CN101052763A - 改善热稳定性的方法 - Google Patents

改善热稳定性的方法 Download PDF

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CN101052763A
CN101052763A CNA2005800370614A CN200580037061A CN101052763A CN 101052763 A CN101052763 A CN 101052763A CN A2005800370614 A CNA2005800370614 A CN A2005800370614A CN 200580037061 A CN200580037061 A CN 200580037061A CN 101052763 A CN101052763 A CN 101052763A
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E·哈姆
H·-J·彼得
C·布林克曼
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Huntsman Advanced Materials Switzerland GmbH
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Abstract

本发明涉及一种改善未染色、荧光增白或用除金属配合物染料之外的活性或分散染料染色的天然或合成聚酰胺纤维材料热稳定性的方法，其中的纤维材料用包含式(1)化合物的液体处理，Y1－X－Y2 (1)其中X是二价脂族或环脂族基，并且Y1和Y2彼此独立地为－OH、－CO－OR1、－NR1R2、－CO－NH－NR1R2或－NH－CO－NH－NR1R2，其中R1和R2彼此独立地为氢；未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C1－C12烷基；未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C5－C24－芳基；未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C6－C36芳烷基；或未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C5－C24环烷基。

Description

改善热稳定性的方法
本发明涉及一种改善未染色、荧光增白或染色的天然或合成聚酰胺纤维材料热稳定性的方法，并且涉及用于该方法的纺织助剂。
在各种纺织品加工程序中(预处理、荧光增白剂的应用、染色、整理)，聚酰胺纤维材料都暴露于热处理中。特别是在未染色物品和已经荧光增白物品的情况下，热处理常常导致不期望的黄化。
在染色之前或之后，热的作用还经常导致不期望的效果。例如，热处理可导致聚酰胺氧化损害，这一点可以，例如，黄化增强或撕裂强度损失证明，而且可能对可染性具有不利影响。在染色处理期间或之后，热处理可导致不可接受的色泽改变
现在已经发现，通过使用特殊纺织助剂可显著减少上述不利效果。
本发明涉及一种改善未染色、荧光增白或用除金属配合物染料之外的活性或分散染料染色的天然或合成聚酰胺纤维材料热稳定性的方法，其中的纤维材料用包含式(1)化合物的液体处理，
Y1-X-Y2    (1)
其中X是二价脂族或环脂族基，并且
Y1和Y2彼此独立地为-OH、-CO-OR1、-NR1R2、-CO-NH-NR1R2或-NH-CO-NH-NR1R2，
其中R1和R2彼此独立地为氢；未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C1-C12烷基；未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C5-C24-芳基；未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C6-C36芳烷基；或未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C5-C24环烷基。
式(1)中的脂族基团X为，例如，亚乙基(ethylene)、亚丙基(propylene)、三亚甲基、丙烷-1，1-二基、四亚甲基、六亚甲基、八亚甲基和十二亚甲基或被一个或多个氧原子或-NH-、-N(烷基)-或-N(亚烷基-NH2)-基团间隔的直链或支化亚烷基。
合适的环脂族基团X为，例如，环己烷-1，2-二基、环己烷-1，3-二基以及
Figure A20058003706100051
作为R1或R2的C1-C12烷基可以是，例如，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、正己基、正辛基或正十二烷基。
作为基团R1-R5之一的C5-C24芳基为，例如，苯基、甲苯基、2，4，6-三甲苯基、2，4，6-三异丙基苯基(isityl)、萘基或蒽基。
合适的C6-C36芳烷基为，例如，苄基和2-苯乙基。
C5-C24环烷基的实例为环戊基和环己基。
在本发明方法中，优选使用其中X为亚乙基、四亚甲基、六亚甲基或八亚甲基的式(1)化合物。
还优选使用其中Y1和Y2为-NR1R2、-CO-NH-NR1R2或-NH-CO-NH-NR1R2并且R1和R2为氢、C1-C12烷基或C5-C24芳基的式(1)化合物。
特别优选其中Y1和Y2为-NR1R2、-CO-NH-NR1R2或-NH-CO-NH-NR1R2并且R1和R2为氢、甲基或苯基的式(1)化合物。
合适的通式(1)化合物的实例为式(101)-(104)化合物，
Figure A20058003706100052
式(1)化合物是公知的并且可商业获得或者可通过公知方法合成。
用于本发明方法的式(1)化合物有利地以0.1g/l-100g/l、优选0.5g/l-50g/l、尤其1.0g/l-40g/l的量存在于所述液体中。
关于聚酰胺纤维材料，考虑范围包括天然聚酰胺纤维材料，例如羊毛或丝，或合成聚酰胺纤维材料，例如聚酰胺6或聚酰胺6.6，或混纺，例如羊毛/纤维素、聚酰胺/纤维素、聚酰胺/羊毛、聚酰胺/聚酯，或，特别是，聚酰胺/弹力混纺(elastane blend)。所述纤维材料优选为合成聚酰胺纤维材料。
所述纺织材料可以任何形式使用，例如纤维、纱线、机织织物、或针织织物。
本发明纺织助剂可通过传统的染色或印刷方法应用于聚酰胺纤维材料，例如通过喷射施加应用或泡沫施加，通过染整方法(exhaustprocess)或，优选地，通过轧染方法。
没有必要使用特殊设备。可以使用，例如，传统染色设备，例如敞开式染缸(open bath)，绞盘染色机(winch beck)，卷染机(jigger)或染色划槽(paddle)，喷射或循环设备。
除包含水和纺织助剂之外，所述液体还进一步包含其他添加剂，例如湿润剂、消泡剂、匀染剂或影响纺织材料性能的试剂，例如，柔软剂、阻燃剂或防垢、防水和防油试剂以及水软化剂和天然或合成增稠剂，例如藻酸盐和纤维素醚。
正如前文所述，本发明方法可有利地用于热稳定未染色聚酰胺(白色物品)和染色聚酰胺，其中未染色聚酰胺可能已经用荧光增白剂处理。
在未染色荧光增白聚酰胺的情况下，防止或减少了在热定型(热空气)期间或成形期间(接触热)由热处理导致的黄化。
本发明方法对于处理荧光增白聚酰胺纤维材料特别有效。
在热稳定染色聚酰胺中，本发明纺织助剂可以在染色之前、期间或之后施加。
当所述助剂在染色之前使用时，可以预防或减少未染色物品在所谓的预定型期间黄化。而且，防止了可能导致染料吸收改变的预定型期间的材料氧化损害。
本发明纺织助剂优选在聚酰胺纤维材料用除金属配合物染料之外的活性或分散染料染色之后施加。用本发明纺织助剂后处理染色聚酰胺材料在后定型(热定型)期间特别为纤维提供了一定程度的保护而且有效地减少了该工艺步骤期间经常出现的色泽改变，更确切地说，色泽保持恒定，不存在消光和色强度损失。
在未染色或荧光增白聚酰胺材料情况下，在用本发明纺织助剂处理后没有观察到可以感知的白度降低。
还令人惊奇地发现，用本发明纺织助剂处理聚酰胺纤维材料还在抵抗臭氧、NOx和氯褪色性能方面带来了改善。
本发明因此还涉及一种改善未染色、荧光增白或用除金属配合物染料之外的活性或分散染料染色的天然或合成聚酰胺纤维材料抵抗臭氧、NOx和氯褪色性能的方法，其中的纤维材料用包含如上定义的式(1)化合物的液体处理。
所谓的贮存黄化，即，在纺织材料贮存期间出现的黄化，通过用本发明纺织助剂处理也可令人惊奇地有效减少。耐贮存黄化的性能一般使用Courtaulds黄化试验测量。用本发明纺织助剂处理的聚酰胺纤维材料具有高Courtaulds色牢度。
本发明纺织助剂可包含其他添加剂，例如，湿润剂、分散剂或pH调节剂。
下述实施例用于说明本发明。除非另有说明，温度以摄氏度给出，份数为重量份，而且百分比涉及重量百分比。重量份涉及以kg/l比例的体积份。
实施例1：处理荧光增白聚酰胺
(a)增白方法
PA 6.6纺织织物(textured tricot)通过染整法用包含2.0％UvitexNFW液(荧光增白剂，Ciba Specialty Chemicals)和1.0g/lUltravonEL(分散剂，Ciba Specialty Chemicals)的水性液体处理。用乙酸将pH调整为4.5。
液体比1∶20，30min/95℃
(b)助剂应用
增白后的织物通过轧染方法用包含不同数量的己二酸二酰肼水性液体处理。
液体吸收100％；在70℃下干燥
依照Ganz的白度：230
然后对所述织物进行成型试验(30s/210℃和60s/210℃)；成型试验后测量的白度值列于表1：
表1：
  己二酸二酰肼[g/l]   成型   白度(Ganz)
  0   30秒/210℃   152
  0   60秒/210℃   93
  2   30秒/210℃   198
  2   60秒/210℃   178
  4   30秒/210℃   205
  4   60秒/210℃   193
  8   30秒/210℃   208
  8   60秒/210℃   200
  12   30秒/210℃   208
  12   30秒/210℃   202
实施例2：处理染色聚酰胺
PA 6.6纺织织物通过染整法用包含0.02％ TectilonRed 2B(Ciba Specialty Chemicals)的水性液体染色。
所述织物然后通过轧染方法用包含20g/l己二酸二酰肼(液体吸收100％；pH＝4-5)的水性液体处理，在120℃下干燥2分钟，然后在不同条件下进行热定型。表2给出了与参照物(未处理的染色织物)对比的色泽偏差(DEF值)。
表2：
  参照物[DEF]   己二酸二酰肼[DEF]
  未处理的   0
  干燥的   0.53   0.67
  定型60秒/195℃   2.80   1.06
  定型30秒/210℃   3.72   1.31
  定型120秒/210℃   12.40   3.15
  定型240秒/210℃   17.98   4.70
实施例3：处理染色聚酰胺
PA 6.6纺织织物通过染整法用包含0.65％TerasilFlavin 8GFF(Ciba Specialty Chemicals)的水性液体染色。
所述织物然后通过轧染方法用包含20g/l己二酸二酰肼(液体吸收100％；pH＝4-5)的水性液体处理，在120℃下干燥2分钟，然后在不同条件下进行热定型。表3给出了与参照物(未处理的染色织物)对比的色泽偏差(DEF值)。
表3：
  参照物[DEF]   己二酸二酰肼[DEF]
  未处理的   0
  干燥的   0.20   1.23
  定型60秒/195℃   4.80   2.18
  定型30秒/210℃   5.95   3.18
  定型120秒/210℃   21.44   6.91
  定型240秒/210℃   32.35   8.99
实施例4：白色物品应用
按照实施例3所述，PA 6.6纺织织物通过轧染方法用包含20g/l己二酸二酰肼(液体吸收100％；pH＝4-5)的水性液体处理，在120℃下干燥2分钟，然后在不同条件下进行热定型。表4给出了与参照物(未处理的染色织物)对比的白度(Ganz)。
表4：
  参照物白度[DEF]   己二酸二酰肼[DEF]
  未处理的   67.7
  干燥的   68.3   62.7
  定型60秒/195℃   28.4   59.7
  定型30秒/210℃   13.5   44.4
  定型120秒/210℃   -73.6   22.6
  定型240秒/210℃   -157.7   -11.1
实施例5：助剂的耐洗性
按照实施例4所述，PA 6.6纺织织物用包含20g/l己二酸二酰肼(ADH)的水性液体处理，然后洗涤处理后的织物三次、六次和十次。
在成型试验后，依照Ganz测量白度(表5).
表5：
  成型                 白度(Ganz)参照(未处理)            白度(Ganz)用ADH处理
  在40℃洗涤   3次   6次   10次   3次   6次   10次
  定型30秒/210℃   27.6   19.2   23.0   39.9   41.4   40.1
  定型120秒/210℃   -114.1   -127.5   -136.9   8.5   10.1   -4.1
  定型240秒/210℃   -140.0   -129.9   -136.4   2.4   9.7   2.4
实施例6：染色聚酰胺的耐成型性
按照实施例2所述，PA 6.6纺织织物用TectilonRed 2B染色，然后用己二酸二酰肼处理。在成型试验后，测量与参照物(未处理的染色织物)对比的色泽偏差(DEF值)(表6)。
表6：
  参照物[DEF]   己二酸二酰肼[DEF]
  未处理的   0
  干燥的   1.30   1.45
  定型60秒/195℃   2.66   1.54
  定型30秒/210℃   8.35   2.00
  定型120秒/210℃   12.83   3.25
实施例7：染色聚酰胺耐成型性
按照实施例4所述，PA 6.6纺织织物用TerasilFlavin 8GFF染色，然后用己二酸二酰肼处理。在成型试验后，测量与参照物(未处理的染色织物)对比的色泽偏差(DEF值)(表7)。
表7：
  参照物[DEF]   己二酸二酰肼[DEF]
  未处理的   0
  干燥的   0.52   1.45
  定型60秒/195℃   4.25   2.22
  定型30秒/210℃   4.84   3.13
  定型120秒/210℃   8.16   4.93
实施例8：处理过的白色物品的耐成型性
按照实施例4所述，PA 6.6纺织织物(白色物品)用己二酸二酰肼处理。在成型试验后，测量与参照物(未处理的织物)对比的白度(Ganz)(表8)。
表8
  参照物白度(Ganz)   己二酸二酰肼白度(Ganz)
  未处理的   68.9
  干燥的   67.9   63.4
  定型60秒/195℃   26.7   45.8
  定型30秒/210℃   16.8   41.8
  定型120秒/210℃   1.1   27.4
实施例9：处理荧光增白聚酰胺
按照实施例1所述，PA 6.6纺织织物用UvitexNFW液体荧光增白，然后用己二酸二酰肼处理，在60℃下干燥，然后在不同条件下进行热定型。表9显示了依照Ganz测量的与参照物(荧光增白织物，未用ADH处理)对比的白度。
表9：
  白度(参照物)   白度(ADH处理)
  未处理的   243.6   204.9
  定型30秒/190℃   230.3   219.3
  定型60秒/190℃   150.7   210.6
  定型30秒/210℃   174.6   216.5
  定型60秒/210℃   -38.2   204.8
实施例10：处理荧光增白聚酰胺
按照实施例1所述，纺织织物通过染整法用UvitexNFW液体荧光增白。然后通过染整法用含2.0％N.N′-二苯基亚乙基二胺(DPEDA)的水性液体处理(pH＝5.0；液体比例1∶20；30分钟/98℃)，之后在不同条件下进行热定型。表10显示了依照Ganz测量的与参照物(荧光增白织物，未用DPEDA处理)对比的白度。
表10：
  白度(参照物)  白度(DPEDA处理)
  未处理的   243.6   197.3
  定型30秒/190℃   223.3   196.7
  定型60秒/190℃   150.7   175.5
  定型30秒/210℃   174.6   179.8
  定型60秒/210℃   -38.2   128.7

Claims (10)

1.一种改善未染色、荧光增白或用除金属配合物染料之外的活性或分散染料染色的天然或合成聚酰胺纤维材料的热稳定性的方法，其中的纤维材料用包含式(1)化合物的液体处理，
Y1-X-Y2    (1)
其中X是二价脂族或环脂族基，并且
Y1和Y2彼此独立地为-OH、-CO-OR1、-NR1R2、-CO-NH-NR1R2或-NH-CO-NH-NR1R2，
其中R1和R2彼此独立地为氢；未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C1-C12烷基；未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C5-C24-芳基；未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C6-C36芳烷基；或未取代的或被一个或多个羟基、氨基或羧基或卤素原子取代的C5-C24环烷基。
2.如权利要求1所述的方法，其包括使用其中X为亚乙基、四亚甲基、六亚甲基或八亚甲基的式(1)化合物。
3.如权利要求1所述的方法，其包括使用其中Y1和Y2为-NR1R2、-CO-NH-NR1R2或-NH-CO-NH-NR1R2，其中R1和R2为氢、C1-C12烷基或C5-C24芳基的式(1)化合物。
4.如权利要求1所述的方法，其包括使用其中Y1和Y2为-NR1R2、-CO-NH-NR1R2或-NH-CO-NH-NR1R2，其中R1和R2为氢、甲基或苯基的式(1)化合物。
5.如权利要求1所述的方法，其包括使用式(101)-(104)化合物：
Figure A2005800370610002C1
Figure A2005800370610003C1
6.如前述权利要求中任意一项所述的方法，其中式(1)化合物在所述液体中的存在量为0.1g/l-100g/l。
7.如前述权利要求中任意一项所述的方法，其中用包含式(1)化合物的液体处理纤维材料通过轧染方法进行。
8.如前述权利要求中任意一项所述的方法，其中处理荧光增白聚酰胺纤维材料。
9.如前述权利要求中任意一项所述的方法，其中用包含如权利要求1所述的式(1)化合物的液体处理已经用除金属配合物染料之外的活性或分散染料染色的聚酰胺纤维材料。
10.一种改善未染色、荧光增白或用除金属配合物染料之外的活性或分散染料染色的天然或合成聚酰胺纤维材料抵抗臭氧、NOx和氯褪色性能的方法，其中纤维材料用包含如权利要求1所述的式(1)化合物的液体处理。
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