CN1204203C - Asymmetricazo-based metal complex dye, preparation thereof and acidic black dye composition containing the same - Google Patents
Asymmetricazo-based metal complex dye, preparation thereof and acidic black dye composition containing the same Download PDFInfo
- Publication number
- CN1204203C CN1204203C CN01802267.7A CN01802267A CN1204203C CN 1204203 C CN1204203 C CN 1204203C CN 01802267 A CN01802267 A CN 01802267A CN 1204203 C CN1204203 C CN 1204203C
- Authority
- CN
- China
- Prior art keywords
- formula
- compound
- following formula
- dyestuff
- representatives
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0046—Mixtures of two or more azo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
- C09B45/26—Disazo or polyazo compounds containing chromium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coloring (AREA)
Abstract
The present invention relates to a novel asymmetric azo-group metal complex dye which has superior high color depth and excellent fastness, a preparation method thereof and an acidic black dye composition comprising the dye.
Description
Invention field
The present invention relates to a kind of asymmetric azo-group metal complex dye of novelty.Particularly, the present invention relates to a kind of novel asymmetric azo-group metal complex dye and preparation method thereof with dark colour very and good fastness.The invention still further relates to and comprise the erie black dye composition of this asymmetric azo metal complex dyestuff as main ingredient.
Background of invention
People have developed and have been used for tynex such as nylon 6 and nylon 66 painted various black dyess.The representative of the black dyes of tynex dyeing usefulness has the acid black dyes of following formula 13 representatives:
Formula 13
Yet when above-mentioned dye dosage was 5-7%o.w.f., most dyestuffs can not be fixed, and caused poor performance such as wash resistant fastness, water-fast fastness, perspiration fastness.
Another problem of this dyestuff is that for improving its repeatedly rinsing of fastness requirement dyestuff, handling waste water like this needs more times and expense.Especially the defective that above-mentioned conventional acid black dye exists has, and dyeing planeness and colouring (build-up) effect be poor, to color expressive force (color expression) deficiency of cellulosic fibre, natural wool fiber and synthetic polyester fibers.And, for showing dark color, require conventional acid black dyes and another kind of dye combinations to use.
EP 0 384 893 A1 (corresponding to United States Patent (USP) 5,229,502) disclose a kind of preparation purity and have been at least 85%, asymmetric 1: 2 chromium coordination azoic dyestuff and/or contain at least two azo methyl dyestuffs that water miscible group can be provided.Represent this dyestuff by following formula 14:
Formula 14
Although above-mentioned patent says that this dyestuff can be applicable to various fibers and comprises real silk, wool knitting yarn, leather, synthetic polyamide fiber etc. and have good fastness, can not be applied to clothing or the goods higher to the dyestuff specification of quality.In addition, this dyestuff mainly is subjected to the restriction of red or orange expressive force.Also do not have document to mention and to show versicolor black dyes.
Generally, black dyes uses with the mixture with the tone of red, orange and/or yellow dyes, to strengthen their black colouring effect.By the prior art for example open clear 58-160362 of communique, flat 2-202956 peace 2-73870 of Japanese Patent and United States Patent (USP) 5,445,654,5,092,905 and 6,126,700, comprise the dye mixture of black dyes and other color dye as can be known, these documents are in full with reference to being incorporated into this.Because the character of the dye mixture that discloses in these documents greatly depends on the black dyes component,, can not desired color expressive force other performance in addition improve under not improving as the black dyes performance of background color (base).
Therefore, still need a kind of energy to solve the anti-jail property problem of conventional acid black dyes and the improved acid black dyes of the economic problems that extra rinse cycle brings, this dyestuff and other dye combinations can provide the shades of colour performance, thereby have high added value (value-added) effect.
Summary of the invention
The inventor draws the present invention after acid black dyes is studied extensively and profoundly, find the asymmetric metal complex of erie black azo-dye, disazo compound wherein and chromium complex coupling, the fastness of very dark color of various fibers and raising can be provided, and find to contain the erie black dye composition of this dyestuff.
So first purpose of the present invention provides the asymmetric metal complex of acid black dyes, this complex compound can produce deep colour dyeing and have good fastness.
Second purpose of the present invention provides the method for the asymmetric metal complex of the convenient acid black dyes of preparation.
The 3rd purpose of the present invention provides the black dye composition based on acid black dyes.
According to first aspect present invention, provide erie black non-ferrous metal complex dyestuff by the asymmetric azo-group of following formula 1 representative:
Formula 1
Wherein, R
1Each other can be identical or different, be selected from hydrogen atom (H), nitro (NO separately
2), chlorine atom (Cl), sulfamyl (SO
2NH
2) and sulfo group (SO
3H); R
2Each other can be identical or different, be selected from hydrogen atom (H), nitro (NO separately
2), chlorine atom (Cl) and sulfo group (SO
3H).
According to second aspect present invention, the method for preparation by the asymmetric azo-group erie black non-ferrous metal complex dyestuff of formula 1 representative is provided, this method comprises the following steps:
A) make diazonium naphthalene (diazonium naphthalene) compound of following formula 2 representatives and the naphthol reaction of following formula 3 representatives, their equivalent ratio is 1: 0.8-1: 1.3, obtain the Monoazo compound of following formula 4 representatives, then, make this Monoazo compound and chromium donor with 1: 0.8-1: 1.3 equivalence ratio reaction produces the chromium complex of following formula 5 representatives;
B) the phenylnaphthalene compound of the amino-benzene compound that makes following formula 6 representative and following formula 7 representatives is with 1.5-2.5: 1 equivalence ratio, reaction in the presence of nitrite, the disazo compound that generation is represented by following formula 8;
C) the disazo compound reaction that chromium complex that 100-120 weight part step a) makes and 60-70 weight part step b) are made,
Formula 2
Formula 3
Formula 4
Formula 5
Formula 6
Formula 7
Formula 8
Wherein, R
1And R
2According to top definition.
According to third aspect present invention, the erie black dye composition of the dyestuff of at least a compound that is selected from following formula 9-12 representative that the asymmetric azo-group metal complex dye of a kind of 80-99% of comprising (weight) formula 1 representative and 1-20% (weight) be provided:
Formula 9
Formula 10
Formula 11
Formula 12
Implement preferred plan of the present invention
The present invention relates to a kind of asymmetric azo-group metal complex dye of novelty of formula 1 representative, this dyestuff is at λ
Max575 wavelength have absorption, and 90 ℃ of solubleness are 100g/l.In addition, novel dyestuff of the present invention has color much at one and has nothing to do with filamentary material.And the novel dyestuff of the present invention has very good wash resistant fastness, water-fast fastness and perspiration fastness than the acid black dyes of routine when using under identical o.w.f. leads.
Below, the preparation of the asymmetric azo-group metal complex compound of this acidity black dyes is described.
At first, by the naphthols of the diazonium naphthalene compound of following formula 2 representative and following formula 3 representatives with 1: the reaction of 0.8-1.3 equivalence ratio produces the Monoazo compound that following formula 4 is represented.
Formula 2
Formula 3
Formula 4
Wherein, R
1Each other can be identical or different, be selected from hydrogen atom (H), nitro (NO separately
2), chlorine atom (Cl), sulfamyl (SO
2NH
2) and sulfuryl (SO
3); R
2Each other can be identical or different, be selected from hydrogen atom (H), nitro (NO separately
2), chlorine atom (Cl) and sulfuryl (SO
3).
Particularly, under stirring the diazonium naphthalene compound is dissolved in the 0-10 ℃ of water, control pH is 3-5.For control pH, can use sodium acetate, sodium bicarbonate or SODA ASH LIGHT 99.2, wherein be preferably sodium acetate.
In addition naphthols being added in the entry, is 10-11 at 70-90 ℃ with alkali such as sodium hydroxide control pH, and this solution is cooled to 20-30 ℃ subsequently.Naphthol solution is added diazonium naphthalene solution, stir and to make it under the pH of 10-11 coupled reaction 5-6 hour down, the Monoazo compound of production 4.Then, remove impurity by currently known methods, for example dialysis, suction strainer and washing improve the purity of Monoazo compound.
During 1: 1 of the representative of preparation following formula 5 chromium complex, Monoazo compound is dispersed in the water, and stir down with the chromium donor with 1: 0.8-1.3 equivalent mol ratio, react under the 1.0-5.0 with pH at 125-135 ℃.
Formula 5
Wherein, R
1And R
2According to top definition.
Be suitable for chromium donor of the present invention and be selected from chromic formate, chromium chloride and chromic oxide.By currently known methods such as dialysis, suction strainer and the washing impurity in the product that can be removed.
Except that 1: 1 chromium complex of preparation, the amino-benzene compound of following formula 6 representatives reacts in the presence of nitrite with the phenylnaphthalene compound of following formula 7 representatives, obtains the disazo compound that following formula 8 is represented.For example, amino-benzene compound is dissolved in the water and the cooling liqs preparation.Adding acid, better be hydrochloric acid, be more preferably concentrated hydrochloric acid (to remove excessive nitrite salt) afterwards, this liquid preparation and nitrite better are that the aqueous solution of Sodium Nitrite mixes at 0-30 ℃.
Afterwards, the phenylnaphthalene aqueous solution that is added with alkali such as sodium hydroxide is added in this amino-benzene solution, its amount for the equivalence ratio of amino-benzene and phenylnaphthalene at 1.5-2.5: 1 scope is the coupled reaction of carrying out under the 9-11 5-6 hour at pH subsequently.The solution that makes is further purified by dialysis, suction strainer and washing.
Formula 6
Formula 7
Formula 8
Wherein, R
1And R
2According to top definition.
Be dissolved in 1: 1 chromium complex of 60-70 weight part disazo compound and 100-120 weight part in the water together, afterwards, this solution reacts under the 4.0-10.0 condition with pH at 50-90 ℃, obtains the asymmetric metal complex into the erie black azo-dye of needle-like black crystalline formula 1 representative.Separate by dialysis, suction strainer, 40-60 ℃ of drying, obtain highly purified metal complex subsequently.
According to the present invention, the asymmetric metal complex of above-mentioned erie black azo-dye can mix with other dyestuff, the performance shades of colour.In this case, dye composite comprises the acid black dyes of 80-99% (weight) and at least a dyestuff that is selected from by the compound of following formula 9-12 representative of 1-20% (weight):
Formula 9
Formula 10
Formula 11
Formula 12
Less than the auxiliary dyestuff of 1% (weight) very little, to bathochromic effect and colour-change without any effect.On the other hand, when auxiliary dye dosage during greater than 20% (weight), the look soundness of black dyes itself descends.
Can understand the present invention better by the following examples, these embodiment are used for explanation, are not construed as limiting the invention.Unless otherwise indicated, term " part " refers to weight part in the following example.
Embodiment 1
Stir down, at 10 ℃, 29.5 parts of 1-diazo-beta naphthal-6-nitro-4-sulfonic acid, 100 parts of water and 100 parts of ice mixed 30 minutes.In this mixture, add 2 parts of zinc chloride (ZnCl
2), afterwards, with 20 parts of sodium acetate (CH
3COONa) solution transfers to 3.0. with this mixture pH in 100 parts of water
In 150 parts of 80 ℃ of water, add 15 parts of beta naphthals (2-Naphthol), and dissolve fully, afterwards, add 150 parts of ice this solution is cooled to 30 ℃ with the NaOH of 10N.In this solution, add the mixture for preparing previously and mix, and regulate pH to 10, then, make them under agitation in 40 ℃ of coupled reactions of carrying out 5 hours.The dialysis in saturated brine solution of product solution obtains the Monoazo compound of following formula 15a representative, is the crystallization of needle-like black, and this crystallization is washed and carry out drying in about 50 ℃ under vacuum through suction strainer with 5% sodium chloride solution.In the presence of the NaOH of 10N, 43.9 parts of Monoazo compounds are dissolved in 300 parts of water, and with 10 parts of CrO
3Solution in 20 parts of water mixes.This Monoazo compound and CrO
3PH be 3.0 times in 130 ℃ of reactions 5 hours, produce the chromium complex of following formula 15b representative.After being cooled to 50 ℃, the solution that makes dialysis in saturated brine obtains crystallization, carries out suction strainer then, with the washing of 5% sodium chloride solution, and in vacuum-drying.
Also separately carry out, be mixed together 30 minutes under 30.8 parts of 4-nitro-2-amino-phenols and 150 parts of ice and 150 parts of water stir.Add 40 parts of concentrated hydrochloric acids subsequently, in 4-nitro-2-amino-phenol solution, add the solution of 14 parts of Sodium Nitrites in 40 parts of water, and stirred 30 minutes in 10 ℃.After removing excessive nitrite salt, the solution (about 10 ℃) that adds 31.5 parts of 6-amino-N-phenyl-3-sulfone-naphthols, 200 parts of water and 100 parts of ice in the NaOH of 10N in the solution that makes, then, stirring was carried out coupled reaction 5 hours, obtain the disazo compound of following formula 15c representative, this product carries out dialysis, suction strainer then, washs with saturated brine, and carries out drying in vacuum.
108.6 part chromium complex and 64.5 parts of disazo compounds in 500 parts of water are 9 times reactions 4 hours in 80 ℃ with pH, dialysis in NaCl subsequently, acquisition is the crystallization of needle-like black by the dyestuff of following formula 15d representative, separates and is concentrated into dried for following 50 ℃ in vacuum by suction strainer.This dyestuff is applied to nylon or tynex, obtains green black.
Formula 15a
Formula 15b
Formula 15c
Formula 15d
Embodiment 2
According to carrying out with embodiment 1 identical mode, difference is, use 25 parts of 1-diazo-beta naphthals-4-sulfonic acid to replace 1-diazo-beta naphthal-6-nitro-4-sulfonic acid, obtain the compound of following formula 16a representative and the chromium complex of following formula 16b representative, prepare the complex compound of following formula 16c representative at last by this complex compound.This dyestuff is applied to nylon or tynex, produces black-and-blue.
Formula 16a
Formula 16b
Formula 16c
Embodiment 3-25
According to carrying out with embodiment 1 identical mode, difference is Monoazo compound that use table 1 is listed and disazo compound.The dyestuff that obtains is applied to nylon or tynex, and its result is beneficial to table 1.
Table 1
Measure the dyestuff that obtains among these embodiment, show that its fastness is identical with the dyestuff of 2 preparations with embodiment 1.
Embodiment 26
The dyestuff of Chemical formula 1 5d representative is mixed by 97: 3 weight ratio with the dyestuff of formula 9 representatives.The solubleness of this dye composite is 100g/l (190 ℃).Find that the dye composite that makes is applied to tynex acquisition dyeing with the 5%o.w.f. amount compares with the conventional acid black dyes of formula 13 representatives, its water-fast fastness, washable fastness and perspiration fastness improve 2-2.5 grade.
Embodiment 27
The dyestuff of formula 16c representative is mixed by 96.5: 3.5 weight ratio with the dyestuff of formula 10 representatives.Find that the dye composite that makes is applied to tynex acquisition dyeing with the 5%o.w.f. amount compares with the conventional acid black dyes of formula 13 representatives, its water-fast fastness, washable fastness and perspiration fastness improve about 2 grades.
Embodiment 28
The dyestuff that embodiment 3 is made mixes by 94: 6 weight ratio with the dyestuff of formula 9 representatives.Find that the dye composite that makes is applied to tynex acquisition dyeing with the 5%o.w.f. amount compares with the conventional acid black dyes of formula 13 representatives, its water-fast fastness, washable fastness and perspiration fastness improve 2.5 grades and also present green black.
Embodiment 29
The dyestuff that embodiment 17 is made mixes by 98: 2 weight ratio with the dyestuff of formula 11 representatives.Find, the dye composite that makes is applied to tynex acquisition dyeing with the 5%o.w.f. amount to be compared with the conventional acid black dyes of formula 13 representatives, its water-fast fastness, washable fastness and perspiration fastness improve about 2 grades, show bluish black.
Embodiment 30
The dyestuff of formula 15d representative is mixed by 96: 4 weight ratio with the dyestuff of formula 12 representatives.Find, the dye composite that makes is applied to tynex acquisition dyeing with the 5%o.w.f. amount to be compared with the conventional acid black dyes of formula 13 representatives, its water-fast fastness, washable fastness and perspiration fastness improve about 2 grades, show bluish black.
Embodiment 31
The dyestuff that embodiment 4 is made mixes by 97.5: 2.5 weight ratio with the dyestuff of formula 9 representatives.Find, the dye composite that makes is applied to tynex acquisition dyeing with the 5%o.w.f. amount to be compared with the conventional matching stain of formula 13 representatives, its water-fast fastness, washable fastness and perspiration fastness improve about 2.5 grades, show bluish black.
Comparative example 1-5
Use conventional acid black dyes 52,222,107 and 172 respectively on nylon, cotton and wool fiber, obtain dyeing, measure the washable fastness of these printing products, water-fast fastness, perspiration fastness and anti-chlorine fastness, the result is beneficial to table 2.
Determine the fastness performance according to following standard:
-washable fastness (60 ° of ISO 105/C03)
Equipment: Launder-o-meter
Temperature: 60 ± 2 ℃ * 30 minutes
Washing composition: (5g/l)/Na
2CO
3(2g/l)
With liquid fraction: 50: 1
-water-fast fastness (ISO 105/E01)
Equipment: Perspirometer (4.5kg pressure)
Temperature: 37 ± 2 ℃ * 4 hours
-perspiration fastness (salt) (ISO 105/E04)
Equipment: sweating test instrument (perspiration tester)
Temperature: 30 ± 2 ℃ * 4 hours
Dissolving 0.5 gram hydrochloric acid L-Histidine monohydrate, 5 gram Sodium phosphate dibasics, 5 gram sodium-chlor in 1 premium on currency.
-Nai chlorine fastness (KS K 0725)
Equipment: sweating test instrument
Temperature: 38 ± 2 ℃ * 2 hours
Material is immersed in the sodium perchlorate solution that available chlorine is the 0.5g/ premium on currency reaches 4 hours, this pH value of solution is 8.0 ± 0.2, and temperature is 27.2 ± 2 ℃.
Table 2
| Embodiment | Washable fastness (grade) | Water-fast fastness (grade) | Perspiration fastness (grade) | Anti-chlorine fastness (grade) | ||||||||
| Nylon | Cotton | Wool | Nylon | Cotton | Wool | Nylon | Cotton | Wool | Nylon | Cotton | Wool | |
| 1 | 4 | 4-5 | 4 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 5 | 5 | 5 |
| 2 | 4 | 4-5 | 4 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 5 | 5 | 5 |
| 3 | 4 | 4-5 | 4 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 5 | 5 | 5 |
| 4 | 4 | 4-5 | 4 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 5 | 5 | 5 |
| 5 | 4 | 4-5 | 4 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 4-5 | 5 | 5 | 5 |
| C.1 | 2 | 2-3 | 2-3 | 2 | 3 | 3 | 2 | 1-2 | 2 | 2-3 | 2-3 | 2-3 |
| C.2 | 2 | 4-5 | 2-3 | 4 | 4-5 | 4-5 | 4 | 4-5 | 4 | 4-5 | 5 | 5 |
| C.3 | 1-2 | 4 | 2 | 3-4 | 4 | 4 | 4 | 4 | 4-5 | 4-5 | 5 | 5 |
| C.4 | 2-3 | 4 | 3-4 | 3-4 | 4 | 4 | 3-4 | 3-4 | 4 | 4 | 4-5 | 4 |
| C.5 | 2 | 4-5 | 3 | 3-4 | 4-5 | 4-5 | 4 | 4-5 | 4-5 | 4-5 | 5 | 4-5 |
By table 2 data as can be known, when using the dyestuff of comparative example 1-5 of 5-7%o.w.f., because the dyestuff residue on fixing yet, the washable fastness of dyeing, water-fast fastness and perspiration fastness are second or the tertiary gradient.In dyeing industry, conventional dyeing washes with water three times or four times, removing the dyestuff on fixing, thereby improves their fastness, and this can cause producing a large amount of waste water.And, need more times and expense to handle these waste water, therefore reduce productivity.
Different with it, dyestuff of the present invention except that dyeing high density dyestuff is provided, the good fastness that dyeing is had needn't wash.Acid black dyes of the present invention is because its high dye strength and good fastness have solved pollution and economic problems that conventional black dyes faces.In addition, dyestuff of the present invention can with incompatible performance shades of colour of other dye set and dark color.
Describe the present invention in detail in the explanation mode, should understanding as used herein, term is used for describing and is not construed as limiting.Can carry out various modifications and changes to the present invention according to the content that discloses above.So, should understand within claims scope, can implement the present invention and needn't specifically describe.
Claims (6)
1. asymmetric azo-group erie black non-ferrous metal complex dyestuff, by following formula 1 expression:
Formula 1
Wherein, R
1Each other can be identical or different, be selected from hydrogen atom H, nitro NO separately
2, chlorine atom Cl, sulfamyl SO
2NH
2And sulfo group-SO
3H; R
2Each other can be identical or different, be selected from hydrogen atom H, nitro NO separately
2, chlorine atom Cl and sulfo group-SO
3H.
2. method for preparing by the asymmetric azo-group erie black non-ferrous metal complex dyestuff of following formula 1 representative, this method comprises the following steps:
A) make the diazonium naphthalene compound of following formula 2 representatives and the naphthol reaction of following formula 3 representatives, their equivalent ratio is 1: 0.8-1: 1.3, obtain the Monoazo compound of following formula 4 representatives, then, make this Monoazo compound and the chromium donor that is selected from chromic formate, chromium chloride and chromic oxide with 1: 0.8-1: 1.3 equivalence ratio reaction produces the chromium complex of following formula 5 representatives;
B) the phenylnaphthalene compound of the amino-benzene compound that makes following formula 6 representative and following formula 7 representatives is with 1.5-2.5: 1 equivalence ratio, reaction in the presence of nitrite, the disazo compound that generation is represented by following formula 8;
C) the disazo compound reaction that chromium complex that 100-120 weight part step a) makes and 60-70 weight part step b) are made,
Formula 1
Formula 2
Formula 3
Formula 4
Formula 5
Formula 6
Formula 7
Formula 8
Wherein, R
1Each other can be identical or different, be selected from hydrogen atom H, nitro NO separately
2, chlorine atom Cl, sulfamyl SO
2NH
2And sulfo group-SO
3H; R
2Each other can be identical or different, be selected from hydrogen atom H, nitro NO separately
2, chlorine atom Cl and sulfo group-SO
3H.
3. method as claimed in claim 2 is characterized in that described step a) comprises:
Stir down, the diazonium naphthalene compound is dissolved in the 0-10 ℃ of water;
Regulate the pH to 3-5 of this solution, add naphthol solution therein, between diazonium naphthalene and naphthols, carry out coupled reaction, produce Monoazo compound;
This Monoazo compound is scattered in the water, makes this Monoazo compound and chromium donor at 125-135 ℃, pH is coupling under the 1.0-5.0.
4. method as claimed in claim 2 is characterized in that described step b) comprises:
Stir down, described amino-benzene compound is dissolved in the water in 0-30 ℃;
Add the solution of phenylnaphthalene compound in water therein, making amino-benzene compound and phenylnaphthalene compound is to carry out coupled reaction under the 9-11 at pH.
5. method as claimed in claim 2 is characterized in that described step c) carries out under the 4.0-10.0 condition at 50-90 ℃ and pH.
6. erie black dye composition, described composition comprises
The asymmetric azo-group erie black non-ferrous metal complex dyestuff of following formula 1 representative of 80-99% weight;
1-20% weight at least a is selected from the dyestuff of following compound by formula 9-12 representative:
Formula 1
Formula 9
Formula 10
Formula 11
Formula 12
Wherein, R
1Each other can be identical or different, be selected from hydrogen atom H, nitro NO separately
2, chlorine atom Cl, sulfamyl SO
2NH
2And sulfo group-SO
3H; R
2Each other can be identical or different, be selected from hydrogen atom H, nitro NO separately
2, chlorine atom Cl and sulfo group-SO
3H.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2001/000515 WO2002079326A1 (en) | 2001-03-29 | 2001-03-29 | Asymmetric azo-based metal complex dye, preparation thereof and acidic black dye composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1406266A CN1406266A (en) | 2003-03-26 |
| CN1204203C true CN1204203C (en) | 2005-06-01 |
Family
ID=19198366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01802267.7A Expired - Fee Related CN1204203C (en) | 2001-03-29 | 2001-03-29 | Asymmetricazo-based metal complex dye, preparation thereof and acidic black dye composition containing the same |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1204203C (en) |
| TW (1) | TW570960B (en) |
| WO (1) | WO2002079326A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177544B (en) * | 2007-11-28 | 2010-06-16 | 上虞新晟化工工业有限公司 | Acid black dye composition |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100503736C (en) * | 2006-01-26 | 2009-06-24 | 浙江龙盛集团股份有限公司 | Bisazo metal complex dye and preparation method thereof |
| CN100560651C (en) * | 2006-02-24 | 2009-11-18 | 浙江龙盛集团股份有限公司 | Azo-based metal complex dye and preparation method thereof |
| CN101139466B (en) * | 2007-09-29 | 2012-02-01 | 杭州下沙恒升化工有限公司 | Method for producing acid dye product |
| CN101565555B (en) * | 2009-04-14 | 2013-01-09 | 华东理工大学 | Rare earth complex red pigment with excellent pigment performance and application thereof |
| CN101712815B (en) * | 2009-11-23 | 2012-08-22 | 浙江大井化工有限公司 | Environment-friendly acid black dye composition |
| TWI518142B (en) * | 2011-03-31 | 2016-01-21 | 住友化學股份有限公司 | A salt for dye |
| CN102796400B (en) * | 2011-05-25 | 2013-12-04 | 上海雅运纺织化工股份有限公司 | Yellow azo metallized dye composition, method and application thereof |
| CN103265822A (en) * | 2013-05-24 | 2013-08-28 | 南通市争妍颜料化工有限公司 | Process for producing solvent yellow GR |
| CN103756362B (en) * | 2013-12-28 | 2015-09-02 | 浙江龙盛染料化工有限公司 | A kind of acid black dye composition |
| CN105385186B (en) * | 2015-10-19 | 2017-03-29 | 广州市纬庆化工科技有限公司 | A kind of resistance to migration orchil, preparation method and application |
| CN109054430A (en) * | 2018-09-05 | 2018-12-21 | 杭州下沙恒升化工有限公司 | A kind of preparation method of acid dye finished product |
| CN109370256B (en) * | 2018-11-20 | 2020-06-26 | 恒升化工有限公司 | Mixed black dye and preparation method thereof |
| CN111171594A (en) * | 2019-12-31 | 2020-05-19 | 恒升化工有限公司 | Preparation method of metal complex dye with low residual chromium ions |
| CN116694100A (en) * | 2023-06-01 | 2023-09-05 | 天津三环化工有限公司 | Green-light black dye and preparation method and application thereof |
| CN117004248A (en) * | 2023-08-08 | 2023-11-07 | 约克夏(浙江)染化有限公司 | Black acid dye composition, black acid dye, and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0774314B2 (en) * | 1988-09-08 | 1995-08-09 | 三菱化学株式会社 | Water-soluble dye mixture |
| DE59007014D1 (en) * | 1989-02-23 | 1994-10-13 | Ciba Geigy Ag | Process for the preparation of asymmetric 1: 2 metal complex dyes. |
| GB2236542B (en) * | 1989-10-06 | 1992-04-15 | Sandoz Ltd | Dye mixtures and their use in trichromatic dyeing processes |
| TW268967B (en) * | 1992-11-28 | 1996-01-21 | Hoechst Ag |
-
2001
- 2001-03-29 WO PCT/KR2001/000515 patent/WO2002079326A1/en active IP Right Grant
- 2001-03-29 CN CN01802267.7A patent/CN1204203C/en not_active Expired - Fee Related
-
2002
- 2002-07-11 TW TW091115462A patent/TW570960B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177544B (en) * | 2007-11-28 | 2010-06-16 | 上虞新晟化工工业有限公司 | Acid black dye composition |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002079326A1 (en) | 2002-10-10 |
| CN1406266A (en) | 2003-03-26 |
| TW570960B (en) | 2004-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1204203C (en) | Asymmetricazo-based metal complex dye, preparation thereof and acidic black dye composition containing the same | |
| CN1084769C (en) | Mixtures of reactive dyes and their use | |
| CN100343341C (en) | Dispersing dye mixture and dye products | |
| CN1912014A (en) | Dark black active dyestuff having high colour fixing rate | |
| CN1140667C (en) | Process for printing textile fibre materials in accordance with ink-jet printing process | |
| CN1344763A (en) | Azoic disperse dye mixture | |
| CN1399032A (en) | Three primary color dyeing or printing method for synthetic polyamide fiber material | |
| CN1861695A (en) | Yellow ozo dye mixture and its use | |
| CN1810892A (en) | Novel reactive yellow dye compounds and mixture thereof | |
| CN1102842A (en) | Dye mixture which can react with fibres and dyeing fibres with same | |
| CN1103085A (en) | Mixture of dye with group which is able to react with fibres and application of same | |
| CN1029141C (en) | Phthalocyanine fibre-reactive dyes | |
| CN1861693A (en) | Reactivity dye composition and its application | |
| CN1505666A (en) | Reactive dye mixtures | |
| CN1098122A (en) | Phthalocyanine fibre-reactive dyes | |
| CN1249173C (en) | Fibre reactive dye | |
| CN1923906A (en) | Reactivity dye composition and application thereof | |
| CN1317336C (en) | Quaternary ammonium salt bis-azo reactive dye and its use | |
| CN1056636C (en) | Dye composition and dyeing method using the same | |
| CN1146468A (en) | Dye mixtures, processes for their preparation and their use | |
| CN1633473A (en) | Azo dyestuffs | |
| CN1136614A (en) | Dye assistant product and its use on wool dyeing | |
| CN1211436C (en) | Mixtures of reactive dyes and their use | |
| CN1257233C (en) | Monoazo reactive red dyestuff | |
| CN1286922C (en) | Trichromatic dyeing process and dye mixtures used therein |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20050601 Termination date: 20120329 |