CN1200977C - 偶氮染料,它们的制备方法及其在疏水性纤维材料染色和印染中的应用 - Google Patents
偶氮染料,它们的制备方法及其在疏水性纤维材料染色和印染中的应用 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
- C09B29/0823—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by CN
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
- C09B29/0813—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by OH, O-C(=X)-R, O-C(=X)-X-R, O-R (X being O,S,NR; R being hydrocarbonyl)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/921—Cellulose ester or ether
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/922—Polyester fiber
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
本发明涉及化学式(1)的染料，其中，R1是氢、溴、氯、氰基；R2是氢、乙基、乙酰氨基；R3是未被取代的乙基，或者是被氰基或酰氧基取代的乙基；R4是未被取代的乙基或者是被氰基或酰氧基取代的乙基。本发明也涉及这些染料的制备方法，以及它们在疏水性纤维材料染色或印染中的应用。
Description
本发明涉及偶氮染料，它们的制备方法以及它们在半合成的或合成的疏水性纤维材料印染中的应用。
偶氮染料及其在半合成或合成的疏水性纤维材料印染中的应用是已知的。但是，我们也知道，此类染料并不总能充分满足最高要求，尤其是在高温条件下耐光照和/或颜色强度方面。因此，需要一些新的染料。它们有强烈的着色能力，高温条件下耐光照，并有耐各方面影响因素，而不褪色的性质。
现在已经发现，本发明的染料能较好地达到上述要求的指标。
本发明涉及化学式(I)的一些染料
其中
R1是氢、溴、氯、氰基，
R2是氢、甲基和乙酰氨基，
R3是未被取代的乙基，或者是被氰基或酰氧基取代的乙基，
R4是未被取代的乙基，或者是被氰基或酰氧基取代的乙基，
R1优选的是溴或氰基，
R2优选的是氢或乙酰氨基，更优选的是氢，
R3优选的是氰乙基，
R4优选的是氰乙基，
下列化学式的染料提供作为特别优选：
本发明也涉及到化学式(1)的染料的制备方法。例如，按照本发明，染料制备方法如下：
将化学式(50)的化合物，
按常规方法进行重氮化，然后同偶合成分化学式(51)进行偶联
其中R1、R2、R3和R4定义如上。
化学式(50)化合物的重氮化，实际上是按已知方法来进行。例如，在酸性介质中(含有盐酸或硫酸的水溶液中)用亚硝酸钠进行重氮化。也可能采用其它重氮化试剂，例如亚硝酰基硫酸，来实现重氮化。在此重氮化过程中，反应介质里也可能有其它的酸，例如磷酸、硫酸、乙酸、丙酸或盐酸，或者这些酸的混合物，例如丙酸和醋酸的混合物。反应温度-10℃到30℃之间，有利于重氮化的进行，例如从-10℃到室温。
化学式(50)的重氮化合物同化学式(51)的偶合成分的偶联，也通过已知方法进行，例如，在酸性条件下，在水溶液中或水-有机介质中进行。反应温度在-10℃到30℃之间，特别是低于10℃，有利于偶联反应的进行。采用的酸，例如盐酸、醋酸、丙酸、硫酸和磷酸。
化学式(50)的化合物是已知的，也可以通过已知的方法来制备。化学式(51)的偶合成分也是已知的，亦可通过已知方法来制备。
本发明的染料，能用来染色，或者用来印染半合成的，尤其是合成的疏水性纤维材料，特别适合于纺织品。含有这类半合成的和/或合成的疏水性纺织材料混合物的纺织品，也能用本发明的染料来染色或印染。
考虑的半合成纺织材料，特别是指二代醋酸纤维素和三醋酸纤维素。
合成的疏水性纺织材料，尤其是直链的、芳香聚酯，例如对苯二酸和二元醇，特别是1，2-亚乙基二醇的聚酯，或者是对苯二酸同1，4-二(羟甲基)环己烷的缩合产物；聚碳酸酯，例如α，α-二甲基-4，4-二羟基-二苯基甲烷和光气的聚酯，聚氯乙烯纤维以及聚酰胺纤维。
本发明染料对纺织材料染色应用，可按照已知的染色方法进行。例如，聚酯纤维材料的染色是在80-140℃温度下，在通常的阴离子或非离子分散剂以及任选的常规膨胀剂(载体)存在条件下，在水分散液中的吸尽方法(exhaust process)。二代醋酸纤维素染色，优选地是在65-85℃下进行，三醋酸纤维素染色的温度直到115℃。
本发明的染料，将不会使同时存在于染缸中的毛织品和棉织品着色，或者使那些物品染上很浅的颜色(颜色能很好地保留住)，这样，它们能用来很好地印染聚酯/毛和聚酯/纤维素纤维混纺的纺织物。
本发明的染料适合于按照热溶胶方法进行染色，采用批式的或连续的方法，也适合于采用印染方法。批式方法是优选的。母液的比率取决于设备的种类、基质以及构成的形式。但是选择的范围很宽，例如1∶4到1∶100，优选的是1∶6到1∶25。
上述纺织材料可以是多种加工形式，例如纤维，纱线或者是无纺制品，也可以是织成品或编织品。
本发明的染料在使用前最好转变成一定形式的制剂形式。为此，将染料磨成平均0.1-10微米的颗粒。研磨可在分散剂存在的条件下进行。例如，将干燥染料同分散剂一起研磨，或者同分散剂一起和成浆糊状，然后真空干燥或者喷雾干燥。如此获得的制剂，能在加水后使用，制成印染浆糊和染料浴。
为了印染，可采用通常的增稠剂，例如改进过或未改进的天然产物，如藻酸盐，糊精、阿拉伯胶、结晶胶、刺槐豆粉、黄蓍胶、羧甲基纤维素、羟乙基纤维素、淀粉或合成产品，例如聚丙烯酰胺、聚丙烯酸或其共聚物，或者聚乙烯醇。
按照本发明的染料印染上面提到的材料，尤其是聚酯材料，能使它们色调均匀，有很好的耐用性，如耐光照、特别是耐高温下的光照，耐热固化，耐打褶、耐氯的腐蚀，耐潮湿、如耐水、耐汗浸和洗涤等。染上的颜色有独特的耐磨性质。
本发明的染料能很好地与其它染料混合，产生混合色调。
本发明的染料特别适合作为三色染色或印染技术的染料。
本发明的染料也很适用于印染那些采用超临界CO2处理的疏水性纺织材料。
本发明也涉及本发明染料的上述应用，以及给半合成或合成的疏水性纤维物质染色或印染的方法，尤其是用这些材料织成的纺织品的染色或印染方法。该方法包括将本发明染料施用到所述材料上，或将其掺入这些材料中。所谓的疏水性纤维物质，首先是指聚酯纤维纺织品。另外，能够按照本发明方法处理的基质以及该方法中优选的条件，在上面本发明染料的使用方法中有详细介绍。
本发明也涉及上述方法染色或印染的疏水性纤维物质，尤其是聚酯纺织材料。
本发明的染料也适用于现代翻印方法，例如传热印染(thermotransfer printing)。
下面的举例用以解释本发明。在各例中，除特别说明外，份额和百分数均按重量计算。温度为摄氏温度。重量份和体积份之间的关系与克和立方厘米之间的关系相同。
例1：
A，在实验室反应装置内，将103.0g 2-氨基-5-硝基苯的三氟化物在室温下溶介于625ml甲醇中。然后，在2小时内，将95.9g溴的250ml甲醇溶液滴加到上述溶液中，室温下，将反应混合物搅拌24小时。
用64ml的30％NaOH水溶液调pH到7-8；加600ml水稀释混合物，真空抽滤出再沉淀产物，水洗后，60℃下真空干燥。得到126.4g化学式(50a)的化合物。
B，在实验室反应装置中，在20-30℃温度下，30分钟时间内，将57.0g化学式(50a)的化合物，在搅拌条件下，加入到100g 97％硫酸中，然后冷却到0℃。然后在0-5℃下，30分钟时间内，将65.0g的40％亚硝酰基硫酸溶液加入反应物中，在亚硝酸盐稍微过量情况下。反应完成时，搅拌5小时。加氨基磺酸搅拌15分钟，消除过剩的亚硝酸盐。
C，在升高的温度下，1小时过程中，将39.8g N，N-二(2-氰乙基)苯胺溶于500g的80％醋酸中。通过添加50g冰，将溶液冷却到5℃。再在0到5℃温度下，15分钟过程中，将“B”制成的重氮化物加入到反应混合物中。通过加入200g冰，控制温度的升高。
加完所有材料后，反应混合物再搅拌3小时。
得到的偶氮染料加水再沉淀折出、过滤、反复用水洗涤，并干燥。得到96.0g化学式(106)的染料，用它染聚酯材料，呈亮橙色的色调。
D，将20.4g化学式(106)的染料和300ml 1-甲基-2-吡咯烷酮加入到实验室反应装置内，室温下搅拌22小时，将温度提高到40℃，混合物再搅拌2小时。室温下加入3.6g CuCN。混合物搅拌4小时，再滴加45ml水，再搅拌30分钟。抽滤出沉淀的染料。用水，15％氨水，再用水洗到中性，最后干燥。得到16.0g化学式(100)的染料。
它能将聚酯染成亮红色色调。
例2-20
表1中的染料，能够通过与例1相似的方法来制备。
表1
| 实施例号 | R1 | R2 | R3 | R4 |
| 2 | -CN | -H | -CH2CH3 | -CH2CH2CN |
| 3 | -CN | -H | -CH2CH2CN | -CH2CH2OCOCH3 |
| 4 | -CN | -NHCOCH3 | -CH2CH2CN | -CH2CH2CN |
| 5 | -CN | -H | -CH2CH2OCOCH3 | -CH2CH2OCOCH3 |
| 6 | -CN | -H | -CH2CH3 | -CH2CH2OCOCH3 |
| 7 | -Br | -H | -CH2CH3 | -CH2CH2CN |
| 8 | -Br | -H | -CH2CH2CN | -CH2CH2OCOCH3 |
| 9 | -Cl | -CH3 | -CH2CH2CN | -CH2CH2CN |
| 10 | -Br | -H | -CH2CH2OCOCH3 | -CH2CH2OCOCH3 |
| 11 | -Br | -H | -CH2CH3 | -CH2CH2OCOCH3 |
| 12 | -H | -NHCOCH3 | -CH2CH2CN | -CH2CH2CN |
| 13 | -H | -H | -CH2CH2CN | -CH2CH2CN |
| 14 | -H | -H | -CH2CH2CN | -CH2CH2OCOCH3 |
| 15 | -H | -H | -CH2CH3 | -CH2CH2CN |
| 16 | -H | -H | -CH2CH3 | -CH2CH2OCOCH3 |
| 17 | -Br | -CH3 | -CH2CH2CN | -CH2CH2CN |
| 18 | -CN | -CH3 | -CH2CH2CN | -CH2CH2CN |
| 19 | -Cl | -H | -CH2CH2CN | -CH2CH2CN |
| 20 | -H | -CH3 | -CH2CH2CN | -CH2CH2CN |
Claims (3)
1.一种染料，化学式为(1)
其中
R1是溴，R2是氢，R3是氰乙基，和R4是氰乙基。
2.按照权利要求1的化学式(1)的染料制备方法，其中化学式(50)化合物按常规方法重氮化，
然后同化学式(51)的偶联成分偶联，
式中R1、R2、R3和R4的定义同化学式(1)。
3.按照权利要求1化学式(1)的染料在半合成或合成的疏水性纤维材料的染色或印染中的用途。
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| EP99810836.9 | 1999-09-20 |
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| JP (1) | JP5203545B2 (zh) |
| CN (1) | CN1200977C (zh) |
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| US20050155163A1 (en) * | 2004-01-21 | 2005-07-21 | Griffin Bruce O. | Dye mixtures |
| WO2007058209A1 (ja) * | 2005-11-16 | 2007-05-24 | Kiwa Chemical Industry Co., Ltd. | 分散染料、分散染料組成物、インクジェット捺染用インク、これらを用いた染色方法及び染色物 |
| JP2013515811A (ja) * | 2009-12-23 | 2013-05-09 | カラーテックス・インダストリーズ・リミテッド | 分散染料 |
| CN102086307A (zh) * | 2010-12-27 | 2011-06-08 | 中南林业科技大学 | N，n-二氰乙基间氯苯胺系列偶氮染料 |
| CN104603214B (zh) | 2012-09-12 | 2017-08-08 | 亨斯迈先进材料（瑞士）有限公司 | 用于喷墨印刷织物纤维材料的油墨和方法 |
| WO2018114140A1 (en) | 2016-12-20 | 2018-06-28 | Huntsman Advanced Materials (Switzerland) Gmbh | Inks and a process for ink-jet printing textile fibre materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2891942A (en) * | 1955-07-13 | 1959-06-23 | Saul & Co | Water-insoluble monoazo dyestuffs |
| US3407189A (en) * | 1956-07-25 | 1968-10-22 | Sandoz Ltd | Water-insoluble monoazo dyestuffs |
| US2941992A (en) * | 1957-10-11 | 1960-06-21 | Ciba Ltd | Water-insoluble azo dyestuffs |
| BE636342A (zh) * | 1960-06-09 | |||
| CH475309A (de) * | 1963-02-15 | 1969-07-15 | Sandoz Ag | Verfahren zur Herstellung in Wasser schwer löslicher Azofarbstoffe |
| GB1050675A (zh) | 1963-02-15 | |||
| JPS4867565A (zh) * | 1971-12-18 | 1973-09-14 | ||
| JPS4930417A (zh) * | 1972-07-20 | 1974-03-18 | ||
| NL7416601A (nl) * | 1973-12-22 | 1975-06-24 | Bayer Ag | Azokleurstoffen. |
| FR2346409A1 (fr) * | 1975-11-10 | 1977-10-28 | Ugine Kuhlmann | Colorants monoazoiques insolubles dans l'eau polyfluores |
| DE3161758D1 (en) * | 1980-04-30 | 1984-02-02 | Ciba Geigy Ag | Colour photopgraphic material for the silver-dye bleaching process, process for the production of this material and its use in the production of photographic images |
| JPH0887040A (ja) * | 1994-09-16 | 1996-04-02 | Toyota Central Res & Dev Lab Inc | 高分子非線形光学材料 |
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| ATE280201T1 (de) | 2004-11-15 |
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| ES2230053T3 (es) | 2005-05-01 |
| DE50008309D1 (de) | 2004-11-25 |
| US6540794B1 (en) | 2003-04-01 |
| JP5203545B2 (ja) | 2013-06-05 |
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