CN1296438C - Black and active dye - Google Patents

Black and active dye Download PDF

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Publication number
CN1296438C
CN1296438C CNB2005100471354A CN200510047135A CN1296438C CN 1296438 C CN1296438 C CN 1296438C CN B2005100471354 A CNB2005100471354 A CN B2005100471354A CN 200510047135 A CN200510047135 A CN 200510047135A CN 1296438 C CN1296438 C CN 1296438C
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dye
acid
component
black
dyestuff
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CN1730565A (en
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吴祖望
冯柏成
王专
林莉
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Dalian University of Technology
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Dalian University of Technology
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Abstract

The present invention provides the black composite reactive dye composed of three primary color components, which comprises a diazo component, a blue disazo dye, a red disazo dye and a yellow disazo or polyazo dye, wherein the ethylene series arylamine or an aniline derivative is taken as the diazo component, the H-acid of the blue disazo dye is a coupling component, one or more than one sulfoalkyl J acid or carboxymethyl J acid derivative of the red disazo dye is the coupling component, and one or more than one 3, 5-diaminobenzoic acid or sulfoalkyl derivative of the yellow disazo or the polyazo dye is the coupling component. The dye is suitable for intermittent and continuous dyeing for cellulose fiber, protein fiber and polyamide fiber and fiber mixed fabrics thereof. The dyeing fabric has excellent blackness, level dyeing property and lifting force.

Description

Black and active dye
Technical field
The present invention relates to the composition and the synthesis technique of a multi-component dark black active dyestuff.It is close to the colouring speed of fiber that its characteristics are to form each component of this dyestuff, and coloured fibre has good pitch black degree, level-dyeing property and good fastness.This dyestuff is applicable to cellulosic fibre, protein fibre and tynex dip-dye, pad dyeing-decatize, pad dyeing-bake and pad dyeing-bank up and jet dyeing.
Background technology
Black dyes is to use the look kind more, that output is bigger in the dyestuff.Wherein the C.I. reactive black 5 is the reactive dyestuffs kind of global current output maximum.But as black dyes, its pitch black degree is not enough.Korea S went into the pitch black degree that following orange component is improved dyeing back fiber with the complementary color principle with assembly in 1988, made the output of reactive black turn over liter at double.Simultaneously, become the first sign of improving the reactive black quality by the commercialization of dyes technology.
Figure C20051004713500041
Although the composite reactive black output that obtains of above-mentioned dyestuff has reached ten thousand tons of meters, this pieces together the union dyeing material and exists following critical defect: (1) pitch black degree is still not ideal enough, does not reach black degree; (2) both water-soluble reaching have than big difference the cellulosic fibre substantivity, the dyeing behavior compatibleness is poor: fiber affinity is also differed bigger, and orange O1 dyestuff is higher to fiber affinity, is adsorbed onto on the fiber earlier, cause different period coloured light differences in the dyeing course, easily cause the look flower; When adding the alkali fixation, orange component easily precipitation is separated out, and causes color spot especially; (3) both reactivities have difference.Orange component has the dichlorotriazine active group, and speed of response is higher than reactive black 5 (B1).
Over past ten years, mainly be in the adjustment of dark blue composite dye structure and each component ratio of mixture for the improvement of reactive black.The inventor proposed at " dyestuff and dyeing " magazine in 2004: under the theoretical direction of the supramolecular chemistry of dyestuff, the introducing substituting group makes the highest absorption red shift of absorption curve and increases water soluble group and introduce character and the suitable active group of quantity in red, orange component in dark blue component, adapt with fixing property, improve the dyeing compatibleness with the avidity of dark blue component.In the domestic and international patent in recent years the improvement of black and active dye is carried out according to above-mentioned thinking just.Wherein relatively success as US6537332, propose with above-mentioned cyan dye B1 and following orchil R1 and composite pitch black degree and all good reactive black of level-dyeing property of obtaining of orange dye O2 among the USP5849887.
Figure C20051004713500051
Other provides the close patent of invention of black and active dye composition to also have CN195678A, WO2004069937, US6160101 etc.
Summary of the invention
The purpose of this invention is to provide one group the polycomponent black composite active dye that good dyeing behavior, pitch black degree, level-dyeing property and lifting force are good, synthetic conveniently, raw material is easy to get is arranged.At least by following general formula (1), (2), (3) are dark blue, red, Yellow active dye is formed.Its dyeing behavior is characterised in that each component dyestuff good and compatibleness and lifting force.Its DYED FABRICS has excellent pitch black degree and painted level-dyeing property.
The constitutional features of dyestuff of the present invention is that the structure of three primary colors component dyestuff has very approaching wetting ability/lipophilicity, wherein: be contained in the navy tetrazo type reactive dyestuffs shown in the formula (1):
With contain the tetrazo type reactive dyestuffs shown at least a formula (2):
Figure C20051004713500062
With contain tetrazo shown at least a formula (3) or trisazo-type reactive dyestuffs:
Above-mentioned general formula (1), (2) are in (3);
X=H or
Group on Y=vinyl or the ethyl β position can come off under alkaline condition and generate the group of vinyl sulfone(Remzaol,
As chlorine, beta-hydroxyethyl sulfuric ester, especially good is vinyl sulfone(Remzaol and beta-hydroxyethyl sulfuric ester;
Z=hydrogen, CH 2SO 3M, CH 2CH 2SO 3M or CH 2COOM;
W=CH 2SO 3M, CH 2CH 2SO 3M or CH 2COOM;
M=hydrogen or basic metal are as lithium, sodium and potassium;
R 1~R 12=hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or chlorine;
R 13, R 14=hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, carboxyl, sulfonic group or sulfuric acid ester ethyl sulfone.
As the active diazo component of blue or green, red, yellow dye as:
Figure C20051004713500081
Or the vinyl sulfone(Remzaol derivative 01V-13V of compound 01-13
Figure C20051004713500082
Figure C20051004713500101
The general structure of red component dyestuff (2) is:
Figure C20051004713500102
(2) used coupling component is (30):
Figure C20051004713500111
In the formula
W=CH 2SO 3M, CH 2CH 2SO 3M or CH 2COOM;
M=hydrogen or alkalimetal ion are as lithium, potassium, sodium ion;
This compound (30) is made by J acid and sodium hydroxymethane sulfonate, chloroethyl sodium sulfonate or chloroacetate reaction.For example the available methylol sulfonic acid of sulphur methyl J acid is azochlorosulfonate methyl agent.The latter then can very easily be got by formaldehyde and sodium bisulfite addition smoothly.
(2) contain R on the ring in 5, R 6, R 7, R 8Substituent active diazo component can be some among 01-13 or the 01V-13V in the top literary composition.
The general formula of synthetic dyestuff (3) is:
(3) used coupling component is 3 in, the 5-Diaminobenzoic acid derivatives:
Z=hydrogen or AlkSO in the formula 3M
Alk=methylene radical or ethylene group;
M=hydrogen or lithium, potassium, sodium metal ion.
R in the diazo component 9, R 10, R 11, R 12Substituent active diazo component can be some among 01-13 or the 01V-13V in the top literary composition.X can be H ((3) are disazo dyess) or contain R 13, R 14The ring diazo component (trisazo dye) can be in the top literary composition 01,02 or 21-29 in some.
Figure C20051004713500121
In three kinds of component dyestuffs, raw material is easy to get, the cyan component commonly used (1) of better performances is as 101,102, and 103 etc.:
Figure C20051004713500131
The red component commonly used (2) of better performances is as 201,202, and 203,204,205 etc.:
The yellow color component of better performances (3) is as following dyestuff (301)-(308) etc.
Figure C20051004713500142
The preparation method of dyestuff (1) be with H acid with etc. the diazonium salt of mol ratio beta-hydroxyethyl sulfone sulfate ester aniline derivative under the condition of pH<2, carry out earlier a coupling obtain in the middle of dyestuff, again under pH=4~7 conditions and the diazonium salt of another part beta-hydroxyethyl sulfone sulfate ester aniline derivative carry out the secondary coupling and obtain dyestuff (1).The diazonium salt of twice coupling can be identical, also can be different.Under the identical situation of the diazo component of twice coupling, the H acid solution can be added drop-wise in the diazonium liquid that two moles doazo reaction finishes, control by pH and finish twice coupling.Permission slightly adjusts in the proportioning of diazo component and coupling component, to adjust the coloured light of dark blue component.Can be directly after coupling finishes or desalt through membrane sepn and to carry out spraying drying after concentrating and obtain solid dye (1).
The preparation method of dyestuff (2) carries out diazotization (mixture of also available two kinds of components in case of necessity) with any arylamine among compound 01-13 or the 01V-13V, under the condition of pH<2, carry out earlier a coupling with corresponding coupling component then, and then under pH=4~7 conditions, carry out the secondary coupling, reaction solution can be directly or membrane sepn desalt and carry out spraying drying after concentrating and obtain solid dye (2).
The preparation method of dyestuff (3) carries out diazotization with the arbitrary arylamine among the compound 21-31, then with 3,5-diaminobenzoic acid or derivatives thereof is under promoter effect, under pH<3.2 conditions, carry out the coupling first time, and then and compound 01-13 or 01V-13V in any arylamine diazonium salt (can be the mixture of two kinds of components in case of necessity) time carry out the coupling second time in pH<4, time carry out coupling for the third time in pH<6.3, reaction solution is saltoutd after acidifying, and drying obtains solid dye (3).
Blue or green: red: the weight percent of yellow three primary colors component is 50~90: 25~5: 25~5.
Composite active dye can be with structure the dyestuff shown in (1), (2), (3) in specified ratio mechanical means mixed preparing, also can do by the water-soluble back spray of proportioning.
Black composite active dye of the present invention is suitable for dying natural fiber, as cotton, fiber crops, regenerated fibre, is applicable to protein fibre and tynex too.Above-mentioned textile fiber can take various forms, as fiber, yarn, fabric or tricot.Dip-dye is after pollutant is adsorbed in the dye bath of specified mix, to use the alkaline purification fixation again, and dyeing and color fixing temperature are 50~70 ℃, the level-dyeing property of this dyestuff, lifting force are good, the compatibleness of three components is good, and coloured light is more stable in the dyeing course, and has good pitch black degree.
Among the following embodiment, as do not have especially and indicate, hundred mass fractions (with g or kg metering) are rolled in being of referring to.
Embodiment
Embodiment 1
Synthesizing of sodium hydroxymethane sulfonate:
In the 500ml there-necked flask, 104g sodium bisulfite (1mol) is used the 150ml water dissolution, under 35 ℃, drip 88g36% formaldehyde solution (1.05mol), in stirring reaction 3-5 below 50 ℃ hour.In 60-70 ℃ of following decompression dehydration 100ml, obtain concentrated solution.With the concentrated solution cooling, add a certain amount of recrystallisation solvent, under 0-5 ℃, left standstill crystallization 5 hours, filter, filter cake 30ml absolute ethanol washing, drying gets 125g sodium hydroxymethane sulfonate white solid.
Embodiment 2
Synthesizing of sulfomethylation J acid:
In the 500ml there-necked flask, 23.9gJ acid is scattered in the 200ml water, uses 20%Na 2CO 3Solution is regulated pH to 6-7, adds the 15g sodium hydroxymethane sulfonate, in reacting 3-6h below 50 ℃, gets sulfomethylation J acid solution, content 〉=95% (HPLC) of wherein sulfomethylation J acid in the organism.
Embodiment 3
Synthesizing of orchil 201:
56.2g para-ester and 13g sulfuric acid are mixed, add the 350g mixture of ice and water, making beating 30min, 0-5 ℃ drips 47g30%NaNO down 2Solution keeps NaNO in dropping and the reaction process 2Excessive.Drip the back and continue stirring reaction 2h, excessive N aNO 2Destroy with thionamic acid, get the para-ester diazonium salt.
The para-ester diazonium salt is joined in the sulfomethylation J acid solution of embodiment 2, control pH≤2 down at 0-5 ℃, coupled reaction 3h is transferred to pH 5-6 again, and coupled reaction 3h is concentrated with the dye solution of gained, fries and does, and pulverizes, and gets the 125g dye powder.
Embodiment 4
Synthesizing of yellow dyes 301
17.2g Sulphanilic Acid is used 23g 30%NaNO about 5 ℃ 2Solution, 20g 36% concentrated hydrochloric acid carry out diazotization.Reaction is finished with thionamic acid or the unnecessary NaNO of urea destruction 2The 0.5g dispersion agent is joined in the diazonium liquid, and after stirring, with 3,5-diaminobenzoic acid 15.5g dissolves in the 100ml6% hydrochloric acid soln, cools to the coupling component solution that obtains about 5 ℃ and is added in the above-mentioned diazonium salt, carries out a coupling.Control reaction solution pH≤3, complete to a coupling.56.2g the diazonium salt solution that para-ester is made is added drop-wise in the above-mentioned coupling solution, at room temperature, pH progressively brings up to 6.0-6.2, to reacting completely.The dye solution acidifying is saltoutd with NaCl.Filtration cakes torrefaction is pulverized, and gets the about 112g of pale brown look dye powder.
Embodiment 5
70g dyestuff (101), 15g dyestuff (201), 15g dyestuff (301) and appropriate amount of addition agent are carried out dry powder blend in tempering tank, or common dissolving back spraying drying, and the black dyes that obtains dyes the cotton aterrimus that is.Have good dyeing ability and satisfied dyefastness.
But other dyestuff synthetic method reference example 1-5
Embodiment 6-20
The dye set of embodiment 6-20 becomes to see Table 1, is undertaken by embodiment 5 similar methods.Form by following dyestuff and all can obtain all excellent reactive black of coloured light and dyeing behavior.
The dyestuff of embodiment 6-20 is formed
Sequence number Cyan dye 1 Orchil 2 Yellow (orange) look dyestuff 3 Weight ratio: green grass or young crops: red: yellow (orange)
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 101 101 101 101 103 103 101 101 102 101 101 102 101 101 101 201 205 201 202 201 201 201 201 205 203 201 205 201 204 201 306 306 302 302 308 301 302 305 306 301 307 302 304 301 308 65∶15∶25 62∶15∶17 70∶15∶15 65∶10∶25 60∶20∶20 65∶17∶1/8 75∶10∶25 75∶15∶10 60∶10∶30 73∶5∶22 60∶20∶20 65∶25∶10 70∶15∶15 60∶18∶22 65∶15∶20
Embodiment 21
The 100g cotton by the black dyes that embodiment 5-20 obtains, is pressed fabric and is weighed 2%, is in 20: 1 the dye bath containing 50g/L Sodium sulfate anhydrous.min(99), bath raio, and 60 ℃ of absorption 30min down add soda ash (consumption 15-20g/L) fixation 45min.DYED FABRICS is through washing, soap boiling, drying.The black cotton that obtains has the black and the satisfied Exposure to Sunlight and the moisture resistant fastness of homogeneous.

Claims (1)

1. compound black and active dye of being made up of blue or green, red and yellow three primary colors is characterized in that this dyestuff is made up of (1), (2), (3) general structure:
Figure C2005100471350002C1
In above-mentioned general formula (1), (2), (3):
R 1~R 12=hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, sulfonic group or chlorine atom;
X=H or
R 13, R 14=hydrogen, methyl, ethyl, methoxyl group, oxyethyl group, carboxyl, sulfonic group or sulfuric acid ester ethyl sulfone;
Y=vinyl or beta-hydroxyethyl sulfuric ester;
Z=hydrogen, CH 2SO 3M, CH 2CH 2SO 3M or CH 2COOM;
W=CH 2SO 3M, CH 2CH 2SO 3M or CH 2COOM;
M=hydrogen or lithium, sodium, potash metal ion;
In above-mentioned compound black and active dye, (1): (2): the weight percent of (3) is 50~90: 25~5: 25~5.
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CN103804248A (en) * 2012-11-07 2014-05-21 嘉兴学院 Method for synthesizing 3-(beta-sulfate ethyl sulfuryl)-N-ethyl aniline
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CN103992659B (en) * 2012-12-31 2016-08-17 浙江瑞华化工有限公司 A kind of Black reactive dye composition
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CN104073024B (en) * 2014-07-10 2016-07-06 浙江瑞华化工有限公司 A kind of Black reactive dye composition and its purposes
CN104861739A (en) * 2015-04-29 2015-08-26 浙江亿得化工有限公司 Red reactive dye and preparation method thereof
CN105778563B (en) * 2016-03-17 2017-08-08 浙江瑞华化工有限公司 A kind of Black reactive dye composition and its production and use
CN105694533A (en) * 2016-03-17 2016-06-22 浙江瑞华化工有限公司 Black reactive dye composition and preparation method and application thereof
CN105778560B (en) * 2016-03-17 2017-08-08 浙江瑞华化工有限公司 A kind of red reactive dye composition and its production and use
CN107501996A (en) * 2017-09-07 2017-12-22 上海万得化工有限公司 A kind of synthetic method of black and active dye compound
CN109971209B (en) * 2019-04-23 2020-12-04 南京林业大学 Amino naphthol sulfonic acid azo type reactive dye and preparation method thereof

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