CN1155283A - 荧光增白剂 - Google Patents
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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Abstract
用于纺织品、纸张、洗涤剂的、相应于通式I的荧光增白剂,式中R、R1优选地衍生于氨基酸、尤其谷氨酸和亚氨基二乙酸。
Description
本发明涉及基于4,4′-二氨基茋-2,2′-二磺酸的新型有机化合物。
4,4′-二氨基茋-2,2′-二磺酸通常被称为“DAS”,它是许多用于工业的重要产品,最重要的各种染料和荧光增白剂的原料。基于DAS的荧光增白剂(OBAs)在洗涤剂、纸张、纺织品等方面具有广泛的用途。
制造荧光增白剂的标准方法之一是用取代的三嗪来取代DAS中的氨基。例如,这可以通过使DAS与氰尿酰氯反应,然后进一步使氰尿酰氯部分上剩余的氯反应来完成。用于这些氯之一的普通取代基由磺胺酸提供。
现已发现可以制造出一类基于DAS的新的化合物,其性能要比已知的基于磺胺酸的材料好得多。因此本发明提供一种呈游离酸或盐形式的式I化合物:其中:R、R1是可以相同或不同的式-NR2R3所示的部分,其中:(a)R2选自:
(i)氢;
(ii)C1-6烷,可任选地被巯基、C1-6硫烷基、OH和SO3M中至少1个基团取代;和
(iii)-R4(CO2M)x
其中R4是含有1-6个碳原子的脂族部分,不与基团CO2M连接的那些价键与H、巯基、C1-6硫烷基、OH和SO3M中至少1个基团连接,x是1-4的整数,M选自氢、无色阳离子或由胺衍生的阳离子;
其条件是:当R2只选自(i)或(ii)时,任何基团(ii)均至少被OH和SO3M这两者取代;
(b)R3选自基团R2、氢和C3-6烷基,其条件是:R2和R3不能都是氢,且当R2和R3中之一是氢时,另一个不能是-(NHCH2CO2H);
或者R2和R3与氮原子合在一起形成一个5-6元的环,其中只有1个是杂环(原子),该环由-COOM或-SO3M单取代;R5独立地选自氢、甲基、C1-6烷氧基或卤素。
在本发明的一个优选实施方案中,R5是氢,且在连接到三嗪环上的亚苯基环上的磺酸基相对于连接的氨基而言是间位或对位的,也就是说,连接在三嗪环上的特别部分是从磺胺酸或间胺酸衍生来的。
R和R1部分可从本技术中已知的任何适当的化合物衍生而来。较好的是,它们是氨基酸残基。适合的酸的例子包括甘氨酸、天冬氨酸、丝氨酸、羟基谷氨酸和丙氨酸,但优选的酸是谷氨酸和亚氨基二乙酸。
最优选的化合物是从间胺酸或磺胺酸衍生来的化合物,且其中R是从谷氨酸或亚氨基二乙酸衍生来的。
在R2和R3与基团R、R1中的氮原子一起形成一个环时,优选的是该环应是一个被-COOM取代的吡咯烷环。
按照本发明的化合物可以制备成游离酸的形式或诸如与碱金属阳离子形成的盐形式,有机胺盐,混合盐或部分盐的形式。
材料M优选是金属阳离子,特别是钠和钾,或简单的链烷醇胺,如单一、二-或三乙醇胺。
按照本发明的化合物可以通过标准合成方法用易得到的试剂来制备。
这类化合物可以单独使用或以混合物形式使用。已经发现,这类化合物中的某些化合物,特别是上面提到的由氨基二乙酸/谷氨酸-磺胺酸衍生来的材料显示出优异的荧光增白特性。因此,按照本发明的化合物作为纸张、纺织品等材料的荧光增白剂(OBAs)特别有用。
本发明的化合物当用作纸张的荧光增白剂时特别有效。它们可以通过在纸张成形之前加入到纸浆中或者通过掺入到随后施涂到纸张上的涂料组合物中而施加到纸张上。掺入到随后用在纸张上的一种胶料中是特别有效的方法。这类化合物也可以与某些熟知的用来提高荧光增白剂性能添加剂,如羧甲基纤维素、聚乙二醇、链烷醇胺、聚乙烯醇等结合,一起施涂到纸张的表面上。
因此,本发明提供一种造纸方法,包括将式I的化合物加入到纸浆中。
此外,本发明还提供一种造纸方法,包括将式I的化合物加入到纸张涂料组合物中。
本发明还进一步提供一种处理纺织品的方法,包括在其中加入式I的化合物。
本发明也提供含有式I化合物的纸张,以及含有式I化合物的纺织品。
本发明还进一步提供式I化合物作为洗涤剂、纸张或纺织品的荧光增白剂的用途,尤其在纸张成形后的涂布方法中作为荧光增白剂的用途。
下面参照下列非限制性实例进一步说明本发明,在这些实例中所有份额均以重量表示。
制备实例
式III化合物的制备
步骤1
在冷却下将18.4份氰尿酰氯在100份丙酮中的溶液倒入到300份碎冰和500份水的混合物中。在0-5℃的温度范围内将20.7份4,4′-二氨基-2,2′-茋二磺酸钠在150份水中的溶液滴入到上述的混合物中,加入碳酸氢钠使该反应混合物保持弱酸性至试纸显刚果红。在0-5℃继续搅拌直到用重氮化方法检测不到芳族伯胺基团为止。
步骤2
将19.6份磺胺酸钠盐在200份水中的溶液慢慢加入到从步骤1得到的反应混合物中,将温度保持在5-10℃,同时加入稀的氢氧化钠溶液使pH保持中性。添加完毕后将混合物加热到50℃,并继续搅拌直到用重氮化方法检测不到芳族伯(胺)基团为止。
步骤3
将15份谷氨酸加入到步骤2的反应混合物中,并将所得混合物加热至回流。在该过程中加入氢氧化钠稀溶液使pH保持8。蒸出丙酮,将混合物回流5小时。将反应混合物浓缩,加入盐使产物沉淀出来。滤出产物,用10%盐水洗涤。
应用实例1
将10份式III化合物溶解在50份蒸馏水中。100份典型施胶压榨淀粉配入1000份水中,然后在90℃蒸煮。然后冷却到60℃。再将该增白剂溶液掺入到该淀粉溶液中。在施胶压榨机或压膜机中用该淀粉/增白剂溶液对纸基或纸板进行表面涂布,然后在造纸机的干燥部中于80-120℃下进行干燥。
于是得到一种白度大大提高的纸或纸板。
应用实例2
在搅拌下将式III化合物的水溶液按剂量加入到阴离子氧化的马铃薯淀粉(商品名“Perfectamyl”A4692)的温热(60℃)溶液中,与水一起得到一种含5%和已知量化合物的淀粉溶液。
将该增白淀粉溶液倒入到实验室用的施胶压榨机的转动辊之间(形成一个槽),然后让原纸(市售白纸75g/m2,中性涂胶,CIE白度72,没有施胶压榨机涂层)经该溶液从两辊之间通过。然后将涂布了这种湿淀粉溶液的纸置于平板干燥器中于70℃下干燥5分钟。
在涂布前及湿态时将该纸称重,以测定湿淀粉溶液的吸收量,从而计量出淀粉的吸收量。
干燥后,让纸张平衡,然后根据用校准光谱仪所测得的参数计算出各张纸的CIE白度(W10)。
用等量市售OBA(商品名“Leucophor”U)代替本发明的化合物重复上述过程。
对纸张测得的本发明化合物和市售产品的CIE白度值示于图1中。白度值W10由下式(按ISO 105-502)计算:
W10=Y10+800(0.3138-X10)+1700(0.3310-y10)
本发明化合物的优异性能可从其低比例看出。
应用实例3
在搅拌下将式III化合物的水溶液按剂量与水一起加入到涂料组合物中(见下面的叙述)得到一种固含量恒定和已知量化合物的涂料组合物溶液。然后用一台自动线绕棒状涂布器以标准设定速度和标准棒载荷将该增白涂料组合物溶液涂布到适当的基纸上。再将涂布了该溶液的纸置于热空气流中干燥5分钟。涂布前及干燥后将已知面积的纸称重以测定所施涂的涂层重量。
干燥后,让纸张平衡,然后根据用同一校准光谱仪上所测得的参数计算出各张纸的CIE白度(W10)。
该涂料组合物配方为:
颜料-陶土SPS 100份
水 64.4份
分散剂1 0.6份
胶乳2 20份
20%淀粉溶液3 25份
固含量约=55%
1.使用“Polysalz”(商标),一种聚丙烯酸的钠盐。
2.使用“Acronal”(商标)S320D,一种丙烯酸酯共聚物。
3. “Perfectamyl”A4692。
用相同量的市售荧光增白剂重复上述实验。结果示于图2。同样可以看出本发明的化合物的增白性能比市售荧光增白剂好得多。
Claims (11)
1、呈游离酸或盐形式的式I化合物:
其中:
R、R1是可以相同或不同的式-NR2R3所示的部分,其中:
(a)R2选自:
(i)氢;
(ii)C1-6烷,可任选地被巯基、C1-6硫烷基、OH和SO3M中至少1个基团取代;和
(iii)-R4(CO2M)x
其中R4是含有1-6个碳原子的脂族部分,不与基团CO2M连接的那些价键与H、巯基、C1-6硫烷基、OH和SO3M中至少1个基团连接,x是1-4的整数,M选自氢、无色阳离子或由胺衍生的阳离子;
其条件是:当R2只选自(i)或(ii)时,任何基团(ii)均至少被OH和SO3M这两者取代;
(b)R3选自基团R2、氢和C3-6烷基,其条件是:R2和R3不能都是氢,且当R2和R3中之一是氢时,另一个不能是-(NHCH2CO2H);
或者R2和R3与氮原子合在一起形成一个5-6元的环,其中只有1个是杂环(原子),该环由-COOM或-SO3M单取代;R5独立地选自氢、甲基、C1-6烷氧基或卤素。
2、按照权利要求1的化合物,其中R5是氢,在连接到三嗪环上的亚苯基环上的SO3M基团相对于连接的氨基而言是间位或对位。
3、按照权利要求1的化合物,其中R、R1是氨基酸残基。
4、按照权利要求3的化合物,其中所述氨基酸选自甘氨酸、天冬氨酸、丝氨酸、羟基谷氨酸和丙氨酸,且优选谷氨酸和亚氨基二乙酸。
6、一种造纸方法,包括将式I的化合物加入到纸浆中。
7、一种造纸方法,包括将式I的化合物加入到纸张涂料组合物中。
8、一种处理纺织品的方法,包括在其中加入式I的化合物。
9、含有式I化合物的纸张。
10、含有式I化合物的纺织品。
11、式I化合物作为洗涤剂、纸张或纺织品的荧光增白剂的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9412590A GB9412590D0 (en) | 1994-06-23 | 1994-06-23 | Organic compounds |
GB9412590.3 | 1994-06-23 |
Publications (2)
Publication Number | Publication Date |
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CN1155283A true CN1155283A (zh) | 1997-07-23 |
CN1127489C CN1127489C (zh) | 2003-11-12 |
Family
ID=10757191
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN95194490A Expired - Lifetime CN1127489C (zh) | 1994-06-23 | 1995-06-22 | 荧光增白剂 |
Country Status (17)
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US (1) | US5873913A (zh) |
EP (1) | EP0766678B1 (zh) |
JP (1) | JP4060352B2 (zh) |
CN (1) | CN1127489C (zh) |
AT (1) | ATE212016T1 (zh) |
AU (1) | AU697354B2 (zh) |
BR (1) | BR9508097A (zh) |
CA (1) | CA2192788C (zh) |
CO (1) | CO4410391A1 (zh) |
DE (1) | DE69525051T2 (zh) |
ES (1) | ES2170155T3 (zh) |
FI (1) | FI112654B (zh) |
GB (1) | GB9412590D0 (zh) |
NO (1) | NO309650B1 (zh) |
PT (1) | PT766678E (zh) |
WO (1) | WO1996000221A1 (zh) |
ZA (1) | ZA955237B (zh) |
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CN100410253C (zh) * | 2005-10-17 | 2008-08-13 | 山东大学 | 三嗪基氨基二苯乙烯类荧光增白剂 |
CN103562188A (zh) * | 2011-04-27 | 2014-02-05 | 克拉里安特国际有限公司 | 新型双-(三嗪基氨基)-二苯乙烯衍生物 |
CN101999020B (zh) * | 2008-03-26 | 2014-06-11 | 科莱恩金融(Bvi)有限公司 | 改良的荧光增白组合物 |
CN105102712A (zh) * | 2013-03-21 | 2015-11-25 | 昂高知识产权有限公司 | 用于高质量喷墨印刷的光学增白剂 |
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GB0100610D0 (en) * | 2001-01-10 | 2001-02-21 | Clariant Int Ltd | Improvements in or relating to organic compounds |
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GB0125177D0 (en) * | 2001-10-19 | 2001-12-12 | Clariant Int Ltd | Improvements in or relating to organic compounds |
GB0127903D0 (en) * | 2001-11-21 | 2002-01-16 | Clariant Int Ltd | Improvements relating to organic compounds |
EP1612209A1 (en) * | 2004-06-28 | 2006-01-04 | Clariant International Ltd. | Improvements relating to optical brightening agents |
DE102004031101B4 (de) * | 2004-06-28 | 2010-04-08 | Kemira Oyj | Verwendung von Triazinylflavonataufhellern |
US20060005935A1 (en) * | 2004-07-06 | 2006-01-12 | Harris Edith E | Multi-function starch compositions |
DE102004038578A1 (de) * | 2004-08-06 | 2006-03-16 | Lanxess Deutschland Gmbh | Alkanolammoniumhaltige Triazinylflavonataufheller |
US7638016B2 (en) | 2005-02-19 | 2009-12-29 | International Paper Company | Method for treating kraft pulp with optical brighteners after chlorine bleaching to increase brightness |
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-
1995
- 1995-06-22 CN CN95194490A patent/CN1127489C/zh not_active Expired - Lifetime
- 1995-06-22 BR BR9508097A patent/BR9508097A/pt not_active IP Right Cessation
- 1995-06-22 ES ES95924911T patent/ES2170155T3/es not_active Expired - Lifetime
- 1995-06-22 WO PCT/EP1995/002433 patent/WO1996000221A1/en active IP Right Grant
- 1995-06-22 CO CO95027627A patent/CO4410391A1/es unknown
- 1995-06-22 JP JP50279396A patent/JP4060352B2/ja not_active Expired - Lifetime
- 1995-06-22 EP EP95924911A patent/EP0766678B1/en not_active Expired - Lifetime
- 1995-06-22 PT PT95924911T patent/PT766678E/pt unknown
- 1995-06-22 AT AT95924911T patent/ATE212016T1/de active
- 1995-06-22 DE DE69525051T patent/DE69525051T2/de not_active Expired - Lifetime
- 1995-06-22 CA CA002192788A patent/CA2192788C/en not_active Expired - Lifetime
- 1995-06-22 AU AU29237/95A patent/AU697354B2/en not_active Expired
- 1995-06-22 US US08/765,468 patent/US5873913A/en not_active Expired - Lifetime
- 1995-06-23 ZA ZA955237A patent/ZA955237B/xx unknown
-
1996
- 1996-12-17 FI FI965082A patent/FI112654B/fi not_active IP Right Cessation
- 1996-12-19 NO NO965487A patent/NO309650B1/no not_active IP Right Cessation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100410253C (zh) * | 2005-10-17 | 2008-08-13 | 山东大学 | 三嗪基氨基二苯乙烯类荧光增白剂 |
CN101999020B (zh) * | 2008-03-26 | 2014-06-11 | 科莱恩金融(Bvi)有限公司 | 改良的荧光增白组合物 |
CN103562188A (zh) * | 2011-04-27 | 2014-02-05 | 克拉里安特国际有限公司 | 新型双-(三嗪基氨基)-二苯乙烯衍生物 |
CN105102712A (zh) * | 2013-03-21 | 2015-11-25 | 昂高知识产权有限公司 | 用于高质量喷墨印刷的光学增白剂 |
CN105102712B (zh) * | 2013-03-21 | 2017-06-09 | 昂高知识产权有限公司 | 用于高质量喷墨印刷的光学增白剂 |
Also Published As
Publication number | Publication date |
---|---|
NO965487L (no) | 1996-12-19 |
AU697354B2 (en) | 1998-10-01 |
ATE212016T1 (de) | 2002-02-15 |
US5873913A (en) | 1999-02-23 |
ZA955237B (en) | 1996-12-23 |
CA2192788C (en) | 2006-05-09 |
FI965082A (fi) | 1996-12-17 |
ES2170155T3 (es) | 2002-08-01 |
DE69525051T2 (de) | 2002-07-18 |
BR9508097A (pt) | 1997-08-12 |
FI965082A0 (fi) | 1996-12-17 |
CO4410391A1 (es) | 1997-01-09 |
GB9412590D0 (en) | 1994-08-10 |
NO965487D0 (no) | 1996-12-19 |
EP0766678B1 (en) | 2002-01-16 |
WO1996000221A1 (en) | 1996-01-04 |
NO309650B1 (no) | 2001-03-05 |
PT766678E (pt) | 2002-06-28 |
CA2192788A1 (en) | 1996-01-04 |
EP0766678A1 (en) | 1997-04-09 |
JPH10503756A (ja) | 1998-04-07 |
JP4060352B2 (ja) | 2008-03-12 |
DE69525051D1 (de) | 2002-02-21 |
AU2923795A (en) | 1996-01-19 |
CN1127489C (zh) | 2003-11-12 |
FI112654B (fi) | 2003-12-31 |
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