CN100549105C - A kind of painted composite active black dye that is used for cellulosic fibre - Google Patents
A kind of painted composite active black dye that is used for cellulosic fibre Download PDFInfo
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- CN100549105C CN100549105C CNB2007100704122A CN200710070412A CN100549105C CN 100549105 C CN100549105 C CN 100549105C CN B2007100704122 A CNB2007100704122 A CN B2007100704122A CN 200710070412 A CN200710070412 A CN 200710070412A CN 100549105 C CN100549105 C CN 100549105C
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Abstract
The invention discloses a kind of painted composite active black dye that is used for cellulosic fibre, weight percent consists of: 60%～80% the dyestuff A as the described structural formula of specification sheets (I); 15%～40% as the dyestuff B of the described structural formula of specification sheets (II) with as the mixture of the dyestuff C of the described structural formula of specification sheets (III); Surplus is an auxiliary agent; Among the described dyestuff B and the mixture as the dyestuff C of structural formula (III) as structural formula (II), dyestuff B is identical with the content of dyestuff C.Composite active black dye of the present invention is highly suitable for the various dyeings of cellulose materials, have good look rate degree, high levelling property, easy washing property and in the BLENDED FABRIC co-bathing dyeing, the selectivity good to cellulosic fibre, do not contain 23 kinds of harmful aromatic amines and 10 heavy metal species elements in each molecular structure of dye, in use can not decomposite any toxic substance, be a kind of environment-friendly active dye of excellent property.
Description
Technical field
The present invention relates to a kind of dye composite.Especially a kind of reactive black dye composition is mainly used in the dyeing of cellulosic fibre.
Background technology
In the market with reactive black 5
#With reactive orange 82
#The compound active black dye is because its low price, high pitch black degree still occupy the suitable market share.But look flower and color spot phenomenon often appear in above-mentioned composite reactive black dyestuff in dyeing, have a strong impact on quality product.
Disclose a kind of composite active black dye in the Chinese invention patent 200410066669.7, mark meter by weight comprises 40～70% dyestuff A, 15～35% dyestuff B and 8～30% dyestuff C.Composite active black dye in this invention is fit to dye the material fiber of (comprising stamp) hydroxyl or carboxyl, as cellulosic fibre, cotton fibre, synthon etc., by certain improvement, at the level dyeing aspect of performance, still is not very desirable at aspects such as colour fastness, pitch black degree, fixation rates.
Those skilled in the art are also seeking to improve the way of its level dyeing performance always, seek the better substitute of level dyeing performance.
Summary of the invention
The invention provides a kind of painted composite active black dye that is used for cellulosic fibre with high-compatibility, good level-dyeing property.
A kind of painted composite active black dye that is used for cellulosic fibre, weight percent consists of:
60%～80% dyestuff A as structural formula (I);
Structural formula (I)
15%～40% as the dyestuff B of structural formula (II) with as the mixture of the dyestuff C of structural formula (III);
Structural formula (II)
Structural formula (III)
Surplus is an auxiliary agent;
Among the described dyestuff B and the mixture as the dyestuff C of structural formula (III) as structural formula (II), the content of dyestuff B and dyestuff C is roughly the same.
The preparation method of the dyestuff A of structural formula (I) is as follows:
At 0～14 ℃, excessive hydrochloric acid (solvent) exists down and Sodium Nitrite, carries out diazotization, obtains diazonium salt to (2-sulfate group ethyl sulfuryl) aniline.At 15～18 ℃, with 1-amino-8-naphthol-3, the 6-disulfonic acid carries out acid coupling earlier then, at PH 1～2, finished reaction in 3～5 hours, add alkaline agent (sodium bicarbonate) then, adjust rapidly PH 6～6.5, stirring reaction 2～3 hours obtains having the dyestuff A as structural formula (I) of dark blue tone.
Main raw material is as follows:
To (2-sulfate group ethyl sulfuryl) aniline
1-amino-8-naphthol-3, the 6-disulfonic acid
The dyestuff B of structural formula (II) and as follows as the preparation process of mixture of the dyestuff C of structural formula (III):
With 4 molfractions to (2-sulfate group ethyl sulfuryl) aniline, the 4-β of 4 molfractions-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid, 8.5 adding in 30% the hydrochloric acid of 13 molfractions, the Sodium Nitrite of molfraction carries out diazotization at 0-8 ℃, obtain mixture to the diazonium salt hydrochlorate of the diazonium salt hydrochlorate of (2-sulfate group ethyl sulfuryl) aniline and 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid, at-10～10 ℃, add 2 of the 2-amino-5-naphthols-7-sulfonic acid of 1 molfraction and 1 molfraction, 4-diamino benzene sulfonic acid sodium carries out acid coupling reaction 5～8 hours with diazonium salt hydrochlorate to the diazonium salt hydrochlorate of (2-sulfate group ethyl sulfuryl) aniline and 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid, again with sodium bicarbonate in 3～5 hours, adjust pH value to 6.0～6.5, obtain as the dyestuff B of structural formula (II) with as the mixture of the dyestuff C of structural formula (III).
Main raw material is as follows:
To (2-sulfate group ethyl sulfuryl) aniline
4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid
2-amino-5-naphthols-7-sulfonic acid
2, the 4-diamino benzene sulfonic acid
In the mixture process of preparation dyestuff B and dyestuff C, if when coupled reaction to the diazonium salt hydrochlorate of (2-sulfate group ethyl sulfuryl) aniline and the diazonium salt hydrochlorate and the 2-amino-5-naphthols-7-sulfonic acid or 2 of 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid, if the probability of each position coupling of 4-diamino benzene sulfonic acid sodium is identical, can form a large amount of by products, with 2-amino-5-naphthols-7-sulfonic acid is example, and the by product that may occur is as follows:
If consider the existence of above-mentioned three kinds of by products, dyestuff B only accounts for 25% ratio in 2-amino-5-naphthols-7-sulfonic acid coupling product, 2, and the coupling of 4-diamino benzene sulfonic acid sodium also is same situation.But the present invention has used the orientation effect of molecular radical cleverly, is example with 2-amino-5-naphthols-7-sulfonic acid, and dyestuff B accounts for more than 90% in 2-amino-5-naphthols-7-sulfonic acid coupling product, 2, and the coupling of 4-diamino benzene sulfonic acid sodium also is same situation.Dyestuff B and dyestuff C account for more than 90% in the product of whole reaction system like this, and very a spot of by product is to the not influence of overall performance of composite dye.
Though there is certain side reaction, reaction process control is also impossible and accurate, but because 2-amino-5-naphthols-7-sulfonic acid and 2, the molfraction of 4-diamino benzene sulfonic acid sodium is identical, makes in the mixture of dyestuff B and dyestuff C the content of dyestuff B and dyestuff C roughly the same.
The used auxiliary agent of composite dye of the present invention be the reactive dyestuffs accessory ingredient of in common use as: as in weighting agent Sodium sulfate anhydrous.min(99) (industrial anhydrous sodium sulfate), Sodium hexametaphosphate 99, Dispersant MF (condensation compound of methyl naphthalene sulfonic acid and formaldehyde), dispersion agent NNO (naphthalene sulfonic acidformaldehyde condensation product), the industrial anhydrous sodium sulfate etc. one or more.
Composite reactive black dyestuff of the present invention has adopted the vinyl sulfone(Remzaol active group fully, and it has identical dyeing temperature and reactive behavior, adapts to the needs of multiple dyeing.Especially the good easy washing of Vinyl-Sulfone Type active group has improved the Washing of DYED FABRICS.
Composite reactive black dyestuff of the present invention has improved the asymmetry between dye molecule, has improved the consistency of each component molecular structure of dye, and Mierocrystalline cellulose is had close avidity and substantivity, dyes the flat step on the each component dyestuff, has realized good level-dyeing property.Adopt three component colorant match, kept the stability of colorant match tone, convenient for users to use.
Orange component wherein (dyestuff B), yellow component (dyestuff C) stain property near 82 to polyamide fibre, nylon fiber
#Orange is slight staining; With reactive black 5
#After compound, kept original reactive black 5
#With reactive orange 82
#Composite reactive black is stained with brocade, advantage that nylon is few, and has remedied reactive black 5
#, reactive orange 82
#Composite reactive black can not discharge defective.And dyestuff B, dyestuff C adopt single stage method to produce simultaneously, have reduced cost, have also simplified the process of mixed assembly.
Composite active black dye of the present invention is highly suitable for the dyeing and the white discharge of cellulose materials, have good colour fastness, high levelling property, easy washing property and in the BLENDED FABRIC co-bathing dyeing, the selectivity good to cellulosic fibre, do not contain 23 kinds of harmful aromatic amines and 10 heavy metal species elements in each molecular structure of dye, in use can not decomposite any toxic substance, be a kind of environment-friendly active dye of excellent property.
Embodiment
The preparation of the dyestuff A of embodiment 1 structural formula (I)
The 4-of 4 molfractions (β hydroxyethyl sulfone) sulfate ester aniline is at 5 ℃, and the hydrochloric acid of 4.4 molfractions exists down, with the Sodium Nitrite of 4 molfractions, carries out diazotization, obtains diazonium salt.Then at 17 ℃, 1-amino-8-naphthol-3 with 1.92 molfractions, the 6-disulfonic acid carries out acid coupling earlier, is 1.15 at PH, reacts 4 hours, add an amount of trash ice then, cool to below 15 ℃, in 15 minutes, add sodium bicarbonate, adjust PH to 6.5 rapidly, stirring reaction 3 hours obtains having the dyestuff A of the structural formula (I) of dark blue tone.
The preparation of the mixture of the dyestuff C of the dyestuff B of embodiment 2 structural formulas (II) and structural formula (III)
The mixture of the 4-β of the 4-of 4 molfractions (β hydroxyethyl sulfone) sulfate ester aniline and 4 molfractions-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid is at 3 ℃, 8.5 volumetric molar concentration is 30% the following and 13 molfraction Sodium Nitrites of hydrochloric acid existence, be to carry out diazotization under 0.7 the condition at 3 ℃, PH, obtain mixing diazonium salt.At 8 ℃, add 1 molfraction 2-amino-5-naphthols-7-sulfonic acid, 1 molfraction 2,4-diamino benzene sulfonic acid sodium mixes, and reacts 8 hours.Adding sodium bicarbonate again, to adjust pH value in 3 hours be 6.5, stirred 5 hours, obtains having dyestuff B and the C mixture that dark red brown is transferred.
The preparation of embodiment 3～8 composite active black dyes
The mixture of the dyestuff C of the dyestuff B of the dyestuff A of structural formula (I), structural formula (II) and structural formula (III) and various auxiliary agent are mixed and be uniformly dispersed according to the proportioning in the table 1, make composite active black dye.
Table 1
Performance test
The composite active black dye of embodiment 3～8 preparation is carried out performance test with universal method, test event and the results are shown in Table 2,
Table 2
In the test of table 2 performance index, the testing standard and the method for employing are as follows:
The general condition regulation that the GB/T2374-1994 dyeing is measured
GB/T8427-1998 textiles colour fastness to light test method (xenon arc)
The test method of the anti-chloride swimming-pool water colour fastness of GB/T8433-1998 textiles
The measuring method of the relative content of hydrolised dye and standard in the GB/T2389-1980 reactive dyestuffs
The test method of GB/T3921.4-1997 textiles colour fastness to washing
The test method of GB/T3922-1995 textiles colour fastness to perspiration
GB/T4841.1-1984 1/1 dyeing standard depth colour atla
The test method of GB/T3920-1997 textiles colour fastness to rubbing
The test method of the heat-resisting pressure of GB/T6152-1997 textiles (flatiron) fastness
GB/T6678-1986 Chemicals sampling general provisions
The mensuration of GB/T3671.1-1996 water-soluble dye solubleness and steady dissolution
The measuring method of insolubles content in the GB/T2381-1994 dyestuff
The measuring method of GB/T2383-1980 dyestuff screening fineness
The measuring method of GB/T2386-1980 dye well dyestuff intermediate moisture content
The GB/T2388-1980 reactive dyestuffs are the measuring method of pattern light and intensity
The measuring method of GB/T2390-1980 reactive dyestuffs pH value
The GB/T2393-1980 reactive dyestuffs are promptly spent the measuring method of degree of fixation
The measuring method of GB/T2392-1980 reactive dyestuffs thermostability
Claims (2)
1, a kind of painted composite active black dye that is used for cellulosic fibre is characterized in that weight percent consists of:
60%～80% dyestuff A as structural formula (I);
Structural formula (I)
15%～40% as the dyestuff B of structural formula (II) with as the mixture of the dyestuff C of structural formula (III);
Structural formula (II)
Structural formula (III)
Surplus is an auxiliary agent;
Among the described dyestuff B and the mixture as the dyestuff C of structural formula (III) as structural formula (II), the content of dyestuff B and dyestuff C is roughly the same.
2, composite active black dye as claimed in claim 1 is characterized in that: the dyestuff B of described structural formula (II) and as follows as the preparation process of mixture of the dyestuff C of structural formula (III):
With 4 molfractions to (2-sulfate group ethyl sulfuryl) aniline, the 4-β of 4 molfractions-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid, 8.5 adding in 30% the hydrochloric acid of 13 molfractions, the Sodium Nitrite of molfraction carries out diazotization at 0-8 ℃, obtain mixture to the diazonium salt hydrochlorate of the diazonium salt hydrochlorate of (2-sulfate group ethyl sulfuryl) aniline and 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid, at-10～10 ℃, add 2 of the 2-amino-5-naphthols-7-sulfonic acid of 1 molfraction and 1 molfraction, 4-diamino benzene sulfonic acid sodium carries out acid coupling reaction 5～8 hours with diazonium salt hydrochlorate to the diazonium salt hydrochlorate of (2-sulfate group ethyl sulfuryl) aniline and 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid, use sodium bicarbonate again in 3～5 hours, adjust pH value to 6.0～6.5, obtain as the dyestuff B of structural formula (II) with as the mixture of the dyestuff C of structural formula (III).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100704122A CN100549105C (en) | 2007-07-31 | 2007-07-31 | A kind of painted composite active black dye that is used for cellulosic fibre |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100704122A CN100549105C (en) | 2007-07-31 | 2007-07-31 | A kind of painted composite active black dye that is used for cellulosic fibre |
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| Publication Number | Publication Date |
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| CN101125966A CN101125966A (en) | 2008-02-20 |
| CN100549105C true CN100549105C (en) | 2009-10-14 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788705A (en) * | 2011-12-14 | 2014-05-14 | 褚平忠 | Black reactive dye composition |
| CN103013176B (en) * | 2013-01-05 | 2014-12-10 | 江苏德美科化工有限公司 | High-performance green reactive dye mixture and application thereof |
| CN103740132B (en) * | 2014-01-24 | 2015-09-30 | 浙江劲光实业股份有限公司 | A kind of preparation method mixing orange reactive dyestuffs |
| CN104927394A (en) * | 2015-05-27 | 2015-09-23 | 江苏沃尔得化工有限公司 | Synthetic process for active dye black |
| CN105038311A (en) * | 2015-05-27 | 2015-11-11 | 江苏沃尔得化工有限公司 | Active printing black synthesis process |
| CN109294276A (en) * | 2018-11-09 | 2019-02-01 | 上海贝通色彩科技有限公司 | A kind of composition of reactive dye and its preparation method and application |
| CN109468864B (en) * | 2018-11-19 | 2019-09-10 | 绍兴百丽恒印染有限公司 | The non-aqueous dyeing method that fixation substep carries out is contaminated on cotton fabric |
| CN110042678B (en) * | 2019-04-18 | 2021-11-05 | 浙江海印数码科技有限公司 | Dark black reactive dye ink and preparation method thereof |
| CN111073341A (en) * | 2019-12-23 | 2020-04-28 | 湖北丽源科技股份有限公司 | Black reactive composite dye and preparation process and application thereof |
| CN112708285B (en) * | 2020-12-29 | 2022-04-29 | 杭州吉华江东化工有限公司 | Production method for improving color matching and efficiency of active black W |
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