CN102046875B - 用靛白泡沫对经纱染色的方法 - Google Patents
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Abstract
本发明涉及用靛蓝对纤维质经纱染色的一种方法，该方法通过将靛白泡沫施用到经纱上并且随后将靛白氧化成靛蓝，其中使这些经纱通过一个入口引入一个密封的泡沫发生室，并且在它们通过一个出口从该泡沫发生室再出来之前在其中对它们施加靛白泡沫，这些经纱的纵向张力受到闭环控制，使它们在该泡沫发生室内处于一种自由悬浮的状态。
Description
(一)技术领域
本发明涉及用靛蓝染色的技术领域。
(二)背景技术
已知，靛蓝在远古时代就是对纺织材料进行染色的一种有用的染料。现如今，它特别是用于在牛仔布物品(例如像牛仔裤)的生产中对经纱进行染色。
靛蓝是水不可溶的并且对纤维不具有亲和力，并且因此必须首先将其还原成水溶性的无色形式，该无色形式对纤维具有适当的亲和力并且在它已经进入有待染色的材料上以后，它被氧化返回靛蓝颜料。
连二亚硫酸钠是用于还原靛蓝的还原剂的一个实例，但也可以使用其他还原剂例如二氧化硫脲以及羟丙酮。然而，更有利的是通过催化氢化进行还原作用以获得靛白的溶液，该靛白的溶液可以直接计量加入染浴中，参见EP 0692042B1。
将该靛白氧化返回靛蓝倾向于非常容易地进行，这样，在该靛白已经进入之后，有待染色的材料充分暴露于大气中的氧中即可。然而，靛白的迅速氧化性具有以下缺点，在另一方面，在许多情况下必需将还原剂加入染浴中以防止过早氧化，并且通过催化氢化获得的上述靛蓝溶液总体上必须在空气不存在时运输和储藏。
因为靛白对于有待染色的纤维材料仅仅具有有限的亲和力，所以必须不止一次地将纤维以四到八次的形式通过浸渍浴并且随后在空气中氧化进行染色直到它具有所希望的色调深度。因此，该方法是相对复杂的并且此外，涉及最终必须经受废水处理的大量的液体。
另一个缺点是所需要的染色机非常大并且具有105米到500米的经纱片长度。
将发泡的着色剂或助剂材料施用到连续的纺织材料是已知的并且描述在例如DE2523062和EP 0162018A1中。后一个参考文献涉及一种方法，其中将纤维质纺织材料用一种发泡的水性制品进行处理，该发泡的水性制品包括一种还原性还原染料作为着色剂。
EP 1591578A2披露了一种方法，其中已经对一种纤维质纺织材料在至少一面施用了一种含靛白的泡沫，并且随后暴露于一种氧化介质中，即，优选空气。借助喷嘴将泡沫发生器中产生的泡沫施用到纺织材料上。此方法的一个特别的优点是织物的前面和后面可以用不同的染料或至少以不同的色调进行染色，从而提供特殊效果。
然而，通过遵循这种方法对经纱或经纱的开放的片(open sheet)进行染色实际上是个很困难的任务，并且更特别地，不能导致对经纱进行均匀的染色。
出人意料地，现在已发现，即使经纱也可以非常成功地借助于靛白泡沫进行染色。
(三)发明内容
本发明涉及一种用靛蓝对纤维质经纱进行染色的方法，该方法是通过将一种靛白泡沫施用到这些经纱上并且随后将该靛白氧化成靛蓝，其中将这些经纱通过一个入口引入一个密封的泡沫发生室，并且在它们通过一个出口从该泡沫发生室再出来之前在其中对它们施加靛白泡沫，这些经纱的纵向张力受到闭环控制使它们在该泡沫发生室内处于一种自由悬浮的状态。
在此，特别的纤维质经纱是棉经纱，而且还有棉与一些材料(如聚酯和聚酰胺)的混合物组成的经纱。
靛白泡沫(例如)通过在一种可商购的泡沫发生器中借助一种惰性气体对靛白的水溶液进行发泡可获得。靛白的水溶液通过用一种还原剂，特别是用连二亚硫酸钠，对靛蓝进行还原可获得。然而，给予优选的是使用一种可商购的所谓的靛蓝溶液，该靛蓝溶液是通过靛蓝的催化氢化制备的并且特别地具有20％至40％的靛蓝浓度。优选可以将靛蓝溶液直接从罐式容器(其中的靛蓝溶液由厂商提供)进料到泡沫发生器。可能的情况是还必须为泡沫发生器供给附加的水。优选地，此附加的水是首先被除气的并且然后与一种惰性气体(优选氮气)混合。
优选所使用的惰性气体是氮气，但也可以是任何其他惰性气体。
对泡沫发生器特别有利的是与二氧化碳连同惰性气体(特别是氮气)进行混合，并且由此来降低泡沫的pH值并且提高靛白对经纱的亲和力。基于该惰性气体，二氧化碳优选是以按体积计5％到80％的量使用，更优选是以按体积计20％到50％的量。泡沫的pH值优选是在从12.6到10.4的范围内，并且更优选是在从11.6到11.0的范围内。
总体来说，发泡是在一个成泡剂的辅助下进行的。有用的成泡剂特别是包括已知的并且可商购的阴离子表面活性剂或非离子型表面活性剂。例如从EP 0162018可辨识出适当的表面活性剂。
发泡可以在另外的助剂的存在下进一步进行。例如可以加入能够提高靛白渗透入经纱的湿润剂。此类湿润剂是可商购的，并且特别有用的是磷酸的单酯和二酯与(例如)2-乙基己醇的混合物。
基于有待发泡的混合物，湿润剂优选以1％到20％，更优选2％到8％的量使用。
发泡可以在使坚牢度发生改进的助剂、以及还有在有害气体(如臭氧或氮氧化物)的影响下使靛蓝染色的纺织材料的发黄最小化的助剂的存在下进一步进行。此类助剂是可得的。
有用的改进坚牢度的助剂包括例如能够在纺织材料表面上交联的活性树脂。此时将发现特别有利的是使用环氧氯丙烷改性的聚酰胺类或聚酰胺型胺类。
有用的黄度抑制剂包括例如脂肪酸与氨基醇的缩合产物。在此，优选的反应组分包括例如硬脂酸、动物脂肪酸以及油酸以及还有二乙醇胺和三乙醇胺以及还有N-(氨乙基)乙醇胺。另外有利的是当反应产物中的氮在第二反应步骤中还被季铵化时。所使用的季铵化剂包括(例如)硫酸二甲酯或对甲苯磺酸甲酯。此外，具有长链烃基链并且形成阻挡层的聚合物作为黄度抑制剂也找到了应用。这些包括(例如)聚乙烯以及还有具有烃基侧链的聚合物，实例是聚丙烯酸酯和聚氨酯。烃基链应优选具有多于12个碳原子的长度，以便可以形成一个有效的阻挡层。
基于有待发泡的混合物，所提及的助剂优选是以1％到15％，并且更优选2％到8％的量使用。
泡沫发生器是已知的并且可以静态地或优选动态地运行。例如，它们被描述于DE 2523062和US 4,118,526中，并且是可商购的。
优选是将泡沫维持在恒温下，在这种情况下，15℃到70℃、特别是25℃到40℃的温度是特别优选的。对此目的特别有帮助的是为该泡沫发生器装备一个双壁的壳体，一种传热介质循环通过该双壁的壳体以维持所希望的温度。
将靛白泡沫在泡沫发生室内施用到这些经纱上。为此，该泡沫发生室装备有或连接到至少一个适当的靛白泡沫涂布装置上，该涂布装置由泡沫发生器供料。所使用的涂布装置可以是将泡沫均匀地挤压或抽吸到这些经纱上的任何装置。此类涂布装置是已知的并且描述在例如DE 2523062中。
优选的涂布装置是那些包括例如在US 4,655,056和EP 1065308A2中描述的一个抛物线形分配室的装置。
优选的是，在本发明的方法中，多个涂布装置(特别是2到5个)以短距离间隔开各自横向地配置到经纱片上，这样该泡沫发生室在经纱片的整个宽度上均匀地提供泡沫。有利的是在此连接中所有涂布装置由一个泡沫发生器供料。
泡沫发生室理想地是在维度上很小并且尽可能严密地封住经纱片。对于经纱片来说，入口和出口有利地是缝隙形状的，这样经纱片可以从中穿过而在顶部或底部不发生接触。
为防止大气中的氧进入该泡沫发生室，优选的是在入口的上游和出口的下游配置多个气封。
在本发明方法的一个优选的实施方案中，在马上要进入该泡沫发生室之前将该经纱片大幅度地冷却。更特别地，将该经纱片冷却到25℃到-10℃，更优选15℃到-5℃的温度。
冷却可以按照任何已知的冷却方法进行，但给予优选的是使用通过冷却缸操作的接触式冷却。特别优选的是通过使经纱片与一种冷却液(例如液氨，或特别是液氮)进行简单的直接接触来进行冷却。
特别优选的是通过对泡沫和经纱片温度进行闭环控制来保持靛白泡沫和经纱片之间的温差恒定。优选的是10℃到70℃、特别是15℃到40℃的温差。
在本发明方法的一个进一步优选的实施方案中，在染色之前，使经纱片经受一个预处理。在此预处理中，可以将助剂和/或着色剂施用到经纱片上。例如，助剂是以上描述的可商购的湿润剂以及还有以上也已描述的坚牢度改进剂。
着色剂是(例如)常规的硫化染料、还原染料、活性染料、以及直接染料。
预处理典型地是跟随有一个干燥步骤，该干燥步骤进而又跟随有一个染色步骤。
本发明的方法特别是以经纱片单次通过泡沫发生室而提供了一种可接受的色调深度。其结果是，产生了相当可观地更少量的废水，这样便实现了相当可观的经济优势。
应该认识到，尽管如此，仍有可能将经纱片按希望的次数通过该泡沫发生室。
Claims (11)
1.一种用靛蓝对纤维质经纱进行染色的方法，该方法是通过将一种靛白泡沫施用到这些经纱上并且随后将该靛白氧化成靛蓝，其中将这些经纱通过一个入口引入一个密封的泡沫发生室，并且在它们通过一个出口从该泡沫发生室再出来之前在其中对它们施加靛白泡沫，这些经纱的纵向张力受到闭环控制使它们在该泡沫发生室内处于一种自由悬浮的状态。
2.如权利要求1所述的方法，其中该泡沫发生室装备有或连接到至少一个适当的靛白泡沫涂布装置上，该涂布装置由泡沫发生器供料。
3.如权利要求1或2所述的方法，其中该泡沫发生室装备有或连接到多个涂布装置上，具体是2至5个，这些涂布装置以短距离间隔开各自横向地配置到经纱片上。
4.如权利要求3所述的方法，其中该泡沫发生室装备有或连接到2至5个涂布装置上。
5.如权利要求1、2或4所述的方法，其中在该泡沫发生室的入口的上游和出口的下游配置多个气封。
6.如权利要求3所述的方法，其中在该泡沫发生室的入口的上游和出口的下游配置多个气封。
7.如权利要求1、2、4或6所述的方法，其中在马上要进入该泡沫发生室之前将该经纱片大幅度地冷却。
8.如权利要求3所述的方法，其中在马上要进入该泡沫发生室之前将该经纱片大幅度地冷却。
9.如权利要求5所述的方法，其中在马上要进入该泡沫发生室之前将该经纱片大幅度地冷却。
10.如权利要求7所述的方法，其中在马上要进入该泡沫发生室之前将该经纱片冷却到25℃至-10℃的温度。
11.如权利要求8～10之一所述的方法，其中在马上要进入该泡沫发生室之前将该经纱片冷却到25℃至-10℃的温度。
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| PCT/EP2009/056709 WO2010000551A2 (en) | 2008-06-09 | 2009-06-02 | Dyeing warp yarns with leucoindigo foam |
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| US20210189643A1 (en) * | 2017-12-21 | 2021-06-24 | Sudhakar Puvvada | Foam dyeing methods using modified indigo compounds |
| WO2020150408A1 (en) * | 2019-01-16 | 2020-07-23 | Indigo Mill Designs, Inc. | Systems and methods for preparing deoxygenated dye compositions |
| CN110016816A (zh) * | 2019-03-13 | 2019-07-16 | 广东前进牛仔布有限公司 | 一种靛蓝染色方法 |
| CN110106723B (zh) * | 2019-05-16 | 2021-10-26 | 广东溢达纺织有限公司 | 一种还原染料或硫化染料的成衣染色方法 |
| CN113756116A (zh) * | 2021-03-31 | 2021-12-07 | 江阴华祥机电科技有限公司 | 一种无水还原性染色工艺 |
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| CN1129008A (zh) * | 1993-08-13 | 1996-08-14 | Basf公司 | 粒状靛白制备物 |
| US6355073B1 (en) * | 1996-04-06 | 2002-03-12 | Gullshield Ltd. | Method and device for continuous dyeing of warp ends |
| CN1498921A (zh) * | 2002-11-11 | 2004-05-26 | 北京慧聚英力医药化学技术发展有限公 | 一种吲哚酚盐在原位直接染色上的用途 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1129008A (zh) * | 1993-08-13 | 1996-08-14 | Basf公司 | 粒状靛白制备物 |
| US6355073B1 (en) * | 1996-04-06 | 2002-03-12 | Gullshield Ltd. | Method and device for continuous dyeing of warp ends |
| CN1498921A (zh) * | 2002-11-11 | 2004-05-26 | 北京慧聚英力医药化学技术发展有限公 | 一种吲哚酚盐在原位直接染色上的用途 |
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| BRPI0914987A2 (pt) | 2015-10-27 |
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