯、或膦酸酯或其盐,或其任何混合物,
C)芳族磺化物或亚磺化物或硫酸化物或其盐,
D)碱土金属盐,
和也是任选的其他添加剂。
这两种特殊的烷氧化物的组合导致特别良好的清洗、湿润和再湿润特性以及极好的白度。
下面混合物同样显示非常良好的特性,其中
A1)中,R1为支链C8-C12烷基,
R2为氢或甲基,和
n的平均值为5至9;
和
A2)中,R1为直链或支链C10-C17烷基,
R2为氢或甲基,
n的平均值为4至8;
和
B为柠檬酸或葡萄糖酸钠或α-羟基聚丙烯酸酯或ATMP、HEDP、DTPMPA、EDTMPA或PBTC或这些膦酸酯的盐或其任何混合物,
C为异丙苯磺酸或萘磺酸或其碱金属/铵盐,和
D为氯化镁、硫酸镁、氯化钙或硫酸钙。
在特别优选的混合物中
A1)中,R1为支链C10烷基,
R2为氢,和
n的平均值为7;
知
A2)中,R1为直链或支链C12-C15烷基,
R2为氢,
n的平均值为6,
和
B为柠檬酸或葡萄糖酸钠或DTPMPA或其任何混合物,
C为异丙苯磺酸或其碱金属/铵盐,和
D为氯化镁或硫酸镁。
非常特别优选的混合物中
B为柠檬酸和葡萄糖酸钠的混合物,
C为异丙苯磺酸钠,和
D为氯化镁。
如下混合物同样是非常优选的,其中:
A1)为平均具有8个环氧乙烷单元和1个环氧丙烷单元的直链或支链C10醇的烷氧化物或其混合物,
和
A2)为平均具有7个环氧乙烷单元的直链或支链C12-C15醇的烷氧化物,
和
B为柠檬酸和葡萄糖酸钠的混合物,
C为异丙苯磺酸钠,和
D为氯化镁。
其他有用的添加剂包括例如抑泡组分或消泡剂,尽管本混合物的泡沫已经非常少。特别有用的抑泡组分为2-乙基己基异壬酰胺(2-ethylhexylisononanonamide)(0.1%至1.0%重量,优选0.5%重量)。
所述组分A(或A1和A2的总和)在水溶液中以基于整个水溶液的1%至40%,优选7%至20%,更优选14%至20%重量的浓度存在。组分B使用的浓度为1%至20%,优选2%至10%,更优选3%至8%重量。组分C和D的每种的使用浓度为0.1%至10%,优选0.4%至5%,更优选0.6%至2.5%重量。
也可以制备更浓的溶液,此时各组分彼此间的比例保持相同。
混合物通过简单混合各组分而制备,各个组分为已知的化合物而且市售可得。
本发明的混合物是低粘度、与水以任何比例互溶、储存稳定的液体,因而可用于自动计量泵系统。本混合物泡沫极低,展示出良好的湿润能力和良好的再湿润能力,特别是对于经过氧化物漂白法漂白的棉。它还具有良好的清洗作用和良好的螯合作用,特别是对铁、锰、碱土金属和重金属。所述混合物具有过氧化物稳定作用且高度耐碱。使用所述的产品进行漂白时可达到惊人的高白度。令人惊讶的低用量的增溶剂进一步组成有用的技术优势。
由于其特殊的性质,本发明的混合物适于可导致泡沫问题的机器上所有的纤维种类。它特别适用于要求单一产品具有良好的湿润、清洗和稳定性质的组合以高效和经济地加工的情形。一些纤维的实例为棉、亚麻、毛、毛-聚酯、粘胶纤维或苎麻纤维。
下面的实例举例说明本发明。所有的百分比要理解为%重量。
用于100%棉针织物的配方实例
煮练染暗色泽
煮练(浴比8∶1至10∶1**)
1-3m//l 本发明混合物
2-3ml/l 50%的氢氧化钠水溶液
化学品优选在40℃加入,以2至4℃/分钟加热至98℃,沸腾处理40分钟,或在120℃处理5分钟,冷却到70℃,倒出浴液。
冲洗
在80℃下热冲洗10至15分钟,倒出浴液,用0.5至1ml/l的不含无机酸中和剂(例如柠檬酸、马来酸、乙酸、甲酸、乳酸或膦酸(例如SirrixNE liquid,Clariant))冷冲洗10至20分钟,倒出浴液。
染色
按通常的方法。
用于100%棉针织物的配方实例
过氧化氢漂白
过氧化物漂白(浴比8∶1至10∶1**)
1-3ml/l 本发明混合物
2-3ml/l 50%的过氧化氢
1.5-2.5ml/l 50%的氢氧化钠水溶液
化学品优选在40℃加入,以2至4℃/分钟加热至98℃,沸腾处理45分钟,或在110℃处理15分钟,冷却到70℃,倒出浴液。
冲洗
在80℃下热冲洗10至15分钟,倒出浴液,用0.5至1ml/l的不含无机酸中和剂(例如柠檬酸、马来酸、乙酸、甲酸、乳酸或膦酸(例如SirrixNE liquid,Clariant))冷冲洗10至20分钟,倒出浴液。
生物去除残余过氧化物
在30至55℃处理0.3至0.4ml/l的过氧化氢酶(例如BactosolARL liquid conc.,Clariant)的含水制剂10至15分钟,pH 6至8.5,织物准备染色,继续进行不用倒出浴液。
**当选择非常小的浴比时,应使用0.3至1ml/l的例如蜡和醇烷氧化物(alcohol alkoxylate)以及聚乙二醇衍生物或例如各种矿物油、酯油、长链羧酸或石蜡的混合物的滑动增进剂(例如ImacolC liquid,Clariant)。
纤维素纤维通常的漂白循环现在描述为纺织前处理工艺的实例。
在EP 1 305 469中作为现有技术而引用的通常准备100%棉机织物染色的典型实例包括:
浸染工艺
a)浴液组成
0.5-2.0g/l的湿润剂/洗涤剂:非离子或阴离子表面活性剂
0.3-0.6g/l的过氧化物稳定剂:基于有机磷酸盐的(例如二亚乙基三胺五亚甲基磷酸(DTPMP)和/或基于氨基有机酸的(例如二亚乙基三胺五乙酸(DTPA))和/或基于聚丙烯酸的(例如葡萄糖酸钠盐)和/或基于硅酸盐的和/或碱土金属盐(例如MgCl2)
以上两种组分可以用1至4g/l的本发明的混合物代替。
1.5-3.0g/l的苛性钠(100%)
1.5-3.0g/l的过氧化氢(100%)
b)常见应用
将纤维素物料装填到浸染机或装置(例如喷射式染色机、绞盘、筒装染色机、经轴等)中。在将物料装填到机器中之前将水加入机器中并可能加入湿润剂配制成浴液。水量通常根据所加入的物料的重量计算并用浴比表示。通常浴比为10∶1,也就是10l液体用于1kg织物。
物料装填到机器中后,加入剩余的化学品并将得到的浴液加热到合适的温度,通常为98℃至110℃。根据机器/装置的构造,物料和/或液体开始运动以确保均匀和高效的前处理。
处理15至30分钟后,将浴液冷却并倒出或排出。必须多次冲洗和/或溢流清洗纤维物料以除去物料中的杂质,特别是残留的碱性,否则将会削弱随后操作的效率。
碱性通常由苛性钠供给,它是活化氧化组分(过氧化氢)和皂化蜡与其他脂肪基棉副产物使这些杂质容易除去所必须的。这种纤维素物料的前处理工艺通常称为漂白循环,在物料染色前进行。
在EP 1 305 469中公开了更新的用于纤维素或纤维素-合成纤维共混底物的前处理方法,该方法避免或至少相当地减少了所要求的冲洗的量。该方法理想地用于在染色之前对纤维素或纤维素纤维共混物料的前处理。该方法可以节省相当数量的水、能量和人工。该方法由以下步骤组成:提供容器;提供纤维素或纤维素-合成纤维共混底物;提供水浴;加入有效量的选自有机酸盐、有机胺衍生物、过渡金属的活化化合物,加入有效量的苛性钠;在漂白循环期间加入有效量的过氧化氢;在规定的时间期间将水浴温度加热到50℃以上;倒出浴液。可能还要加入有效量的湿润剂、研磨剂和过氧化物稳定剂。
在这样的在此以纤维素为实例举例说明的前处理方法中,本发明的混合物非常有用,它替代在EP 1 305 469中的方法的湿润剂和过氧化物稳定剂两者(使用1至4g/l)。
所采用的试验方法为本领域技术人员所知;这里只通过实例引用两个:
Ross-Miles泡沫试验
泡沫体积在一定数量的液体从确定高度倒下后立即测量和等一分钟后测量。
使用1000ml、内径60mm、内高430mm的量筒。将试验液体从2 l独立的漏斗倒出流经长70mm、内径2mm的毛细管,从毛细管的出口至量筒底部测量的高度为600mm。
将500ml的待测溶液加入独立的漏斗中,然后让它通过毛细管控制的约0.17 1/分钟的流出速率流到量筒中。当全部溶液流出时,开动停表并从量筒的刻度读出总体积(泡沫体积加溶液体积)。1分钟后再重复读数。
碱性泡沫性能使用2g/l浓度的表面活性剂的2°Be-NaOH软化水溶液试验,2°Be-NaOH等于12g/l的NaOH固体(30ml/l的NaOH36°Be)。试验温度为20至25℃。
碱性湿润
此试验方法测量织物样品沉到容量1l、高14cm和直径10cm的玻璃烧杯中表面活性剂溶液底部所用的秒数。使用的织物样品为棉试验布,商品号501.2,490g/m2,得自EMPA Testmaterialien AG ofSt.Gallen,Switzerland。将此布切为直径3.5cm的圆片,用特殊的夹具浸入表面活性剂溶液中。湿润作用在25℃的2°Be-NaOH中试验。
用NaOH试验碱稳定性
此试验方法测量在多大的氢氧化钠水溶液的浓度下产品是稳定的。
表面活性剂必须对氢氧化钠水溶液具有一定的稳定性以使纺织工业中与例如煮练、丝光、漂白相关的工艺中确保完善的操作。
所试验的是5g/l的表面活性剂的碱稳定性,每次试验配制100ml的液体。该试验在室温20至25℃进行。将所要求量的氢氧化钠水溶液称到玻璃烧杯中,并用软化水补充到95ml。在搅拌下将5ml的10%的表面活性剂溶液加入到碱液中。将玻璃烧杯在室温下放置24小时,不要搅拌。
所述溶液在24小时后试验稳定性。特别要注意乳状液和沉淀,浑浊而没有可见沉淀是允许的。要确定的是表面活性剂仍然稳定的浓度。碱稳定性以X°Be-NaOH报导。
实施例1
试验本发明的含水混合物,所述混合物包含作为组分A1的7.4%的平均具有8个环氧乙烷单元和1个环氧丙烷单元的直链或支链C10醇的烷氧化物或其混合物,和作为组分A2的7.4%的平均具有7个环氧乙烷单元的直链或支链C12-C15醇的烷氧化物。其他组分为3.6%的葡萄糖酸钠、1.5%的七水合氯化镁、2%的异丙苯磺酸钠的40%水溶液、1%的柠檬酸和0.05%的消泡剂。
比较实施例1
对照试验EP 1 092 804中描述的组合物。所述的混合物此后称为“对照1”。
性能试验
这两种混合物用作纺织前处理剂的试验结果如下:
名称 | TS含量[%] | 泡沫RM[ml]中性 | 泡沫连续方法[ml] | 湿润中性2g/l[s] | 湿润碱性2g/l[s] | 棉喷射-漂白:CIE(白度) | 用H<sub>2</sub>O1∶1稀释 |
实施例1 | 20 | 40 | 50 | 85 | 90 | 69 | 稳定 |
对照1 | 17 | 80 | 150 | 120 | 120 | 67 | 不稳定 |
TS=干固体含量(用Mettler IR干燥器测量);
RM=Ross-Miles方法(DIN 53902-2)
本发明的混合物显示较低的泡沫和同样较低的(也就是出众的)湿润性,达到的白度较高,它可以用水稀释,不同于比较产品。
实施例2
试验本发明的含水混合物,所述混合物包含作为组分A1的10%的平均具有8个环氧乙烷单元和1个环氧丙烷单元的直链或支链C10醇的烷氧化物或其混合物,和作为组分A2的10.0%的平均具有7个环氧乙烷单元的直链或支链C12-C15醇的烷氧化物。其他组分为5%的葡萄糖酸钠、1.8%的七水合氯化镁、7%的异丙苯磺酸钠的40%水溶液、1.10%的一水合柠檬酸、0.15%的消泡剂和0.50%的2-乙基己基异壬酰胺。
对照物再次采用上面实施例1中的“对照1”和作为“对照2”的由脂肪醇乙氧化物、葡萄糖酸盐和增溶剂组成的含水混合物。
性能试验
本发明的混合物和两种对照产品用熟知的各种方法试验它们用作纺织前处理助剂的用途,结果如下:
过氧化氢漂白
在110℃下15分钟
物料:100%棉织物
浴比:9∶1
表2
制剂和过氧化氢漂白结果
制剂 | 1 | 2 | 3 | |
实施例2 | 1.1 | ml/l | ||
对照2 | 1.1 | ml/l | ||
对照1 | 1.1 | ml/l |
H<sub>2</sub>O<sub>2</sub> 50% | 2.2 | 2.2 | 2.2 | ml/l |
NaOH 50% | 1.7 | 1.7 | 1.7 | ml/l |
结果 | 1 | 2 | 3 |
CIE白度 | 67.5 | 66.0 | 67.3 |
吸收mm | 37 | 33 | 34 |
残余过氧化物% | 14 | 13 | 15 |
本发明的制剂显示最佳白度和最佳吸收值,也就是最佳的再湿润性。
表3
其他性能试验
制剂 | 碱稳定性5g/l的°Be-NaOH | 碱湿润[s] | 泡沫RM[ml]碱性开始/1分钟 |
实施例2 | 7 | 142 | 25/5 |
对照1 | 6 | 209 | 50/50 |
对照2 | 1 | 90 | 50/20 |
碱湿润和Ross-Miles泡沫试验用1.1ml/l的试验产品进行,用2.2ml/l的50%的H2O2和2.2ml/l的50%NaOH。
本发明的实施例2显示最高的碱稳定性,只是在碱湿润上落后于对照1,是目前用Ross-Miles试验时发泡最低的。
中性清洗试验
图1显示在50℃、pH 7时将EMPA污染的棉布(商品号107)清洗试验30分钟后的结果。只用2g/l,本发明的实施例2比对照制剂明显更高地使污染布发亮(即清洁)。
碱性清洗试验
图2显示在50℃、pH 8.5时将EMPA污染的棉布清洗试验30分钟后的结果。在此本发明的实施例2比对照制剂明显更高地使污染布发亮(即清洁)。
碱稳定性试验
图3显示本发明的混合物具有最佳的碱稳定性。
Claims (9)
1.一种含水混合物,所述混合物包含
A)两种不同的式(I)烷氧化物A1)和A2)
R1-O-(CH2-CHR2-O)n-CH2-CH2-OH (I)
或其磷酸酯,
其中
A1)R1为支链C6-C14烷基,
R2为氢、甲基或乙基,和
n的平均值为3至11;
A2)R1为直链或支链C8-C19烷基,
R2为氢、甲基或乙基,和
n的平均值为3至10;
B)至少一种选自以下的化合物:简单形式的羟基羧酸、低聚羟基羧酸、简单形式的羟基羧酸的盐、低聚羟基羧酸的盐、聚丙烯酸酯、膦酸酯、聚丙烯酸酯盐、膦酸酯盐和其混合物,
C)芳族磺化物或亚磺化物或硫酸化物或其盐,
D)碱土金属盐,
其中所述组分A)的浓度为1%至40%重量,所述组分B)的浓度为1%至20%重量,所述组分C)和D)的每种的浓度为0.1%至10%重量,基于含水混合物。
2.权利要求1的含水混合物,其中
A1)R1为支链C8-C12烷基,
R2为氢或甲基,
n的平均值为5至9,
A2)R1为直链或支链C10-C17烷基,
R2为氢或甲基,
n的平均值为4至8,
B)为柠檬酸、葡萄糖酸钠、α-羟基聚丙烯酸酯或ATMP、HEDP、DTPMPA、EDTMPA、PBTC或这些膦酸酯的盐或其混合物,
C)为异丙苯磺酸、萘磺酸、异丙苯磺酸碱金属盐、萘磺酸碱金属盐、异丙苯磺酸铵盐或萘磺酸铵盐,和
D)为氯化镁、硫酸镁、氯化钙或硫酸钙。
3.权利要求2的含水混合物,其中
A1)R1为支链C10烷基,
R2为氢,
n的平均值为7;和
A2)R1为直链或支链C12-C15烷基,
R2为氢,
n的平均值为6,
B)为柠檬酸、葡萄糖酸钠、DTPMPA或其混合物,
C)为异丙苯磺酸、异丙苯磺酸的碱金属盐或异丙苯磺酸的铵盐,知
D)为氯化镁或硫酸镁。
4.权利要求3的含水混合物,其中
A1)为平均具有8个环氧乙烷单元和1个环氧丙烷单元的直链或支链C10醇的烷氧化物或其混合物,
A2)为平均具有7个环氧乙烷单元的直链或支链C12-C15醇的烷氧化物,
B)为柠檬酸和葡萄糖酸钠的混合物,
C)为异丙苯磺酸钠,和
D)为氯化镁。
5.权利要求4的含水混合物,其中
B)为柠檬酸和葡萄糖酸钠的混合物,
C)为异丙苯磺酸钠,和
D)为氯化镁。
6.权利要求1的含水混合物,其中所述组A)的浓度为7%至20%重量,组分B)为2%至10%重量,组分C)和D)每种的浓度为0.4%至5%重量,基于含水混合物。
7.权利要求1的含水混合物,其中所述组分A)的浓度为14%至20%重量,组分B)为3%至8%重量,组分C)和D)的每种的浓度为0.6%至2.5%重量,基于含水混合物。
8.权利要求1的含水混合物,其中所述混合物还包含抑泡组分和消泡剂。
9.一种纺织品,所述纺织品用权利要求1的含水混合物预处理。
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CN101880962B (zh) * | 2010-07-05 | 2011-12-28 | 五邑大学 | 一种活性染料的前处理剂 |
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