CN1426500A - 用于纤维材料预处理的组合物 - Google Patents
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Abstract
包括三种不同乙氧基化醇的混合物以及具有或不具有其它产品的组合物被用于预处理织物材料,特别是棉织物。所述组合物具有可接受的粘度并且优选以水溶液或水分散体的形式使用。这些组合物具有极小的发泡性,与酶高度相容,并且赋予经其处理的织物以优异的再润湿性。
Description
发明领域
本发明涉及包括至少三种不同乙氧基化醇的组合物在预处理纤维材料方面的用途。
织物形式的纤维材料如机织织物或编织织物,特别是棉织物在染色前通常必须进行预处理。预处理的一个目的是确保染色顺利均匀。根据织物先前的经历和来源或适合设备的情况,所述预处理可包括退浆、脱脂/煮练和漂白织物的措施。这些措施可分别进行,但在个别情况下也可以将多个这些措施在单一工艺中综合进行以节省费用。
为了满足可用预处理方法的需要,预处理中使用了各种化学品。根据所述对象这些化学品可包括润湿剂、洗衣用洗涤剂、酶、漂白剂、稳定剂、络合剂等。这里特别重要的是表面活性剂,它可有效地向织物提供良好的润湿性以及良好的洗涤和清洁效果。但是带来良好润湿性的理想产品应当不会使包含预处理产品的染液的发泡倾向增高或只带来不明显的增高。这不仅在预处理分批进行如在注射机中进行时非常重要,而且在连续进行时也非常重要。预处理产品通常要求低发泡性的原因是在许多情况下不希望再通过加入消泡剂如硅氧烷来抑制发泡性的增加。
由于传统的预处理步骤诸如退浆、脱脂/煮练和漂白在许多情况下被整合成一个合并的预处理工艺,因此也存在着对可用于这种合并预处理工艺的组合物的需求。所述组合物一般是在预处理开始时赋予织物材料良好润湿性以及在预处理结束时赋予织物材料良好亲水性的含水体系。这种良好的亲水性产生染色过程所需的良好再润湿性。
人们可从例如EP-A274350、EP-A360736、EP-A462059、EP-A114788得知可用于预处理织物形式的纤维材料并包括作为表面活性剂的乙氧基化醇或其封端衍生物的产品。包括乙氧基化醇或其衍生物的混合物的组合物也描述于例如EP-A696661和WO92/15664中。
在上述文献中所述的组合物尽管原则上适用于织物预处理但各方面均没有最佳性能。更具体地说,形成泡沫的倾向、过高的粘度、与酶的相容性以及强酸性pH在许多用于预处理织物的已知组合物的情况下都存在问题。在连续和分批预处理方法中,例如在喷射机器中的分批预处理过程中,形成泡沫的倾向特别引人注目。实际上泡沫可通过硅氧烷得到控制,但这通常是不理想的。
本发明的一个目标是开发一种优异地适用于预处理纤维材料特别是棉织物的组合物,它能赋予织物材料良好的再润湿性、与酶高度相容、具有便于处理的可接受粘度并且即使在没有使用高效消泡剂如硅氧烷时也不会产生不可接受的泡沫。
这种目标通过使用包括下面组分A)、B)和C)的组合物预处理纤维材料来获得:
这里R1是具有6-14个碳原子的直链或支链烷基,R2和R3各为具有10-18个碳原子的直链或支链烷基,
m为3-12并优选为4-10,
n为3-18,
x为5-20,
R2和R3各比R1多包含至少2个碳原子并且x-n不低于2。
按照本发明使用的组合物优选为水溶液或水分散体的形式,即包括作为组分D)的水。在这种情况下组合物进一步包括组分E)可能是有益的,组分E)为2-10个碳原子的脂族二醇,优选为具有4-8个碳原子的支化烃链的二醇(其中两个OH基团不连接在相邻碳原子上)。
按照本发明使用的组合物对于纤维材料、特别是织物如机织织物或编织织物的预处理非常有用。它们尤其可用于预处理50-100%重量为纤维素特别是棉花的纤维材料。
可以在不包括水的情况下以没有过高粘度并因此可进行有效操作的形式提供按照本发明使用的组合物。
水分散体或水溶液形式的按照本发明使用的组合物具有3-5的pH,即使在包括除上述三种乙氧基化醇以外的成分的情况下也是如此。这使得它们优于具有更强酸性pH的已知产品,这是因为存在在强酸pH下酶不相容的危险。本发明的织物预处理赋予了织物优良的处理后再润湿性。这对随后的染色过程有正面影响。
按照本发明使用的组合物可在没有加入磷化合物的情况下用于预处理。这对于环境、特别是对于废水来说是有益的。
水溶液形式的按照本发明使用的组合物具有极少(如果有的话)形成不想要的泡沫的倾向,所以预处理过程不受发泡的干扰。最后,只要没有其它与酶具有差相容性的组分包括进来,则按照本发明使用的组合物可与酶高度相容。当预处理操作是在导致浆料酶解的酶如α-淀粉酶的存在下进行时,这种良好的酶相容性是有益的。
按照本发明使用的组合物提供了织物特别是棉制品的快速容易的润湿性。因此,预处理过程从开始起就有效起作用。
按照本发明使用的组合物必须包括至少上述组分A)、B)和C)。所有三种组分均是可以买到的。它们通过使相应的醇与环氧乙烷按通常人们熟悉的方法反应来制备。
这里R1为6-14个碳原子的直链或支链烷基。优选R1为8-12特别是9-11个碳原子的支链烷基。表明乙氧基化程度的m值为3-12,优选4-10。
组分B)为通式(II)的乙氧基化醇
这里R2为10-18个碳原子的直链或支链烷基,优选10-16个碳原子的支链烷基。乙氧基化度n为3-18,优选4-10。
组分C)为通式(III)的乙氧基化醇
这里R3为10-18个碳原子的直链或支链烷基,优选10-16个碳原子的支链烷基。乙氧基化度x为5-20,优选6-16。
三种组分A)、B)和C)的每一种均可以是乙氧基化醇的混合物,而非化学纯产品。因此,这三种组分各自均可使用各分子在基团R1或R2或R3的链长方面不同的工业用或天然醇混合物来制备。这些醇的乙氧基化产生其组分不仅基团R1或R2或R3的链长不同而且乙氧基化度不同即m或n或x的值不同的混合物。但重要的是在用作组分A)的乙氧基化醇的混合物中,大部分分子即不少于80%的分子具有含6-14个碳原子的烷基链长和3-12的乙氧基化度。同样,组分B)和组分C)中不低于80%的分子具有10-18个碳原子的烷基基团和3-18(组分B))或5-20(组分C))的乙氧基化度。
如果要获得按照本发明使用的组合物的益处,那么不仅R2而且R3比R1多包含至少2个碳原子是更为重要且绝对必需的。此外,组分C)的乙氧基化度x应比组分B)的乙氧基化度n大至少2,即x-n应不小于2。
对于在烷基基团碳原子数和乙氧基化度差异方面的两个前述条件均必须满足。已经在实验的基础上确定,就可通过织物预处理获得的效果而言,使用平均所有三种的烷基均具有相同碳原子数或平均所有三种均具有相同乙氧基化度的三种乙氧基化醇的混合物劣于使用按照本发明的组合物。因为通常三种组分A)、B)和C)的每一种都是乙氧基化醇的混合物,因此可能会出现这种情况,即个别分子中的R2和R3基团不是都比所存在的全部R1基团多至少两个碳原子。但是各个基团R1、R2和R3的平均碳原子数必须满足该上述条件。同样,并不是组分C)的每个分子都需要具有比组分B)的任何分子高至少2的乙氧基化度。但是C)的平均乙氧基化度必须比B)的平均乙氧基化度高至少2。
因此当在按照本发明使用的某些组合物中的组分A)是例如平均具有12个碳原子的烷基基团(R1)的乙氧基化醇混合物时,组分B)和C)中烷基基团(R2和R3)的平均长度在任何情况下都必须不低于14个碳原子。同样,当所用组分B)具有14的平均乙氧基化度时,组分C)的平均乙氧基化度x必须不低于16。
所有三种组分A)、B)和C)都不含丙氧基化单元-CH(CH3)-CH2-O-并且在链的一端具有烷基而在另一端具有OH基团。这可将它们与先有技术中为人们熟悉的用于织物预处理的众多产品区分开来。
按照本发明使用的组合物优选包括相对于彼此具有下述量的组分A)、B)和C):
10-40重量份的A)
3-30重量份的B)
0.1-10重量份的C)。
在一优选的实施方案中,按照本发明使用的组合物除组分A)、B)和C)外还包括下面组分D)、E)、F)、G)和H)中的一种或多种:
D)水
E)2-10个碳原子的脂族二醇
F)一种或多种3-8个碳原子的一元或多元羧酸或其碱金属盐
G)水解的聚马来酸酐
H)烷基多苷。
组分E)在上面已描述。
组分G)是水解的聚马来酸酐。它可以是一种所有聚马来酸酐的酸酐基已经水解成酸基的产物即聚马来酸。但是组分G)也可以是只有一些酸酐基水解的部分水解物。组分G)也可以是含水解马来酸酐基的共聚物。例如,马来酸酐和一些其它单体的共聚物(也可包含芳香单元)可在部分或完全水解后用作组分G)。可用作组分G)的聚合物的分子量优选为400-1000。组分G)如同下面所述的组分F)一样可用作金属离子的络合剂。可用作组分G)的产品是可以买到的,例如可购自Great Lakes,GB的聚马来酸水溶液“BELCLENE200”。
组分F)是一种3-8个碳原子的脂族一元或多元羧酸或其碱金属盐,特别是钠盐或钾盐。组分F)也可以不是单一化合物,而是这类化合物的混合物,例如一种酸和一种其它酸的碱金属盐的混合物。组分F)如同组分G)一样可在织物预处理领域用作金属离子的络合剂。尤其可用作组分G)的是柠檬酸或葡糖酸或这些酸的碱金属盐或这类化合物的混合物。
组分H)是烷基多苷。它可有助于使按照本发明使用的组合物对碱性物质的作用更稳定。烷基多苷是人们熟悉的商品化产品,可通过相应的糖与醇的酸催化反应制备。有用的组分H)的一个例子是可购自德国Cognis的Glucopon600CS UP(一种低聚烷基吡喃葡糖苷的水溶液)。
在一个按照本发明使用的组合物的优选实施方案中,组合物包括下述相对量的组分A)到H):
10-40重量份的A)
3-30重量份的B)
0.1-10重量份的C)
0-100重量份的D)
0-20重量份的E)
0-20重量份的F)
0-10重量份的G)
0-15重量份的H)。
按照本发明使用的组合物通常可通过在室温下将组分A)到C)以及其它所需组分以任何顺序搅拌混合来制备而没有任何问题。在个别情况下,一定的顺序混合和/或升温可能对存贮稳定性有益。当按照本发明使用的组合物包括其它组分例如上面更具体描述的组分D)到H)时,这些叙述也适用。
如果需要,尤其对于特定的预处理工艺和要求,按照本发明使用的组合物可以包括其它成分。这些成分可以是例如酶、络合剂或其它表面活性剂;它们可以以预处理方法的常用量使用。但是,建议在各种使用这种成分的情况下进行检查以确认按照本发明使用的组合物的稳定性或上述优点是否降低到不可接受的水平。
按照本发明使用的组合物对于预处理纤维材料非常有用,特别是对于预处理机织织物或编织织物形式的织物纤维材料非常有用。所述的纤维材料可以是包含纤维素、再生纤维素或合成聚合物或这类纤维的共混物的织物。按照本发明使用的组合物特别可用于有50-100%重量棉的织物预处理。其它的纤维可以是例如合成纤维。按照本发明使用的组合物对于连续工艺非常有用,但是也适用于分批预处理工艺例如在喷射机中的预处理。
按照本发明使用的组合物可按照常用的预处理方法如浸渍、浸轧等施加到织物材料上。用于预处理的水溶液有利地具有常规的浓度,例如基于总液体,组分A)、B)和C)之和总计为0.03-2%重量。预处理后,织物材料进一步通过常规的已知方式例如通过有或没有中间烘燥的染色进行处理。
下面将通过实施例说明本发明。
按照下面的表I制备组合物,其中在各个实施例下的数字是指所述组分的重量百分比。
组合物a)是一个非本发明的对比例。组合物b)、c)和d)各包括表面活性剂1、表面活性剂2和表面活性剂3,因此是本发明的实施例。
表1
组合物 | 表面活性剂1 | 表面活性剂2 | 表面活性剂3 | 表面活性剂4 | 表面活性剂5 | 柠檬酸+D-葡糖酸 | 脂族二醇 | 烷基多苷 | 聚合酸 | 膦酸 | 水 |
a) | --- | --- | 2.9 | 37.2 | 1.8 | 6+3 | 6 | --- | 4.8 | 4.5 | 33.8 |
b) | 27 | 12 | 2 | --- | --- | 5+3 | 8 | 5 | 1.5 | --- | 36.5 |
c) | 22 | 17 | 2 | --- | --- | 5+3 | 8 | 5 | 1.5 | --- | 36.5 |
d) | 22 | 17 | 2 | --- | --- | --- | 8 | 5 | --- | --- | 46 |
组合物a)是也包括三种表面活性剂的可买到的预处理产品,三种表面活性剂均是乙氧基化异十三烷醇,即并不是按照本发明使用的组合物的组分A)、B)和C)。
组合物a)必须包括一种有机膦酸以适合于织物的预处理,因此是强酸性的。
表面活性剂1是一种具有平均11个碳原子的支化脂族醇,其平均乙氧基化度为5。
表面活性剂2-5是具有下述平均乙氧基化度的乙氧基化异十三烷醇:
表面活性剂2:5
表面活性剂3:9
表面活性剂4:7
表面活性剂5:10
柠檬酸和D-葡糖酸部分以其钠盐的形式存在。它们构成了金属离子的络合剂。
所用脂族二醇是具有6个碳原子和一个分支碳链的二醇。两个羟基并不连接到相邻碳原子上。
用于组合物b)、c)和d)的聚合酸是水解聚马来酸酐(购自GreatLakes的Belclene200)。
所用的烷基苷是具有10-16个碳原子的相连烷基的D-吡喃葡糖苷(来自德国Cognis的Glucopon600CS UP)。所述组合物通过在室温下搅拌的简单混合制备。
测试组合物a)到d)的粘度(自身)、pH(自身)、润湿性、发泡性和酶相容性,另外测试组合物a)、c)和d)的再润湿性。
粘度:
在室温下使用Rheomat RM180粘度计在剪切法的基础上测定。
形成泡沫的倾向:
使用各含3g/l组合物a)到d)的水溶液用Ahiba-Texomat泡沫计测定。在第二系列,所述液体各自还包含10g/l的苛性钠。在各种情况下,将200ml的水溶液加热到30℃并任何转移到一个1000ml的量筒中。用机械搅拌产生泡沫,目视读出量筒上的泡沫高度。形成泡沫的倾向越高,在表II中记载的形成的泡沫高度越高。
初润湿性:
使用“形成泡沫的倾向”中所述的液体进行测定。测定浸入到液体中的机织棉样品完全沉下去的时间(单位:秒)。时间越少表明织物被所述液体润湿越好/越快。
再润湿性:
这是进行预处理后对织物润湿性的测量。工业实践中需要经预处理的织物可有效快速地再湿润从而确保顺利染色。
制备水溶液,使各种情况下每升水包含0.5g组合物a)、c)或d)。它们还包括常规的碱性漂白配方。
将上述水溶液用于处理针织棉样品,所述样品已经用水重复洗涤,然后在水中机械揉搓、甩水并干燥。然后以秒为单位测量再润湿性。为此,将经这样处理的样品条部分浸入到染色水溶液中。测量染色溶液上升到未浸入的那部分织物上1cm所需要的时间。表II中更低的再润湿性值(单位为秒)表示更快/更好的再润湿。
酶相容性:
预处理过程中通常在预处理液中使用酶来确保可从织物经酶除去浆产品。理想情况下这些酶的活性不应被预处理液中的其它成分损害。尤其在存在强酸产品时特别容易出现酶活性受到损害的情况。
间接测定组合物a)到d)的酶相容性,即可能的酶活性的降低。该方法的基础在于如果组合物的酶相容性差,则酶效能将被极大地降低并且浆产物不能完全从织物去除。测量所用的方法是:在用各含10g/ll的组合物a)到d)中一种组合物的液体适当处理后,测量织物上残余浆料的水平。所述液体还各自包含5ml/1α-淀粉酶含水制剂。
这些组合物a)到d)的含酶液体被用于在室温下对带有淀粉基浆料的100%棉织物进行处理。在织物处理前,将处理液老化8小时,这是因为可能产生酶活性的降低。用处理液浸渍后,将织物在室温下存贮16小时进行浆料的去除。然后将织物用热水洗涤并随后使用校准等级(calibrated scale)测定脱浆的后处理程度。在下面的表II中,在“酶相容性”栏中“差”是指相当部分原存在的浆料仍然存在于织物上。“好”是指在织物上残留极少量的浆料。
测试结果记录于下面的表II。
表II
组合物 | PH,20℃,自身 | 粘度,20℃(自身)mPa sec | 润湿性(秒) | 再润湿性(秒) | 形成的泡沫(cm) | 酶相容性 | ||
无NaOH | 有NaOH | 无NaOH | 有NaOH | |||||
a) | 1.6 | 680 | 5 | 6 | 15 | 93 | 50 | 差 |
b) | 3.6 | 69 | 4 | 5 | -- | 56 | 30 | 好 |
c) | 3.8 | 74 | 5 | 7 | 10 | 20 | 30 | 好 |
d) | >11*) | 43 | 5 | 7 | 12 | 20 | 30 | 好 |
*)组合物d)的高pH是由于烷基多苷本身具有11.5-12.5的pH。不象组合物b)和c),在d)的制备中没有加入酸。
Claims (13)
2.权利要求1的方法,其中R1是8-12个碳原子的支链烷基。
3.权利要求1或2的方法,其中R2和R3各独立为10-16个碳原子的支链烷基。
4.权利要求1-3中一项或多项的方法,其中n为4-10,x为6-16。
5.权利要求1-4中一项或多项的方法,其中所述组合物包括下述相对量的组分A)、B)和C):
10-40重量份的(A)
3-30重量份的B)
0.1-10重量份的C)。
6.权利要求1-5中一项或多项的方法,其中所述组合物还包括组分D)、E)、F)、G)和H)中的一种或多种:
D)水
E)2-10个碳原子的脂族二醇
F)一种或多种3-8个碳原子的一元或多元羧酸或其碱金属盐
G)水解的聚马来酸酐
H)烷基多苷。
7.权利要求6的方法,其中组分E)为具有支链饱和烷基的二醇,其中两个OH基团不连接在相邻碳原子上。
8.权利要求6或7的方法,其中组分F)为柠檬酸或其碱金属盐。
9.权利要求6或7的方法,其中组分F)为葡糖酸或其碱金属盐。
10.权利要求1-9中一项或多项的方法,其中所述组合物包括下述相对量的组分A)到H):
10-40重量份的A)
3-30重量份的B)
0.1-10重量份的C)
0-100重量份的D)
0-20重量份的E)
0-20重量份的F)
0-10重量份的G)
0-15重量份的H)。
11.权利要求1-10中一项或多项用于预处理织物的方法。
12.权利要求11的方法,其中所述织物为机织织物或编织织物。
13.权利要求11或12的方法,其中所述纤维材料为50-100%重量的纤维素,特别是棉。
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EP0598973A1 (en) * | 1992-11-26 | 1994-06-01 | The Procter & Gamble Company | Multi-purpose liquid cleaning composition |
EP0616027A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Concentrated cleaning compositions |
DE4416303A1 (de) * | 1994-05-09 | 1995-11-16 | Bayer Ag | Schaumarmes Netzmittel und seine Verwendung |
DE59510431D1 (de) * | 1994-08-11 | 2002-11-28 | Ciba Sc Holding Ag | Multifunktionelle Textilhilfsmittel-Zusammensetzungen |
DE19523117A1 (de) * | 1995-06-26 | 1997-01-02 | Henkel Ecolab Gmbh & Co Ohg | Wäßriges saures Reinigungsmittel |
US5858955A (en) * | 1997-12-16 | 1999-01-12 | Colgate Palmolive Company | Cleaning compositions containing amine oxide and formic acid |
-
2000
- 2000-04-29 EP EP00109303A patent/EP1149945A1/de not_active Withdrawn
-
2001
- 2001-04-27 BR BR0110264-8A patent/BR0110264A/pt not_active Application Discontinuation
- 2001-04-27 US US10/258,688 patent/US20030122101A1/en not_active Abandoned
- 2001-04-27 MX MXPA02010528A patent/MXPA02010528A/es not_active Application Discontinuation
- 2001-04-27 CN CN01808775A patent/CN1426500A/zh active Pending
- 2001-04-27 KR KR1020027014480A patent/KR20020092456A/ko not_active Application Discontinuation
- 2001-04-27 EP EP01938133A patent/EP1278908A1/en not_active Withdrawn
- 2001-04-27 AU AU2001263870A patent/AU2001263870A1/en not_active Abandoned
- 2001-04-27 WO PCT/EP2001/004762 patent/WO2001083879A1/en not_active Application Discontinuation
-
2005
- 2005-06-29 US US11/172,063 patent/US20060053566A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
WO2001083879A1 (en) | 2001-11-08 |
US20060053566A1 (en) | 2006-03-16 |
EP1278908A1 (en) | 2003-01-29 |
EP1149945A1 (de) | 2001-10-31 |
AU2001263870A1 (en) | 2001-11-12 |
MXPA02010528A (es) | 2003-03-10 |
BR0110264A (pt) | 2003-03-05 |
KR20020092456A (ko) | 2002-12-11 |
US20030122101A1 (en) | 2003-07-03 |
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