CN101121827B - 具有硫烷基-s-三氮嗪反应基的反应性染料 - Google Patents

具有硫烷基-s-三氮嗪反应基的反应性染料 Download PDF

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CN101121827B
CN101121827B CN2006101121047A CN200610112104A CN101121827B CN 101121827 B CN101121827 B CN 101121827B CN 2006101121047 A CN2006101121047 A CN 2006101121047A CN 200610112104 A CN200610112104 A CN 200610112104A CN 101121827 B CN101121827 B CN 101121827B
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陈文政
夏贤忠
邓肯A·S·飞利浦
约翰A·泰勒
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Ethical International Trading & Warehousing (shanghai) Co Ltd
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Abstract

一种如下式(I)的具有硫烷基-s-三氮嗪反应基的反应性染料

Description

具有硫烷基-s-三氮嗪反应基的反应性染料
技术领域
本发明是有关一种新颖反应性染料，特别是关于一种具有硫烷基-s-三氮嗪的反应性染料。
背景技术
具有硫烷基-s-三氮嗪(alkylthio-s-triazine)单反应基反应性染料技术开发从1960年代一直到1980年代早期。主要是具有-s-三氮嗪(s-triazine)或嘧啶衍生物(pyramine)的硫代/硫磺单反应基反应性染料的技术，如英国专利GB 923068所公开。
1986年到1996年间虽有反应性染料的研究开发，但是反应性染料研究开发只局限在特定的染料发色团范围，如欧洲专利EP 0264878、日本专利JP 10-001618所公开。以一氯均三嗪(monochloro triazine)和乙烯砜(Vinylsulfone)作为双反应基的反应性染料，为现今60℃中温型反应性染料的市场主流，但由于两个反应基的活性相差很大，染色应用时，主要以乙烯砜反应基将染料固着到纤维素纤维，而一氯均三嗪反应基的利用率偏低，因为一氯均三嗪反应基是属于80℃固色的反应基。如果用中温型一氟均三嗪反应基取代一氯均三嗪，虽然可以和乙烯砜反应基的活性趋于一致，增加上色率，但三氟均三嗪(trifluoro triazine)的生产成本太高，染料产品的经济效益低。本发明提供以硫烷基做一氯均三嗪的取代基，提升反应基活性与乙烯砜相当，有效增加反应基利用率，染料表现高固着和优良染深性，而且比一氟均三嗪(monofluoro triazine)更具经济效益。本发明的新颖反应性染料可以表现出更好的反应性、固着率、染深性，以及具有更稳定的纤维和染料键结、更优良的水洗牢度、日光牢度和湿牢度特性。
利用本发明的硫烷基取代基提升一氯均三嗪的活性，搭配乙烯砜成为反应性一致的新双反应基染料，反应选择性高，可以成为高经济效益的高级中温型染料。
发明内容
本发明的目的在于提供一种具有硫烷基-s-三氮嗪反应基的反应性染料。
为实现上述目的，本发明提供的具有硫烷基-s-三氮嗪反应基的反应性染料如下式(I)所示：
Figure GA20177442200610112104701D00021
其中：
X、Y和Z为各自独立的选自由氢原子(hydrogen)、氯原子(chlorine)、羟基(hydroxy)、胺基(amino)、经取代的胺基、磺酸盐(sulfonate)、芳香族偶氮基(arylazo)、2-氯-4-烷硫三氮嗪-6-胺基(2-chloro-4-alkylthio-triazinyl-6-amino)、烷基(alkyl)、烷氧基(alkoxy)、α，β-卤丙酰基(α，β-halopropionyl)、α-卤丙烯酰基(α-haloacryloyl)、-B-SO2CH2CH2W、-B-SO2CH＝CH2、-SO2CH2CH2W及-SO2CH＝CH2所组成的群；
B为直链或-CONH-(CH2)i-或-O-(CH2)j-CONH-(CH2)k-，i、j和k为各自独立2到4的整数；
W为用碱处理可离去的基团，其选自包括：
Cl、-OSO3H、
Figure GA20177442200610112104701D00031
及季铵盐其中R9、R10、R11各自独立分别为C1～4烷基；
Q为C1-4烷基或经取代的C1-4烷基；
A为一个或多个染料发色团，具有一个或多个磺酸基；
a为1或2；
R为氢原子、C1～4烷基、或经羟基、C1～4烷氧基、或羧基(carboxyl)所取代的C1～4烷基。
本发明的式(I)反应性染料，其包含一个或多个染料发色团，可以连接一个或多个磺酸基(sulfo)和至少两个纤维反应基，其中一个纤维反应基必为2-氯-4-硫烷基-S-三嗪基(2-chloro-4-alkylthio-s-triazinyl)。
本发明的式(I)反应性染料，其中Q，较佳的，为未取代或经一至三个取代基取代的甲烷基或乙烷基，且该甲烷基、乙烷基上的取代基分别选自包括：卤素(halo)、氢氧基(hydroxyl)、磺酸基、氰基(cyano)、胺基(amino)、羰酰胺基(carbonamido)、羧基(carboxyl)、烷氧羰基(alkoxycarbonyl)、酰氧基(acyloxy)及烷氧基。
本发明的式(I)反应性染料，其中该染料发色团A，较佳的，选自包括：甲
Figure GA20177442200610112104701D00033
(formazan)、蒽醌(anthraquinone)、肽花青(phthalocyanine)、三苯二噁嗪(triphendioxazine)、单偶氮(monoazo)、双偶氮(disazo)、多偶氮(polyazo)及金属络合偶氮结构发色团所组成之群。
其中该肽花青(phthalocyanine)发色团，较佳的，为如下式的结构：
Figure GA20177442200610112104701D00034
其中Pc为铜肽花青基(copper phthalocyanine)或镍肽花青基(nickelphthalocyanine)，U为-OH和/或-NH2，E为苯基或乙烯基(ethylene)；c+d≤4。
其中该三苯二噁嗪(triphendioxazine)发色团，较佳的，选自包括：
Figure GA20177442200610112104701D00041
及
Figure GA20177442200610112104701D00042
所组成的族群，其中E为苯基或乙烯基(ethylene)。
其中该单偶氮(monoazo)发色团，较佳的，选自包括：
Figure GA20177442200610112104701D00043
Figure GA20177442200610112104701D00051
及
Figure GA20177442200610112104701D00062
所组成的族群，其中：
R1为C1～4烷基、C1～4烷氧基、羧基、磺酸基、-SO2CH2CH2W或-SO2CH＝CH2，W定义如前所述；
R2为C1～4烷基，C1～4烷氧基，胺基，乙酰基胺基(acetylamino)，脲基(ureido)或磺基；
R4为C1～4烷基或羧基；
m、o及p个别独立的分别为0、1、2或3。
其中该双偶氮(disazo)及多偶氮(polyazo)发色团，较佳的，选自包括：
Figure GA20177442200610112104701D00063
Figure GA20177442200610112104701D00071
所组成的族群，其中：
R8为C1～4烷基、C1～4烷氧基、羧基、磺酸基、乙酰基(acetyl)、乙酰基胺基、脲基、-SO2CH2CH2W或-SO2CH＝CH2，W定义如前所述；
q、r、s、t及u各自独立分别选自0、1、2或3；
R1、Y、m、o及p定义如前所述。
其中该金属络合偶氮结构发色团，较佳的，选自包括：
Figure GA20177442200610112104701D00072
及
所组成的族群，其中m及o定义如前所述。
其中，前述的式(I)为如下式(1)
Figure GA20177442200610112104701D00082
其中，前述的式(I)为如下式(2)
Figure GA20177442200610112104701D00083
其中，前述的式(I)为如下式(3)
Figure GA20177442200610112104701D00084
其中，前述的式(I)为如下式(38)
Figure GA20177442200610112104701D00085
本发明为了说明方便，在说明书中化合物皆以自由酸的形式表示，但本发明中的染料在被制造或使用时，常会以水溶性盐的形式存在，合适的盐可以是碱金属、碱土金属、铵盐或有机胺盐，其中较佳的为钠盐、钾盐、锂盐、铵盐或三乙醇胺(triethanolamine)盐。
本发明的染料适用于纤维材料，尤指纤维素纤维材料，以及含纤维素纤维的纤维材料的染色或印花。此纤维材料并无特殊限制，可以是天然或再生的纤维素纤维，例如棉、麻、亚麻、***、苎麻、黏液嫘萦，或是含纤维素系纤维的纤维材料。本发明的染料同样也适用于含羟基纤维的纤维掺混织物的染色和印花。
本发明的染料可以用各种方式固色于纤维上，特别是以水性染料溶液和印染糊形式。并以浸染、连染、冷压染、印染等方式进行染色与印花。
本发明的染色或印染可照一般公知、惯用的方法进行，浸染法(exhaustion dyeing)是采用熟知的无机中性盐(如无水硫酸钠及氯化钠)及熟知的酸结合剂(如碳酸钠、氢氧化钠)单独或混合使用。无机中性盐和碱的用量并不是很重要，无机中性盐和碱可以依传统方法一次或分次加入染浴中。此外，也可以依传统方法加入助染剂(如均染剂、缓染剂等)，染色温度通常是介于40℃-90℃，较佳的是40℃-70℃。
冷压染法是使欲染色的物质，利用熟知的无机中性盐(如无水硫酸钠及氯化钠)及熟知的酸结合剂(如碳酸钠、氢氧化钠)轧染，然后在室温下，使所得的物质成卷置形式进行染色。
连续染色法是使熟知的酸结合剂(如碳酸钠或碳酸氢钠)和轧染液混合，依常法使欲染色的物质进行轧染，然后使所得物质干热或汽蒸固色；两浴轧染法是以染料使欲染色的物质进行轧染，然后以熟知的无机中性盐(如硫酸钠或硅酸钠)处理，最好依常法将处理过的物质干燥或汽蒸固色。
织物印花法，例如有单相印花法，是以含有熟知酸结合剂(如碳酸氢钠)的印花浆，印在欲印花的物质上，并用干燥或汽蒸固色；两相印花法包含以印花浆欲印花的物质，将所得物质浸入在高温(90℃或以上)的含无机中性盐(如氯化钠)及熟知的酸结合剂(如氢氧化钠或碳酸钠)的溶液中固色。依本发明的方法并不局限前列的染色或印花法。
本发明的染料对纤维素纤维来讲，它是一种具产业价值的反应性染料，具备优良的固色能力，和非常优异的染深性，同时具备高度的洗净能力，并适用于广泛温度范围的染色，因此也适用于棉/聚酯掺混织物的染色。本发明的染料也适用于印染，特别适用于棉或含有毛或丝的掺混织物。在纤维素纤维材料上所进行的染色和印染可以得到各种染色特性良好的染物；尤其在染深性及水洗牢度，可得高质量的染色、印染或压染产品。
具体实施方式
本发明的染料，可由公知方法制备，其中重氮化反应、偶合和缩合反应常见于此领域的文献中，并且为本领域技术人员据以实施。
为方便更进一步说明起见，将列举以下实施例做更具体的说明。以下实例在说明本发明，本发明的申请专利范围并不会因此而受限制。其中化合物是以游离酸的形式表示，但其实际的形式有可能是金属盐，更可能是碱金属盐，尤其是钠盐，除非有特别说明，否则实施例中所使用的份数或百分比皆以重量为单位，温度以摄氏温度℃为单位。
实施例1
(a)取19.45份三聚氯氰(cyanuric chloride)分散于150份的0℃水中，然后加入31.9份2-胺基-5-萘酚-1，7-二磺酸(2-Amino-5-hydroxy-naphthalene-1，7-disulfonic acid)粉末，以15％碳酸钠(Na2CO3)水溶液将反应液pH值调整为3，自然升温至20℃后持温1～2小时备用。
(b)取9.7份硫乙醇酸(Thioglycolic acid)加入上述(a)所得的水溶液中，在20℃以18份碳酸钠(Na2CO3)粉末将反应液pH值调整为7～7.5之间，保持15分钟后用盐酸(HCl)水溶液调整反应液的pH值为6～6.5，经过常用的氯化钠(NaCl)盐析、过滤，取滤饼备用。
(c)取150份、0℃的水加入29.5份1-胺苯基-4-(β-乙烯砜)-2-磺酸(1-aminobenzene-4-(β-sulfatoethyl-sulfone)-2-sulfonic acid)和30份32％盐酸水溶液充分搅拌分散，之后快速加入7.2份的亚硝酸钠水溶液，控制在0～5℃下进行重氮化反应约1.5小时完成，加入上述(b)所得的滤饼，用碳酸氢钠缓慢调整反应pH值达到6～6.5，充分反应后经盐析、过滤和干燥得到橘色产物的结构如下式(1)
Figure GA20177442200610112104701D00111
实施例2
(a)取19.45份三聚氯氰分散于150份的0℃水中，加入31.5份1-萘酚-8-胺基-3，6-二磺酸(1-Naphthol-8-amino-3，6-disulfonic acid)粉末，以15％碳酸钠水溶液将反应液pH值调整为3，自然升温至20℃后持温1～2小时备用。
(b)取9.7份硫乙醇酸加入上述(a)所得的水溶液中，在20℃以18份碳酸钠将反应液pH值调整为7～7.5，保持15分钟后用盐酸水溶液调整混合液的pH值为6～6.5，经过常用的氯化钠盐析、过滤，取滤饼备用。
(c)取150份、0℃的水加入29份对磺乙硫酸胺(p-Aminosulfoethylsulfate)和50份32％盐酸水溶液充分搅拌分散，之后快速加入7.2份的亚硝酸钠水溶液，控制在0～5℃下进行重氮化反应约1.5小时完成，加入上述(b)所得的滤饼，用碳酸氢钠缓慢调整反应pH值达到6～6.5，充分反应后经盐析、过滤和干燥得到红色产物的结构如下式(2)
Figure GA20177442200610112104701D00121
实施例3
(a)取19.45份三聚氯氰分散于150份的0℃水中，加入18.8份1，3-苯二胺(1，3-Phenylenediamine)粉末，以15％碳酸钠水溶液将反应液pH值调整为3，自然升温至20℃后持温1～2小时备用。
(b)取9.7份硫乙醇酸加入上述(a)所得的水溶液中，在20℃以18份碳酸钠将反应液pH值调整为7～7.5，保持15分钟后用盐酸水溶液调整反应液的pH值为6～6.5，经过常用的氯化钠盐析、过滤，取滤饼备用。
(c)取150份、0℃的水加入19.5份上述(b)所得的滤饼和25份32％盐酸的水溶液充分搅拌分散，之后快速加入3.6份的亚硝酸钠水溶液，控制在0～5℃下进行重氮化反应约1.5小时完成，加入16.0份4-胺基-5-羟基-2，7-萘二磺酸(4-amino-5-hydroxy-2，7-naphthalenedisulfonic acid)粉末，用10份碳酸氢钠缓慢调整反应pH值达到3，充分反应后经盐析、过滤，取滤饼备用。
(d)取150份、0℃的水加入16.55份1-胺苯基-4-(β-乙烯砜)-2-磺酸(1-aminobenzene-4-(β-sulfatoethyl-sulfone)-2-sulfonic acid)和12.6份32％盐酸的水溶液充分搅拌分散，之后快速加入3.7份的亚硝酸钠水溶液，控制在0～5℃下进行重氮化反应约1～2小时完成，重氮盐溶液加入上述(c)所得的滤饼，用碳酸钠自然调整反应pH值为5～6，充分反应后经盐析、过滤和干燥得到深蓝色产物的结构如下式(3)
参照实施例1～3合成方式，可获得以下实施例4-37的染料结构式(表中色相为该染料溶于水溶液中的颜色)
Figure GA20177442200610112104701D00141
Figure GA20177442200610112104701D00151
Figure GA20177442200610112104701D00161
Figure GA20177442200610112104701D00171
Figure GA20177442200610112104701D00181
Figure GA20177442200610112104701D00191
Figure GA20177442200610112104701D00201
实施例38
(a)取19.45份三聚氯氰分散于150份的0℃水中，加入18.8份1，3-苯二胺(1，3-Phenylenediamine)粉末，以15％碳酸钠水溶液将反应液pH值调整为3，自然升温至20℃后持温1～2小时备用。
(b)取9.7份硫乙醇酸加入上述(a)所得水溶液中，在20℃以18份碳酸钠粉末将反应液pH值调整为7～7.5，保持15分钟后用盐酸水溶液调整反应液的pH值为6～6.5，经过常用的氯化钠盐析、过滤，取滤饼备用。
(c)取150份、0℃的水加入19.5份上述(b)所得的滤饼和25份32％盐酸水溶液充分搅拌分散，的后快速加入3.6份的亚硝酸钠水溶液，控制在0～5℃下进行重氮化反应约1.5小时完成，加入8.0份4-胺基-5-羟基-2，7-萘二磺酸(4-amino-5-hydroxy-2，7-naphthalene-disulfonic acid)粉末，用10份碳酸氢钠缓慢调整反应pH值达到3使偶合反应完全，待4-胺基-5-羟基-2，7-萘二磺酸(4-amino-5-hydroxy-2，7-naphthalene-disulfonic acid)消耗完后，加入3.5份碳酸钠使pH值维持在6.5，充分反应后经盐析、过滤和干燥得到藏青色产物的结构如下式38
Figure GA20177442200610112104701D00211
参照实施例38合成方式，可获得以下实施例39-47的染料结构式(表中色相为该染料溶于水溶液中的颜色)
Figure GA20177442200610112104701D00212
Figure GA20177442200610112104701D00221
试验例1
取0.25份实施例1所制备的染料溶于250毫升水中做成母液，取上述母液40毫升置于染色瓶中，然后放入棉织物2份，再放入芒硝2.4份，最后放入32％纯碱溶液2.5毫升；将染瓶放入60℃的水平震荡染色机中，保温60分钟。然后将所得到金黄色染物先经冷水洗，再经沸腾热水洗10分钟，然后经沸腾的非离子清洁剂皂洗10分钟，最后再用冷水洗清一次，干燥后所制得的橘色染物具备优良的染深性及上色率。
试验例2
取尿素100份，间-硝基苯磺酸钠盐10份，小苏打20份，海藻酸钠55份，温水815份合计1000份，经搅拌配制可得助剂糊。
取3份实施例2所制备的染料洒于上述100份的助剂糊中，并快速搅拌。以100mesh的45度斜纹版印花网版覆盖在一适当大小的丝光棉斜纹布上，再将上述色糊置于网版上并刮过。
将刮好的布放到65℃烘箱内5分钟烘干；将烘干好的布放入蒸箱以常压饱和蒸气102～105℃蒸处10分钟。
然后将所得到玫瑰红色染物先经冷水洗，再经沸腾热水洗10分钟，然后再以沸腾的非离子清洁剂皂洗10分钟，最后再用冷水洗清一次，干燥后可得到红色染物具备优良的染深性及上色率。
试验例3
取3份实施例3所制备的染料溶于100毫升水中，配制成30份/升压染液；取碱剂25毫升(使用苛性钠15毫升/升和芒硝30份/升)加入于压染液中均匀搅拌，所得混合液倒入罗拉(Roller)压染器中，然后将棉织物经过罗拉压染后，再卷成轴状。此形态棉织物在室温下储存4小时。然后，将所得到橘色染物先经冷水洗，再经沸腾热水洗10分钟，然后经沸腾的非离子清洁剂皂洗10分钟，最后再用冷水洗清一次，干燥后可得到深蓝色染物具备优良的染深性及上色率。
综上所述，本发明确能由所描述的技术思想以达到发明目的。
以上所描述的乃较佳实施例，举凡局部的变更或修饰而源于本发明的技术思想而为熟悉该项技术的人士所易于推知的，俱不脱本发明的专利权范围。

Claims (10)

1.一种如下式(I)的具有硫烷基-s-三氮嗪反应基的反应性染料，其包含一个或多个染料发色团，其连接一个或多个磺酸基和至少两个纤维反应基，其中一个纤维反应基为2-氯-4-硫烷基-s-三嗪基，
Figure FA20191754200610112104701C00011
其中：
X、Y和Z各自独立的选自由氢原子、氯原子、羟基、胺基、经取代的胺基、磺酸盐、芳香族偶氮基、2-氯-4-烷硫三氮嗪-6-胺基、烷基、烷氧基、α，β-卤丙酰基、α-卤丙烯酰基、-B-SO2CH2CH2W、-B-SO2CH＝CH2、-SO2CH2CH2W及-SO2CH＝CH2所组成之群；且
X、Y和Z其中之一至少为：2-氯-4-烷硫三氮嗪-6-胺基、α，β-卤丙酰基、α-卤丙烯酰基、-B-SO2CH2CH2W、-B-SO2CH＝CH2、-SO2CH2CH2W或-SO2CH＝CH2；
B为直链或-CONH-(CH2)i-或-O-(CH2)j-CONH-(CH2)k-，i、j和k为各自独立2到4的整数；
W为用碱处理可离去的基团，其选自包括：
Cl、-OSO3H、
Figure FA20191754200610112104701C00012
、及季铵盐
Figure FA20191754200610112104701C00013
，其中R9、R10、R11各自独立分别为C1～4烷基；
Q为C1-4烷基或经一至三个取代基取代的甲烷基、乙烷基，且该甲烷、乙烷基上的取代基分别选自包括：卤素、氢氧基、磺酸基、氰基、胺基、羰酰胺基、羧基、烷氧羰基、酰氧基及烷氧基；
A为一个或多个染料发色团，具有一个或多个磺酸基，其选自由甲
Figure FA20191754200610112104701C00021
蒽醌、肽花青、三苯二噁嗪、单偶氮、双偶氮、多偶氮及金属络合偶氮结构发色团所组成之群；
其中该双偶氮及多偶氮发色团选自包括：
所组成的族群，其中：
R8为C1～4烷基、C1～4烷氧基、羧基、磺酸基、乙酰基、乙酰基胺基、脲基、-SO2CH2CH2W或-SO2CH＝CH2，W定义如前所述；
p为1或2；
q、r、s、t及u各自独立分别选自0、1、2或3；
m及o各自独立的分别为0、1、2或3；
a为1或2；
R为氢原子、C1～4烷基、或经羟基、C1～4烷氧基、或羧基所取代的C1～4烷基。
2.如权利要求1的反应性染料，其中Q为甲烷基、乙烷基或经一至三个取代基取代的甲烷基、乙烷基，且该甲烷基、乙烷基上的取代基分别选自包括：卤素、氢氧基、磺酸基、氰基、胺基、羰酰胺基、羧基、烷氧羰基、酰氧基及烷氧基。
3.如权利要求1的反应性染料，其中该肽花青发色团为如下式的结构：
其中Pc为铜肽花青基或镍肽花青基，U为-OH和/或-NH2，E为苯基或乙烯基；c+d≤4。
4.如权利要求1的反应性染料，其中该三苯二噁嗪发色团选自包括：
Figure FA20191754200610112104701C00032
Figure FA20191754200610112104701C00041
所组成的族群，其中E为苯基或乙烯基。
5.如权利要求1的反应性染料，其中该单偶氮发色团选自包括：
所组成的族群；
其中
R1为C1～4烷基、C1～4烷氧基、羧基、磺酸基、-SO2CH2CH2W或-SO2CH＝CH2，W定义如权利要求1所述；
R2为C1～4烷基、C1～4烷氧基、胺基、乙酰基胺基、脲基或磺基；
R4为C1～4烷基或羧基；
m、o及p个别独立的分别为0、1、2或3。
6.如权利要求1的反应性染料，其中，该金属络合偶氮结构发色团选自包括：
Figure FA20191754200610112104701C00061
所组成的族群，其中m及o定义如权利要求5所述。
7.如权利要求1的反应性染料，其中该式(I)为如下式(1)
Figure FA20191754200610112104701C00062
8.如权利要求1的反应性染料，其中该式(I)为如下式(2)
Figure FA20191754200610112104701C00063
9.如权利要求1的反应性染料，其中该式(I)为如下式(3)
Figure FA20191754200610112104701C00071
10.如权利要求1的反应性染料，其中该式(I)为如下式(38)
Figure FA20191754200610112104701C00072
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