CN1643205A - 吡唑啉增白剂的含水液体配方 - Google Patents

吡唑啉增白剂的含水液体配方 Download PDF

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CN1643205A
CN1643205A CNA038063298A CN03806329A CN1643205A CN 1643205 A CN1643205 A CN 1643205A CN A038063298 A CNA038063298 A CN A038063298A CN 03806329 A CN03806329 A CN 03806329A CN 1643205 A CN1643205 A CN 1643205A
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pyrazoline
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G·泽尔肯巴奇
A·勒奇
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D06L4/629—Optical bleaching or brightening in aqueous solvents with cationic brighteners
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/664—Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners

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Abstract

本发明要求保护一种液体配方，其含有有机酸和支链一元醇或二元醇。通过添加所述醇，实现了该液体配方的改进的贮存稳定性。

Description

吡唑啉增白剂的含水液体配方
已知将带有碱性基团并以其与乳酸形成的盐的形式存在的特定的吡唑啉增白剂用于将丙烯酸类纤维增白(DE 3134942)。商业上可以得到这类增白剂的含水液体配方，其除了该增白剂还含有乳酸、甲酸和甲氧基丙醇。但是，这种配方在其贮存稳定性方面还尚可改进。由此，本发明的任务是提供吡唑啉增白剂的含水液体配方，其具有改善的贮存稳定性。现在发现，这个目标可以通过如下方式达到：向这种类型的增白剂的配方中添加支链一元醇和二元醇。
本发明提供具有如下通式的吡唑啉增白剂的含水液体配方：
其中
X表示O、SO2、SO2NZ或一个直接键，
Y表示非必要地被O、S或CONH中断的亚烷基链，
Z表示H或烷基，
R1和R2表示烷基、环烷基或芳烷基或共同表示一个N杂环的其余成员，
Z1表示H或烷基，
Z2表示H、烷基或芳基，和
A表示一种有机酸的阴离子，
其中这些液体配方除了含有上述通式的吡唑啉增白剂以外，还含有有机酸和支链一元醇或二元醇。
合适的烷基R1和R2特别是可以经由如下基团取代的具有1-4个碳原子的烷基：卤素，如氟、氯和溴，羟基，氰基，C1-C4烷氧基，苯氧基，C2-C5烷基羰氧基，或C2-C5烷氧基羰氧基。
合适的环烷基R1和R2是环戊基和环己基。
合适的芳烷基R1和R2特别是苄基和苯乙基。
合适的杂环基，其可以由R1和R2一起与N原子构成，其是例如吡咯烷、哌啶、咪唑、吗啉和硫代吗啉基团。
合适的烷基Z、Z1和Z2特别是具有1-4个碳原子的未经取代的烷基。
合适的芳基Z2特别是苯基，其可以经由一个或多个如下的基团取代：卤素原子，C1-C4烷基，C1-C4烷氧基，氰基，羧酸酯基团和羧酰胺基团。
作为亚烷基Y特别合适的是如下具有2-4个碳原子的亚烷基：
Figure A0380632900051
和  -(CH2)2-O-CHCH3-CH2-
作为阴离子A(-)可以考虑低分子量有机酸的阴离子，例如甲酸根和乳酸根。
优选的吡唑啉增白剂是具有如下通式的那些：
Figure A0380632900052
其中，
D表示
，并优选
Figure A0380632900061
R1’和R2’表示C1-C2烷基，
T1、T2、T3表示H、CH3或Cl，和
A表示乳酸根或甲酸根。
优选T1-T3不同时表示Cl或CH3。
这些吡唑啉增白剂在成品液体配方中的含量可以为1-60重量％，优选5-30重量％。
上面定义的增白剂盐所基于的吡唑啉碱是已知的，并例如在下述专利文献中有直接或间接(作为季盐形式)的描述：DE-A 1 155 418，1 23 124，1 469 222，1 904 424，2 011 552，2 050 725，2 248 772，2 534 180和2 700 996以及US-A 3 131 079和3 135 742。除了所述的增白剂盐以外，本发明的液体配方还含有有机酸和支链一元醇或二元醇。作为有机酸合适的是低分子量有机酸，如它们常用于形成吡唑啉碱的盐，例如甲酸、乙酸和乳酸或这些酸的混合物。这些酸的量基于成品液体配方一般为20-60重量％，优选30-50重量％。
支链一元醇或二元醇在成品液体配方中的含量可以为15-40重量％，优选20-30重量％。作为一元醇或二元醇优选考虑新戊二醇和叔丁醇。
此外，本发明的液体配方还可以含有在荧光增白剂方面常用的助剂，例如助水溶剂(例如尿素)、溶液稳定化试剂(例如乙二醇二乙酸酯)、防腐剂、水溶性阳离子配色染料，每种情况下用量为最高至10重量％。
本发明的液体配方的制备优选按如下方式进行：按下列顺序加入配方的各单个组分并以合适的方式加以混合：有机酸，支链一元醇或二元醇，增白剂盐，水。还可以代替增白剂盐而以其所基于的碱为原料，并增加用于生成盐所需量的有机酸。
本发明的液体配方相对于目前常用的商品形式具有改进的贮存稳定性。这种改进的贮存稳定性在如下方面表现出来：这些配方的色值特别地即使在较长时间的贮存后也只有明显较小幅度的升高。
按已知方式，本发明的液体配方用于引入纺丝物料中，该纺丝物料用于在所谓的湿纺工艺中制备聚丙烯腈纤维，或该液体配方用于在拉丝工艺中将成品聚丙烯酸类纤维增白。
实施例
通过如下方法制备一种液体配方：在室温下按下面的顺序将下列组分充分混合：
40g乳酸；6g甲酸；23.3g新戊二醇(90％)；19.2g增白剂(约79％)；11.5g水。所利用的增白剂具有如下通式：
Figure A0380632900071
将这种液体配方与商业上常用的相同增白剂的液体配方共同测试贮存稳定性(测量色值x和y)。在其它方面与本发明的配方组成相同的情况下，商业上常用的液体配方含有21g甲氧基丙醇和13.8g水，而不是23.3g新戊二醇和11.5g水。
对两种配方测量下面的x值和y值作为用于稳定性的量度。
        本发明配方            商品
    x值     y值     x值     y值
    初始     0.353     0.390     0.354     0.392
  室温/暗处贮存4周后     0.362     0.404     0.368     0.401
  50℃/暗处贮存4周后     0.363     0.402     0.402     0.425
  室温/暗处贮存10周后     0.383     0.433     0.390     0.433
  50℃/暗处贮存10周后     0.386     0.428     0.449     0.466
这些数值表明，在本发明配方情况下的色值比在商品情况下升高的幅度明显小。这意味着含有新戊二醇的本发明配方的稳定性明显改善。

Claims (9)

1.具有如下通式的吡唑啉增白剂的含水液体配方：
Figure A038063290002C1
其中
X表示O、SO2、SO2NZ或一个直接键，
Y表示非必要地被O、S或CONH中断的亚烷基链，
Z表示H或烷基，
R1和R2表示烷基、环烷基或芳烷基或共同表示N杂环的其余成员，
Z1表示H或烷基，
Z2表示H、烷基或芳基，和
A表示一种有机酸的阴离子，
其特征在于，该液体配方除了含有上述通式的吡唑啉增白剂以外，还含有有机酸和支链一元醇或二元醇。
2.根据权利要求1的含水液体配方，其特征在于，其含有作为吡唑啉增白剂的具有如下通式的化合物：
Figure A038063290002C2
其中，
D表示-CH2CH2-，-CH2CH2CH2-，-CH2CH2-OCH2CH2，
Figure A038063290003C1
，并优选
Figure A038063290003C2
R1’和R2’表示C1-C2烷基，和
T1、T2、T3表示H、CH3或Cl。
3.根据权利要求1的含水液体配方，其特征在于，其含有作为有机酸的乳酸或甲酸或乙酸或其混合物。
4.根据权利要求1的含水液体配方，其特征在于，其含有作为支链一元醇或二元醇的新戊二醇或叔丁醇。
5.根据权利要求1的含水液体配方，其特征在于，其含有20-60重量％的有机酸。
6.根据权利要求1的含水液体配方，其特征在于，其含有15-40重量％的支链一元醇或二元醇。
7.根据权利要求1的含水液体配方，其特征在于，其含有1-60重量％的吡唑啉增白剂。
8.根据权利要求1的含水液体配方，其特征在于，其含有在荧光增白剂的液体配方方面常用的助剂。
9.根据权利要求1的含水液体配方用于将聚丙烯酸类纤维增白的用途。
CNB038063298A 2002-02-28 2003-02-20 吡唑啉增白剂的含水液体配方 Expired - Fee Related CN1293254C (zh)

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DE10208773A DE10208773A1 (de) 2002-02-28 2002-02-28 Wässrige Flüssigformulierungen von Pyrazolin-Aufhellern
DE10208773.3 2002-02-28

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WO2008142089A1 (en) * 2007-05-23 2008-11-27 Clariant Finance (Bvi) Limited Stable liquid formulation
WO2009074548A2 (en) 2007-12-12 2009-06-18 Clariant International Ltd Storage stable solutions of optical brighteners

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US3131079A (en) 1960-08-12 1964-04-28 Bayer Ag Brightening of fiber material by coating with 1, 3-diaryl- and 1, 3, 5-triaryl pyrazoline derivatives
GB993055A (en) 1960-10-28 1965-05-26 Hickson & Welch Ltd Improvements in or relating to optical whitening agents
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US7300474B2 (en) 2007-11-27
WO2003072870A1 (de) 2003-09-04
EP1483438B1 (de) 2007-02-14
DE50306499D1 (de) 2007-03-29
US20050251931A1 (en) 2005-11-17
DE10208773A1 (de) 2003-09-04
JP2005526872A (ja) 2005-09-08

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