CN103958767B - 增加纤维材料的耐氯漂牢度的方法 - Google Patents

增加纤维材料的耐氯漂牢度的方法 Download PDF

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CN103958767B
CN103958767B CN201280054268.2A CN201280054268A CN103958767B CN 103958767 B CN103958767 B CN 103958767B CN 201280054268 A CN201280054268 A CN 201280054268A CN 103958767 B CN103958767 B CN 103958767B
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P.奥滋伊
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Abstract

本发明涉及增加染色的合成聚酰胺纤维材料的耐氯漂牢度的方法，其包括在染色之后用包含硫脲/甲醛/双酚缩合物或硫脲/多异氰酸酯加成物的水性液体处理所述纤维材料。

Description

增加纤维材料的耐氯漂牢度的方法
本发明涉及通过用特定硫脲衍生物处理来增加染色的天然或合成纤维材料、特别是聚酰胺(PA)纤维材料的耐氯漂牢度的方法，且涉及适合在所述方法中作为助剂的硫脲/甲醛/双酚缩合产物和硫脲/二异氰酸酯加成物。
使用染料获得的染色和印色常表现出分别对氯气和次氯酸盐的高水平的敏感度。例如，酸性染料因氯气而明显降解，引起其吸收性质改变，且因此引起颜色改变。在PA织物上，例如在织造的聚酰胺地毯织物上基于酸性染料的灰色三色染色的色调在氯气或次氯酸盐的作用下迅速变成黄色。这一缺点通常通过用天然或合成鞣酸衍生物处理染色的聚酰胺纤维材料来解决。然而，改善耐氯性的所述已知组合物具有缺点，例如它们中的大多数强烈改变染色的色调且降低耐光牢度。另一问题在于耐氯性可在PA6.6针织织物上容易地改善，但这些化合物的性能在染色地毯的情况下本质上降低，因此需求明显更强烈。因此，在特别是用酸性染料染色的合成聚酰胺纤维材料的处理中，需要用于增加耐氯性而没有所提到的缺点的改善的组合物。
现在已经发现在聚酰胺纤维材料上的染色的耐氯漂牢度可通过对其用特定的硫脲衍生物进行处理而在不影响或仅稍微不利地影响其他牢度性质的情况下改善。
预料不到的是，这些硫脲衍生物中的一些另外充当着色阻断剂；即它们有效地防止处理过的纤维被常规食品着色剂着色。
本发明涉及增加染色的合成聚酰胺纤维材料的耐氯漂牢度的方法，其包括在染色之后用包含硫脲、甲醛和双酚的缩合产物或下式的硫脲/二异氰酸酯加成物的水性液体处理所述纤维材料：
其中X为1，6-亚己基或下式的基团：
R1代表氢、-CO-NR2R3、-CO-O-N＝CR4R5、-COOR6或-CO-NH-CS-NH2，其中R2表示氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R3为C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R4为氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R5为C1-C6烷基、C6-C30芳基或C7-C36芳烷基，且
R6为氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基。
硫脲/甲醛缩合物是已知的且可通过类似于脲醛树脂使硫脲与甲醛在碱性溶液中反应来制备，例如如H.S.Nalwa等在Mat.Res.Bull.，18，897-902(1983)中描述。
该缩合物的分子量取决于离析物的比率和反应条件。
常获得低聚缩合物，即两分子硫脲与两分子或三分子甲醛的缩合物。
可用于根据本发明的方法中的硫脲/甲醛缩合物为硫脲、甲醛和双酚的缩合产物。适合制备这些缩合产物的双酚为4，4′-二羟基联苯、4，4′-二羟基二苯醚、双酚A、双酚F且特别是双酚S(4，4′-二羟基二苯基砜)。
这些化合物为新的且是本发明的另一目的。
该缩合反应可根据本身已知的方法(例如在美国专利第3,790,344号中所述)通过在碱性水溶液中在高温下使离析物反应来进行。
优选的硫脲/甲醛缩合物由硫脲、甲醛、双酚S和苯酚-4-磺酸制备。
在这些硫脲/甲醛/胺-缩合物之中，特别优选四氢-5-正丁基-(S)-三嗪硫酮(triazinethione)和四氢-5-糠基-(S)-三嗪硫酮。
适用于所要求的方法的另外的硫脲衍生物为硫脲/异氰酸酯加成物。这些化合物可通过单-、二-或多异氰酸酯与硫脲在有机溶剂中在高温下反应且在适当的情况下随后水解或与胺或醇反应来制备。
在二-或多异氰酸酯与硫脲反应之前，可能首先使一些异氰酸酯基团与封端剂反应以 在分子中引入嵌段的异氰酸酯基团。以此方式，可获得具有较佳耐久性的产物。用于异氰酸酯的封端剂是公知的且例如可为酚、肟、内酰胺、醇、酰胺、仲胺和位阻胺、丙二酸酯衍生物、吡唑、1，2，4-三唑、亚硫酸氢盐加成物等。
优选的封端剂为肟，特别是丁酮肟。
优选在根据本发明的方法中施用由1摩尔二异氰酸酯和0.5-2.5摩尔、更优选0.8-2.2摩尔硫脲制备的加成物。
这些化合物为新的且本发明还涉及下式的硫脲/二异氰酸酯加成物：
其中X为1，6-亚己基或下式的基团：
R1代表氢、-CO-NR2R3、-CO-O-N＝CR4R5或-CO-NH-CS-NH2，
其中R2表示氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R3为C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R4为氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基，且
R5为C1-C6烷基、C6-C30芳基或C7-C36芳烷基。
作为基团R2、R3、R4或R5的C1-C6烷基例如可为甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、新戊基或正己基。
指定为R2、R3、R4或R5的芳基优选具有6-24个碳原子，特别是6-14个碳原子。
合适芳基的实例有苯基、甲苯基、均三甲苯基、均三异丙基苯基(isityl)、2-羟基苯基、4-羟基-苯基、2-氯苯基、4-氯苯基、2，6-二氯苯基、2-氨基苯基、3-氨基苯基、4-氨基苯基、4-甲氧基苯基、4-乙氧基苯基、萘基和菲基。
在本发明的上下文中术语“芳烷基”包括含有碳环芳族环的芳烷基以及含有杂环芳 族环的芳烷基。作为R2、R3、R4或R5的含有碳环芳族环的芳烷基优选具有6-30个碳原子，特别是具有7-12个碳原子。
合适芳烷基的实例有苄基、2-苯乙基、甲苯基甲基、均三甲苯基甲基和4-氯苯基甲基。
作为R2、R3、R4或R5的含有杂环芳族环的芳烷基优选在芳族环中含有4或5个碳原子和一个或两个选自O、S和N的杂原子。所述杂芳族部分例如可为吡咯基、呋喃基、噻吩基、噁唑基、噻唑基、吡啶基、吡嗪基、嘧啶基、哒嗪基、吲哚基、嘌呤基或喹啉基。
含有杂环芳族环的优选芳烷基为糠基。
还优选式(1)的化合物，其中R1为氢、-CONH-糠基、-CO-N＝C(CH3)(C2H5)或-CO-NH-CS-NH2。
可在根据本发明的方法中有效施用的式(1)的化合物的实例有式(101)-(107)的化合物：
在根据本发明的方法中采用的硫脲衍生物有利地在地毯上以20-200g/l、优选20-100g/l且特别是30-90g/l的量使用且在PA织物上优选以10-80g/l、特别是10-50g/l的量使用。
合适的聚酰胺纤维材料包括合成聚酰胺纤维材料，例如聚酰胺6或聚酰胺-6，6；和纤维共混物，例如聚酰胺/纤维素纤维共混物、聚酰胺/羊毛纤维共混物或聚酰胺/弹性纤维共混物。
所述纺织材料可以任何形式使用，例如以纤维、纱线、机织织物或针织织物的形式使用。
用所述硫脲衍生物处理所述聚酰胺纤维材料可根据在纺织材料的染色、预处理或整理过程中典型地使用的常规方法如尽染法和轧染法进行。不需要专门的设备。例如，可以使用常规染色设备，例如开放浴、绞盘染槽、卷染机或轧染机、喷射机或循环设备。
优选所述纤维材料根据轧-烘热固着(pad-dry thermofix)法或根据泡沫法处理。
对于地毯的处理优选使用泡沫法。
如果该处理通过泡沫法或轧-烘热固着方法进行，则该方法有利地在80-180℃、100-160℃且特别是120-150℃的温度下进行。热固着化时间例如可为0.5-15分钟且优选为1-5分钟。该液体的pH通常为2-7，优选为3-5且特别是3.5-4.5。
除了根据本发明的助剂之外，该液体还可包含常用的添加剂，诸如电解质如氯化钠或硫酸钠、分散剂和润湿剂、pH调节剂和消泡剂。
在本发明中要求保护的方法对于处理地毯特别方便，因为其不仅增加了纤维的耐氯漂牢度，而且意外地改善了处理过的材料的防着色性。
本发明因此还涉及增加染色的合成聚酰胺地毯的防着色性的方法，其包括在染色之后用包含硫脲/甲醛缩合物的水性液体处理所述地毯。
本发明还涉及增加染色的合成聚酰胺地毯的防着色性的方法，其包括在染色之后用包含硫脲/甲醛缩合物和聚羧酸的水性液体处理所述地毯。
以下实施例用来说明本发明。除非另作说明，否则温度以摄氏度给出，份数为重量份，且百分数是指重量百分数。重量份数涉及以与千克/升相同比率的体积份数。
I.制备实施例
I.1.制备硫脲、甲醛和双酚S的缩合产物
将32g(0.184mol)苯酚磺酸(65％水溶液)用40g水稀释并用41g4N-NaOH中和到pH7.5。将中和的苯酚磺酸分散体加到52g(0.216mol)双酚S和21.6g30％NaOH在170g水中的悬浮液中。在加入14.6g(0.192mol)硫脲之后，将烧瓶加热到85℃。随后，在85℃下在30分钟内引入42.1g(0.519mol)37％甲醛。在该添加完成时，将该混合物在温和回流下加热18小时。 将该产物用水稀释以产生澄清的黄色至浅棕色溶液，固含量为25％。
I.2.制备硫脲、甲醛和双酚S的缩合产物
将32g(0.184mol)苯酚磺酸(65％水溶液)用40g水稀释并用41g4N-NaOH中和到pH7.5。将中和的苯酚磺酸分散体加到置于压力反应器中的52g(0.216mol)双酚S和21.6g30％NaOH在170g水中的悬浮液中。在加入14.6g(0.192mol)硫脲之后，将烧瓶加热到85℃。随后，在85℃下在30分钟内引入42.1g(0.519mol)37％甲醛。在该添加完成时，将该反应器封闭并加热到120℃历时4小时。将该产物用水稀释以产生澄清的黄色至浅棕色溶液，固含量为25％。
I.3.制备硫脲、甲醛、双酚S和4-苯酚磺酸的缩合产物
将44.8g(0.257mol)4-苯酚磺酸(65％水溶液)用70g水稀释并用54g4N-NaOH中和到pH7.5。将中和的苯酚磺酸分散体加到置于压力反应器中的104g(0.431mol)双酚S和42g30％NaOH在170g水中的悬浮液中。在加入29.2g(0.384mol)硫脲之后，将烧瓶加热到85℃。随后，在85℃下在30分钟内引入70.5g(0.869mol)37％甲醛。在该添加完成时，将该反应器封闭并加热到120℃历时4小时。将该产物用水稀释以产生澄清的浅棕色溶液，固含量为25％。
I.4.硫脲、甲醛和双酚S的缩合产物
在搅拌下将8.5g聚甲基丙烯酸溶液(1850，由Rohm and Haas供应)缓慢加到90g在实施例I.3中制备的产物中。获得混浊溶液。
I.5.碲脲、甲醛和双酚S的缩合产物
在搅拌下将15g苯乙烯马来酸酐共聚物溶液(1000HNa，由SARTOMER供应，Mn＝2000，Mw＝5500)缓慢加到85g在实施例I.3中制备的产物中。获得澄清溶液。
I.6.式(101)的硫脲/二异氰酸酯加成物
将139.2g(0.8mol)甲苯-2，4-二异氰酸酯溶解于410ml2-丁酮中。在25-30℃下加入122.4g(1.6mol)硫脲且将该混合物在该温度下搅拌3小时。在这期间，白色产物沉淀。随后将该混合物加热到80℃历时15小时。加入900ml水并蒸馏出溶剂。随后，将该白色分散体在存在 S(阴离子表面活性剂，由Bayer供应)的情况下研磨到粒度为1μm。在加入水之后，获得具有23％的固含量的粘性分散体。
I.7.式(102/103)的硫脲/二异氰酸酯加成物
将87g(0.5mol)甲苯-2，4-二异氰酸酯溶解于200ml2-丁酮中。在25-30℃下加入38g(0.5mol)硫脲且将该混合物在该温度下搅拌3小时且随后经1小时加热到40℃。在这期间，白色产 物沉淀。加入500ml水并蒸馏出溶剂。然后，将该白色分散体在存在S的情况下研磨到粒度为1μm。在加入水之后，获得具有20％的固含量的粘性分散体。
I.8.式(104/105)的碲脲/二异氰酸酯加成物
将130.5g(0.75mol)甲苯-2，4-二异氰酸酯溶解于300ml2-丁酮中。在25-30℃下加入57g(0.75mol)硫脲且将该混合物在该温度下搅拌3小时且随后经1小时加热到40℃。在这期间，白色产物沉淀。缓慢加入48.6g(0.5mol)糠胺(放热反应)且将该混合物经3小时加热到80℃。加入600ml水并蒸馏出溶剂。然后，将该白色分散体在存在S的情况下研磨到粒度为1μm。在加入水之后，获得具有22％的固含量的粘性分散体。
I.9.式(106/107)的具有嵌段异氰酸酯基团的硫脲/二异氰酸酯加成物
将87g(0.5mol)甲苯-2，4-二异氰酸酯溶解于250ml2-丁酮中。在25-30℃下在60分钟内加入17.4g(0.2mol)丁酮肟。在该添加的最后，将该混合物在40℃下搅拌30分钟。
在40℃下加入60.8g(0.8mol)硫脲且将该混合物在该温度下搅拌3小时且随后经15小时加热到80℃。将500ml水加到该白色分散体中且蒸馏出溶剂。然后，将该白色分散体在存在3％S的情况下研磨到粒度为1μm。在加入水之后，获得具有22％的固含量的粘性分散体。
II.应用实施例
II.1.在PA6上的着色阻断
将PA6地毯小块在pH6.0下使用含有0.069％Yellow MP-R(酸性染料，由HUNTSMAN供应)、0.041％Red2B(酸性染料，由HUNTSMAN供应)和0.081％Blue4R-01(酸性染料，由HUNTSMAN供应)的染料混合物染色。获得着灰色的地毯。
根据轧-烘-热固着法在100％的轧液率下将70g/1在实施例I.1-I.5中制备的产物在pH4下施用在预染色的PA6地毯小块上(干燥步骤：20分钟/80℃，热固着步骤：5分钟/150℃)。
对这样处理的试样根据AATCC175-2003进行防着色性试验并根据稍微改进的AATCC175-2003试验进行耐氯漂牢度试验，其中施用10％溶液(约6000ppm活性氯)来代替染料溶液。结果汇总于表1中。
表1：
染色试验的评分：1-10，最佳分：10
氯试验的评分：1-5，最佳分：5
当将实施例I.1-I.5的产物施用在根据泡沫法染色的地毯上时获得类似的结果，在该泡沫法中，使用5g/1Dicrylan Foamer HP来制备泡沫体，在50℃下干燥30分钟，在150℃下固化5分钟。
II.2.PA6上的耐氯漂牢度
根据轧-烘-热固着方法在100％的轧液率下将实施例I.6-I.9的产物在pH4下施用在预染色的灰色PA6地毯(参见实施例II.1.)上(干燥步骤：20分钟/80℃，热固着步骤：5分钟/150℃)。
对这样处理的试样进行与在实施例II.1中相同的方法的耐氯漂牢度试验。结果汇总于表2中。
表2：
耐氯漂牢度试验的评分：1-5，最佳分：5
II.3PA6.6针织织物上的耐氯漂牢度
PA6.6针织织物根据尽染方法使用含有0.13％Yellow A-3G(酸性染料，由HUNTSMAN供应)和0.089％Blue A-4G(酸性染料，由HUNTSMAN供应)的混合物染色。获得着绿色的织物。
将这些织物用实施例I.3、I.6和I.9中获得的多种产物根据轧-烘-热固着方法(干燥步骤：3分钟/110℃，热固着步骤：0.5分钟/180℃)处理。耐氯漂牢度根据ISO105E03测定，结果汇总在表3中。
表3：
耐氯漂牢度试验的评分：1-5，最佳分：5
耐光牢度度试验的评分：1-5，最佳分：5
CL：纺织助剂(由Huntsman供应)

Claims (7)

1.增加染色的合成聚酰胺纤维材料的耐氯漂牢度的方法，其包括在染色之后用包含硫脲、甲醛、双酚S和苯酚-4-磺酸的缩合产物或下式的硫脲/二异氰酸酯加成物的水性液体处理所述纤维材料，
其中X为1,6-亚己基或下式的基团：
R1代表氢、-CO-NR2R3、-CO-O-N=CR4R5、-COOR6或-CO-NH-CS-NH2，
其中R2表示氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R3为C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R4为氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R5为C1-C6烷基、C6-C30芳基或C7-C36芳烷基，且
R6为氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基。
2.权利要求1的方法，其中所述纤维材料根据轧-烘热固着法或根据泡沫法处理。
3.硫脲、甲醛、双酚S和苯酚-4-磺酸的缩合产物。
4.下式的硫脲/二异氰酸酯加成物，
其中X为1,6-亚己基或下式的基团：
R1代表氢、-CO-NR2R3、-CO-O-N=CR4R5或-CO-NH-CS-NH2，
其中R2表示氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R3为C1-C6烷基、C6-C30芳基或C7-C36芳烷基，
R4为氢、C1-C6烷基、C6-C30芳基或C7-C36芳烷基，且
R5为C1-C6烷基、C6-C30芳基或C7-C36芳烷基。
5.式(101)-(107)的硫脲/二异氰酸酯加成物，
。
6.增加染色的合成聚酰胺地毯的防着色性的方法，其包括在染色之后用包含硫脲、甲醛、双酚S和苯酚-4-磺酸的缩合产物的水性液体处理所述地毯。
7.增加染色的合成聚酰胺地毯的防着色性的方法，其包括在染色之后用包含硫脲、甲醛、双酚S和苯酚-4-磺酸的缩合产物及聚羧酸的水性液体处理所述地毯。
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