CN100535059C - Dark black active dyestuff having high colour fixing rate - Google Patents

Dark black active dyestuff having high colour fixing rate Download PDF

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CN100535059C
CN100535059C CNB2006100474889A CN200610047488A CN100535059C CN 100535059 C CN100535059 C CN 100535059C CN B2006100474889 A CNB2006100474889 A CN B2006100474889A CN 200610047488 A CN200610047488 A CN 200610047488A CN 100535059 C CN100535059 C CN 100535059C
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component
general formula
dyestuff
dyeing
dark blue
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CN1912014A (en
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吴祖望
王专
冯柏成
林莉
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Dalian Huacheng Zhongrui Science & Technology Co Ltd
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Dalian Huacheng Zhongrui Science & Technology Co Ltd
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Abstract

The invention provides an dark black reactive dye having high color fixation rate and compounded of three-primary color components: dark blue, fuchsine and orange components and the synthesizing method thereof, where the weight percents of the navy, fuchsine and orange components are (40-85)%, (5-30)%, and (5-25)%, respectively. And it has characters: it has very high blackening; color fixation rate up to above 80% at standard color and cplor of dyeing liquor residue is low, having good environmental benefits; dyeing curves of component to fiber are completely consistent; the dyed fabrics have good color uniformity. And it is especially applied to exhaustive dyeing of fibrin, protein fibre and polyarmide fiber.

Description

Dark black active dyestuff with high colour-fast rate
Technical field
The present invention relates to the reactive dyestuffs of field of fine chemical.
Background technology
Black and active dye is to use the kind more, that output is bigger in the dyestuff.Since 21 century, a large amount of reactive black patent is come out, but up to now, and to be still with the C.I. reactive black 5 be the navy component to the overwhelming majority in the commodity reactive dyestuffs, with red and yellow color component is composite, obtains pitch black degree reactive black preferably.Cibacron Black WNN for example, Cibacron Supra Black G, Cibacron Supra Black R etc.The advantage of these dyestuffs also has and dyes the curvilinear trend unanimity on trichromatic except DYED FABRICS has preferably pitch black degree, and consistency is better etc.Xiang Guan patent has CN200510047135.4 therewith, CN200510047136.9, WO2004069937, US6537332, USP5849887 etc.
Figure C20061004748800041
But the main deficiency of above-mentioned dyestuff is that the degree of fixation of dyestuff has only 60～65%, the colourity height of dyeing residual liquid, and the dyestuff of a large amount of not sets and hydrolysis remains in the dyeing waste liquid, has not only influenced economic benefit, and has caused environmental pollution.
Improving the reactive black degree of fixation, reduce dyestuff content in the dyeing waste liquid, is the main purpose that the present invention improves black and active dye.
Summary of the invention
The invention provides one group by the polycomponent composite black reactive dyestuffs that good dyeing behavior, pitch black degree, level-dyeing property and lifting force are good, degree of fixation is high, synthetic three primary colors component convenient, that raw material is easy to get is formed.At least by the navy component of following general formula (1), general formula (2), the magenta component of one of (3), general formula (4), (5), the Yellow active dye of one of (6) is formed.Its performance characteristic is each component dyestuff excellent compatibility and lifting force.Its DYED FABRICS has excellent pitch black degree and uniform dyeing property.
Composite dye constitutional features of the present invention is that the structure of three primary colors component dyestuff has very approaching wetting ability/lipophilicity, wherein comprises dark blue, the pinkish red and orange-yellow component of following general formula.
The dark blue reactive dye component is the structure shown in 1～2 kind of general formula (1):
Figure C20061004748800051
In the general formula (1):
Ar 1, Ar 2=phenyl ring, naphthalene nucleus or contain the benzanilide skeleton, but Ar 1, Ar 2In have at least one to be naphthalene nucleus or contain the benzanilide skeleton:
Figure C20061004748800052
R 1～R 4=H, CH 3, OCH 3, SO 3M or Cl;
M=H, Na or K;
Y=Cl ,-CH=CH 2Or-CH 2CH 2OSO 3H;
The red reactive dyes component is the structure shown in 1～2 kind of general formula (2) or (3):
Figure C20061004748800053
Figure C20061004748800054
In general formula (2), (3):
Ar 3=phenyl ring or naphthalene nucleus;
R 5～R 11=H, CH 3, OCH 3, SO 3M or Cl;
M=H, Na or K;
W=H, CH 3Or CH 2SO 3M;
X=SO 3M or SO 2Y;
Y=Cl ,-CH=CH 2Or-CH 2CH 2OSO 3H;
Yellow color component is 1～2 kind of general formula (4), the structure shown in (5) or (6):
Figure C20061004748800061
Figure C20061004748800063
General formula (4), (5), in (6):
Ar 4～Ar 7=phenyl ring or naphthalene nucleus;
R 12～R 18=H, CH 3, OCH 3, SO 3M or Cl;
R 19～R 21=H or SO 3M;
M=H, Na or K;
Q=H, SO 3M, C 6H 5Or C 6H 4SO 3M;
W＝H、-CH 3、-CH 2SO 3M；
X=SO 3M or SO 2Y;
Y=Cl ,-CH=CH 2Or-CH 2CH 2OSO 3H;
Z=H or COOH;
The proportioning of above-mentioned three primary colors reactive dyestuffs component is: dark blue: magenta: orange weight percent is (40～85): (5～0): (5～25), each component concentration sum is 100%.
As the active diazo component of Huang, product, blue or green three primary colors component dyestuff such as (01-13) of benzene compounds:
Figure C20061004748800064
Figure C20061004748800071
Figure C20061004748800081
Naphthalene is a diazo component as (14-16):
The diazo component of benzanilide (BZA) derivative as:
Figure C20061004748800083
Figure C20061004748800091
Or the vinyl sulfone(Remzaol derivative 01V-20V of compound 01-20:
Figure C20061004748800092
Figure C20061004748800101
Figure C20061004748800111
The structure of navy component dyestuff has front general formula (1) constitutional features.The dark blue reactive dye of for example following naphthalene system (101-128) and two series of BZA (201-220):
Figure C20061004748800112
Figure C20061004748800121
Figure C20061004748800131
Figure C20061004748800141
Figure C20061004748800161
Figure C20061004748800171
The red component dyestuff is at least one or two orchil of the feature of have general formula (2) or general formula (3) structure.Dyestuff (301-307) or (401-408) in for example following two series:
Figure C20061004748800191
Figure C20061004748800201
Figure C20061004748800211
At least one or two have the structure of formula (4), (5) or (6) the yellow color component dyestuff.Be exemplified below row dyestuff (501-508), (601-605), (701-704), (801-804) etc.
Figure C20061004748800212
Figure C20061004748800221
Figure C20061004748800231
Figure C20061004748800241
Figure C20061004748800251
Above-mentioned diazotization, the couling process preparation of respectively organizing dyestuff can be conventional.Can concentrate by the membrane sepn desalination in case of necessity, to make the dyestuff of high density.
Black dyes can be composite by a certain percentage by orange, pinkish red, dark blue component, makes the reactive black of high colour-fast rate.Each component of three primary colors can be a dyestuff, also can be the mixture of two dyestuffs.The characteristics of gained reactive black are that the consistency of three primary colors component is good, and dyeing speed is approaching, the degree of fixation height, and the colourity of dyeing residual liquid is more shallow.Composite method can be each component powder dye (dry method) intermingling in mixing machine, also can dissolve back (wet method) spraying drying again by designated ratio.
Dark blue, magenta, the ratio range of orange three primary colors component is generally (40～85): (5～30): (5～25).
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.
Embodiment
Among the following embodiment, as do not have especially and indicate, hundred parts by weight (with g or kg metering) are rolled in being of referring to.
Embodiment 1
0.1mol para-ester (compound 01) and 0.13mol sulfuric acid are mixed, add the 350g mixture of ice and water, making beating 30min drips 30%NaNO at 0～5 ℃ under liquid level 2Solution 0.1mol keeps NaNO in dropping and the reaction process 2Excessive.Diazotization behind terminal point, excessive N aNO 2Destroy with thionamic acid.
0.1mol 1-amino-8-naphthol-3,6-disulfonic acid (H acid) solution adds in the above-mentioned diazonium salt, carries out acid coupling under 5～8 ℃.After reaction is finished, 6-sulfuric ester hydroxyethyl sulfone-2-naphthylamines-1-sulfonic acid (compound 14) diazonium salt is added drop-wise in the monoazo-dyes reaction solution of above-mentioned acid coupling, keeps 10 ℃, pH 6～6.5 and be reacted to terminal point.Make navy component dyestuff 105 after membrane sepn desalination, the spraying drying.
Embodiment 2
In 10%J acid solution (0.1mol), add the 15g sodium hydroxymethane sulfonate, reacting 4h below 50 ℃, get 2-sulphur methylamino--5-naphthols-7-sulfonic acid solutions.0.1mol the para-ester diazonium salt solution adds in the above-mentioned coupling component, controls pH≤2, is coupled to react completely under 0～5 ℃; PH is transferred to 5～6 and the diazonium salt of 0.1mol 2-methoxyl group-4-sulfuric acid ester ethyl sulfone aniline is added drop-wise in this monoazo-dyes again, control pH 6～6.5, after the secondary coupled reaction is finished, desalination, spraying drying, reddish-brown powdery red component dyestuff 302.
Embodiment 3
0.1mol add 0.5 part of condensation compound of methyl naphthalene sulfonic acid and formaldehyde in the ORTHO AMINO PHENOL SULPHONIC diazonium salt solution as dispersion agent, after stirring, join concentration and be 10% 3, in the 5-diaminobenzoic acid sodium (0.1mol), carry out a coupling at 5 ℃.Control reaction solution pH≤3, complete to a coupling.0.2mol the para-ester diazonium salt solution is added drop-wise in the above-mentioned coupling solution, at room temperature, pH progressively brings up to 6～6.2, to reacting completely.Saltout, drying and crushing, pale brown brown yellow component dyestuff 501.
Embodiment 4
58 parts of dyestuffs (105), 17 parts of dyestuffs (302), 15 parts of dyestuffs (501) and 10 parts of naphthalene sulfonic acidformaldehyde condensation products carry 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.
Embodiment 5
With reference to the synthesis technique of embodiment 1, replace compound 14 with 6-sulfuric ester hydroxyethyl sulfuryl-2-naphthylamines (compound 16), synthesized dark blue component dyestuff 112.
Embodiment 6
Para-ester diazonium salt and 2, the 4-diamino benzene sulfonic acid carries out coupling at pH about 4, conditioned reaction liquid pH 6～6.5 then, the diazonium salt coupling with 2-sulfo group-5-sulfuric ester ethyl sulfonyl-aniline (compound 11) obtains yellow color component dyestuff 605.
Embodiment 7
Dark blue component dyestuff 112, red component dyestuff 302, yellow color component dyestuff 501 carry out composite with weight ratio at 55: 18: 17, after 10 parts of methods by embodiment 4 of 90 parts of dyestuffs that obtains and auxiliary agent condensation compound of methyl naphthalene sulfonic acid and formaldehyde are mixed, the reactive black three primary colors consistency that obtains is good, dye cellulosic fibre and have good pitch black degree, higher degree of fixation and the colour fastness of being satisfied with, dyeing residual liquid colourity is low.
Embodiment 8
Synthesis technique with reference to embodiment 1 dark blue component 105; replace 6-sulfuric ester hydroxyethyl sulfuryl-2-naphthylamines-1-sulfonic acid (compound 14) with 4-sulfuric acid ester ethyl sulfone-(4 '-amino-benzoyl)-aniline (compound 20), i.e. the dark blue component dyestuff 203 that para-ester diazonium salt and H acid acid coupling, compound 20 diazonium salt alkaline couplings obtain.
Embodiment 9
Dark blue component dyestuff 203, red component dyestuff 301, yellow color component dyestuff 703 carry out composite with weight ratio successively at 60: 20: 12, after 8 parts of methods by embodiment 4 of 90 parts of dyestuffs that obtains and auxiliary agent condensation compound of methyl naphthalene sulfonic acid and formaldehyde are mixed, the reactive black three primary colors consistency that obtains is good, dye cellulosic fibre and have good pitch black degree, higher degree of fixation and the colour fastness of being satisfied with, dyeing residual liquid colourity is low.
Embodiment 10-20
The synthetic complex process that reaches of the dyestuff of embodiment 10-20 can carry out with reference to the method for embodiment 1-4.The component utilized dyestuff is as shown in table 1.The proportioning of each component dyestuff can be adjusted at 0 proportional range that the present invention provides according to required coloured light in the black dyes.
The dyestuff of embodiment 10-20 is formed
Figure C20061004748800271
Embodiment 21
100 parts of cottons by the black dyes that embodiment 5-20 obtains, are pressed fabric and are weighed 2%, are 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 60min.DYED FABRICS is through washing, soap boiling, drying.The black cotton that obtains has good pitch black degree and level-dyeing property and satisfied Exposure to Sunlight, moisture resistant fastness is arranged.Dye fixing rate height, dyeing residual liquid colourity is low.

Claims (1)

1. one kind by the composite dark black active dyestuff of forming of dark blue, pinkish red, orange three primary colors, it is characterized in that three primary colors reactive dyestuffs general structure is:
The dark blue reactive dye component is the structure shown in 1～2 kind of general formula (1):
Figure C2006100474880002C1
In the general formula (1):
Ar 1, Ar 2=phenyl ring, naphthalene nucleus or contain the benzanilide skeleton, but Ar 1, Ar 2In have at least one to be naphthalene nucleus or contain the benzanilide skeleton:
R 1～R 4=H, CH 3, OCH 3, SO 3M or Cl;
M=H, Na or K;
Y=Cl ,-CH=CH 2Or-CH 2CH 2OSO 3H;
The red reactive dyes component is the structure shown in 1～2 kind of general formula (2) or (3):
Figure C2006100474880002C3
In general formula (2), (3):
Ar 3=phenyl ring or naphthalene nucleus;
R 5～R 11=H, CH 3, OCH 3, SO 3M or Cl;
M=H, Na or K;
W=H, CH 3Or CH 2SO 3M;
X=SO 3M or SO 2Y;
Y=Cl ,-CH=CH 2Or-CH 2CH 2OSO 3H;
Yellow color component is 1～2 kind of general formula (4), the structure shown in (5) or (6):
General formula (4), (5), in (6):
Ar 4～Ar 7=phenyl ring or naphthalene nucleus;
R 12～R 18=H, CH 3, OCH 3, SO 3M or Cl;
R 19～R 21=H or SO 3M;
M=H, Na or K;
Q=H, SO 3M, C 6H 5Or C 6H 4SO 3M;
W＝H、-CH 3、-CH 2SO 3M；
X=SO 3M or SO 2Y;
Y=Cl ,-CH=CH 2Or-CH 2CH 2OSO 3H;
Z=H or COOH;
The proportioning of above-mentioned three primary colors reactive dyestuffs component is: dark blue: magenta: orange weight percent is (40～85): (5～30): (5～25), each component concentration sum is 100%.
CNB2006100474889A 2006-08-15 2006-08-15 Dark black active dyestuff having high colour fixing rate Expired - Fee Related CN100535059C (en)

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