CN102796400B - Yellow azo metallized dye composition, method and application thereof - Google Patents

Yellow azo metallized dye composition, method and application thereof Download PDF

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CN102796400B
CN102796400B CN2011101379191A CN201110137919A CN102796400B CN 102796400 B CN102796400 B CN 102796400B CN 2011101379191 A CN2011101379191 A CN 2011101379191A CN 201110137919 A CN201110137919 A CN 201110137919A CN 102796400 B CN102796400 B CN 102796400B
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general formula
group
dyestuff
composition
cobalt complex
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CN102796400A (en
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谢兵
郑怡华
曾建平
顾喆栋
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Argus Shanghai Textile Auxiliary Co ltd
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SHANGHAI ARGUS TEXTILE CHEMICAL CO Ltd
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Abstract

The invention provides a yellow azo 1:2 metallized dye composition, and a method and application thereof. The yellow azo 1:2 metallized dye composition comprises at least one type of 1:2 unsymmetrical cobalt complex dye compounds and at least two types of 1:2 symmetrical cobalt complex dye compounds. The composition has a bright color and excellent color fastness and application performance; the dye composition has good sunproof fastness and moisture-proof fastness; and the dye composition has excellent improving property and dye-uptake and also has good compatibility with other metallized dyes. The color fastness and the application performance of the yellow azo 1:2 cobalt metallized dye are obviously better than those of C.I. acid yellow 220, namely the representative type of one of dyes made by the yellow azo 1:2 metallized dye composition.

Description

Yellow azo-group metal complex dye composition and method of making the same and application
Technical field
The present invention relates to a kind of azo-group metal complex dye composition and method of making the same and application.Particularly, the present invention relates to a kind of yellow azo-group cobalt complex dyestuff composition and method of making the same and application.
Background technology
As everyone knows, acid azo-group metal complex dye is widely used in dyeing and the stamp of wool, silk and polyamide fibre, but can use separately also colorant match application.
Acid azo-group metal complex dye, beautiful in colour, soluble in water, there is dyefastness preferably, be easy to processing, therefore be widely used.
Along with the deepening constantly of environmental protection requirement, people pay attention to the dyeing requirement of acid metal complex dye gradually in recent years.According to European Union's regulation, when acid metal complex dye is used for relevant dyeing keratin-fiber, dye liquor is discharged in waste water needs the amount of being processed should be less than 7%, and the dye uptake of metallized dye must surpass 93%.Meanwhile, to the dyeing behavior of acid azo-group metal complex dye, as level-dyeing property, enhancing all have requirements at the higher level.Its dyefastness is also had to new demand.
Yellow azo-group cobalt complex dyestuff---C.I. turmeric yellow 220 is a kind of acid metal complex dyes of commonly using.Its structural formula is as shown in the representative structure of general formula (4):
Figure BDA0000063733830000021
C.I. turmeric yellow 220
C.I. turmeric yellow 220 coloured light are bright-coloured, cheap, have good dyefastness.But also there are many defects, are difficult to meet the strict demand of current dyeing and printing process.For example, dyeing enhancing rate and the level-dyeing property of this dyestuff are not high, not good with the compatibleness of the metallized dye of other color and lusters.These defects have a strong impact on the industrial application of this dyestuff.
Summary of the invention
The inventor puts into practice by lot of experiments, finds to comprise that C.I. turmeric yellow 220 has excellent dyefastness and application performance as the yellow azo-type cobalt complex dyestuff composition of one of component pleasantly surprisedly.The printing and dyeing application of this composition can be considered the improvement of C.I. turmeric yellow 220 kinds.
1: 2 cobalt complex dyestuff composition of yellow azo-group of the present invention contains 1: 2 complex dyestuff compound of symmetric form that 1: 2 complex dyestuff compound of asymmetric 1: 2 cobalt complex dyestuff compound that at least one general formula (3) means, symmetric form that at least one general formula (4) means and at least one general formula (5) mean:
Figure BDA0000063733830000031
General formula (3)
Figure BDA0000063733830000041
General formula (4)
Figure BDA0000063733830000051
General formula (5)
In general formula (3), general formula (4) or general formula (5):
R 1For H or C 1-C 4Alkyl;
R 2For H or C 1-C 4Alkyl;
R 3For H, Cl, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or CN;
R 4For H, Cl, C 1-C 4Alkyl or C 1-C 4Alkoxyl group.
The present invention also provides the preparation method of 1: 2 cobalt complex dyestuff composition of a kind of above-mentioned yellow azo-group, and the method comprises that the mixture of the dye composition that dye composition that general formula (1) is meaned and general formula (2) mean carries out network with cobalt salt and reacts:
Figure BDA0000063733830000052
General formula (1)
In formula:
R 1For H or C 1-C 4Alkyl;
R 3For H, Cl, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or CN;
R 4For H, Cl, C 1-C 4Alkyl or C 1-C 4Alkoxyl group;
Figure BDA0000063733830000061
General formula (2)
In formula:
R 2For H or C 1-C 4Alkyl;
R 3For H, Cl, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or CN;
R 4For H, Cl, C 1-C 4Alkyl or C 1-C 4Alkoxyl group.
In addition, the present invention also provides the tint applications of 1: 2 cobalt complex dyestuff composition of above-mentioned yellow azo-group on wool, silk, polyamide fibre.
Practice shows, uses this composition to substitute C.I. turmeric yellow 220 and can receive beyond thought applications well effect.Not only improve dyeing enhancing rate and level-dyeing property, but also improved the performances such as compatibleness with the metallized dye of other color and lusters.
The accompanying drawing explanation
Fig. 1 is embodiment of 1: 2 cobalt complex dyestuff composition of the yellow azo-group of the present invention and the compatibleness trial curve of Xylene Red and acid blue.
Fig. 2 is the compatibleness trial curve of 1: 2 cobalt complex dyestuff of the yellow azo-group of contrast and Xylene Red and acid blue.
Embodiment
1: 2 cobalt complex dyestuff of symmetric form azo-group that 1: 2 cobalt complex dyestuff of the symmetric form azo-group that the asymmetric azo-group that 1: 2 cobalt complex dyestuff composition of yellow azo-group of the present invention is preferably meaned by least one general formula (3) 1: 2 cobalt complex dyestuff compound, at least one general formula (4) mean and at least one general formula (5) mean forms.
In 1: 2 cobalt complex dyestuff composition of the yellow azo-group of the present invention:
The content of asymmetric 1: the 2 cobalt complex dyestuff that general formula (3) means is 40~98%, is preferably 70~90%;
The content of 1: 2 cobalt complex dyestuff of symmetric form that general formula (4) means is 1~30%, is preferably 5~25%;
The content of 1: 2 cobalt complex dyestuff of symmetric form that general formula (5) means is 1~30%, is preferably 5~25%; The gross weight of this complex dyestuff composition of take is benchmark.
One preferred embodiment in, in the dye composition that general formula (3), general formula (4) or general formula (5) mean, R 3Group and R 4Contraposition, a position or the ortho position of be separately located in respectively on benzene nucleus-CONH-group of group.
Another preferred embodiment in, in the dye composition that general formula (3), general formula (4) mean ,-COOH group is separately located on benzene nucleus respectively
Figure BDA0000063733830000071
The ortho position of group, contraposition or a position.
One preferred embodiment in, the C of general formula (3), general formula (4) or general formula (5) 1-C 4Alkyl is preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl or isobutyl-, C 1-C 4Alkoxyl group is preferably methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy or isobutoxy.
The concrete dye composition that general formula (3), general formula (4) and general formula (5) mean as shown in the Examples.
1: 2 cobalt complex dyestuff composition of yellow azo-group of the present invention can be in general formula (3), general formula (4), dye composition that general formula (5) means and optional this area the usual auxiliaries mixed preparing, the mixture of the dye composition that dye composition that also can be by general formula (1) is meaned and general formula (2) mean and cobalt salt carry out network and react directly and make, and then add usual auxiliaries in optional this area.
One preferred embodiment in, the dye composition that general formula (1) means is 1~3: 3~1 with the mol ratio of the dye composition of general formula (2) expression; Be preferably 1~2: 2~1; More preferably 1: 1.
One preferred embodiment in, the R in general formula (1) 3And R 4Group, contraposition, a position or the ortho position of be separately located in respectively on benzene nucleus-CONH group; R in general formula (2) 3And R 4Group, contraposition, a position or the ortho position of be separately located in respectively on benzene nucleus-CONH group.
One preferred embodiment in, in general formula (1)-the COOH group, be positioned on benzene nucleus
Figure BDA0000063733830000072
The ortho position of group, contraposition or a position.
One preferred embodiment in, above-mentioned cobalt salt is the water-soluble inorganic cobalt salt, preferably rose vitriol, halogenation cobalt, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous phosphate or cobaltous carbonate, more preferably rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or cobaltous phosphate.Above-mentioned halogenation cobalt is preferably cobalt chloride or cobaltous fluoride.The total mole number of the dye composition that the common a little higher than general formula of the mole dosage of above-mentioned cobalt salt (1) and general formula (2) mean, preferred high 10-30 % by mole.
Above-mentioned complex reaction is preferably carried out under solvent exists, and more preferably in water, carries out, and most preferably in alkaline aqueous solution, carries out.The pH of the above-mentioned aqueous solution preferably is controlled between 7~14, more preferably is controlled between 8~12.
Alkali used is preferably alkali metal hydroxide, alkaline carbonate, alkaline earth metal hydroxides or their mixture.Alkali used is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood or their mixture more preferably.
Above-mentioned complex reaction, preferably at 30~80 ℃, is more preferably carried out at the temperature of 40~70 ℃.
The azo dyestuff cpds that above-mentioned complex reaction general formula (1) used means for example comprises following example:
Figure BDA0000063733830000081
Dyestuff 1-1
Dyestuff 1-2
Figure BDA0000063733830000091
Dyestuff 1-3
Dyestuff 1-4
Dyestuff 1-5
Figure BDA0000063733830000101
Dyestuff 1-6
Figure BDA0000063733830000102
Dyestuff 1-7
Figure BDA0000063733830000103
Dyestuff 1-8.
The azo dyestuff cpds that above-mentioned complex reaction general formula (2) used means for example comprises following example:
Figure BDA0000063733830000111
Dyestuff 2-1
Figure BDA0000063733830000112
Dyestuff 2-2
Figure BDA0000063733830000113
Dyestuff 2-3
Figure BDA0000063733830000114
Dyestuff 2-4
Figure BDA0000063733830000121
Dyestuff 2-5
Figure BDA0000063733830000122
Dyestuff 2-6
Figure BDA0000063733830000123
Dyestuff 2-7
Figure BDA0000063733830000124
Dyestuff 2-8.
The dye composition that the dye composition that the mixture of the dye composition that the dye composition that above-mentioned complex reaction general formula (1) used means and general formula (2) mean can be meaned by commercially available general formula (1) and commercially available general formula (2) mean is prepared according to the above ratio, and the mixture of the compound that also can be meaned by commercially available general formula (6) and commercially available general formula (7) makes with the compound coupling that general formula (8) means after conventional diazotization.
Figure BDA0000063733830000131
General formula (6)
Figure BDA0000063733830000132
General formula (7)
Figure BDA0000063733830000133
General formula (8).
1: 2 cobalt complex dyestuff composition coloured light of the yellow azo-group of the present invention is gorgeous, has excellent every dyefastness.This yellow complex dyestuff composition, compare with its composition dyestuff, and dyeing speed obviously improves, and the exhaustion rate also improves greatly, thereby contributes to reduce Wastewater Dyes content.As yellow dyes, there is the good compatibility with other color and luster dyestuffs.
Embodiment
Following embodiment comprises synthetic example and the tint applications example thereof of 1: 2 cobalt complex dyestuff composition of the yellow azo-group of the present invention, but these embodiment are only illustratives, and can not be for limiting the scope of the invention.
(1) the present invention's 1: 2 cobalt complex dyestuff composition of yellow azo-group synthesizes
1, synthetic example 1 (dyestuff 1-3 and the preparation of dyestuff 2-3 mixture and cobalt complex reaction thereof)
1) prepare the mixture of 1: 1 (mole ratio) dyestuff 1-3 and dyestuff 2-3
Take 20.22 weight part N-(methyl)-3-amino-4-hydroxy benzsulfamide and 30.83 weight part N-(2-carboxyl phenyl)-3-amino-4-hydroxy benzsulfamide, be incorporated in 800 weight parts waters, in the time of 65-70 ℃, add 20-30%NaOH solution, make the full melt into solution of material.
Then add 69 weight part 20% sodium nitrite solutions.
Above-mentioned solution is cooled to 0-5 ℃, and dropped in 1-1.5 hour in 30% hydrochloric acid soln of 160 weight parts, for maintaining the temperature of 0-5 ℃ of diazotization reaction, can add in right amount ice.
Take 42.4 weight part acetoacet-ortho-chloranilides in 150 part of 20% sodium carbonate solution, be stirred well to uniform suspension, this suspension was added in 0.5 hour in above-mentioned diazo liquid, coupled reaction continues 1.5-2.0 hour, comes to an end.
After filtration, dry bath; Make the dye mixture of dyestuff 1-3 and dyestuff 2-3.(the model: Shimadzu HPLC-10A of liquid-phase chromatographic analysis for product; Moving phase: water: methyl alcohol=20: 80 (volume ratio); UV-visible detector, λ=254nm), through the dyestuff 1-3 with commercially available and dyestuff 2-3, analyze contrast, confirm to obtain the mixture of dyestuff 1-3 and dyestuff 2-3, and, through liquid chromatography peak area contrast, confirm to obtain dyestuff 1-3 that mol ratio is 1: 1 and the dye mixture of dyestuff 2-3.
2) cobalt complex reaction
The above-mentioned dye mixture wet cake made is added in the water of 1500 weight parts, use 20%NaOH solution in the situation that the PH of stirring regulator solution is 10.
Under temperature 50-60 ℃, dripped 64 weight part 25% cobalt sulfate solutions in 0.5-1 hour, frequently add NaOH solution, the PH that maintains reaction solution is 10.Complex reaction continues approximately within 2 hours, to complete.
Saltout, filter, dry, grind.
Make 1: 2 cobalt complex dyestuff composition of yellow azo-group.
1: 2 cobalt complex dyestuff composition of this yellow azo-group liquid-phase chromatographic analysis (model: Shimadzu HPLC-10A for product; Moving phase: water: methyl alcohol=20: 80 (volume ratio); UV-visible detector, λ=254nm), through the corresponding dyestuff analysis contrast with commercially available, confirm to obtain the mixture of dyestuff 3-1 (retention time=7.900), dyestuff 4-1 (retention time=14.542) and dyestuff 5-1 (retention time=5.250), and, through the contrast of liquid chromatography peak area, it consists of:
A, asymmetric cobalt complex dyestuff 85% (weight)
Figure BDA0000063733830000151
Dyestuff 3-1
B, symmetric form cobalt complex dyestuff 5% (weight)
Figure BDA0000063733830000152
Dyestuff 4-1
C, symmetric form cobalt complex dyestuff 10% (weight)
Dyestuff 5-1
The asymmetric cobalt complex dyestuff of dyestuff 3-1, also can make according to the conventional synthetic method of asymmetric metallized dye, its preparation method can consult relevant patent: GB 1336612 (1973) (Hoechst), CN 1831045 (2006) (Zhejiang Province Longsheng Group Co., Ltd), the asymmetric cobalt complex dyestuff made as stated above is through liquid-phase chromatographic analysis (model: Shimadzu HPLC-10A; Moving phase: water: methyl alcohol=20: 80 (volume ratio); UV-visible detector, λ=254nm), obtain identical dye structure dyestuff 3-1 (retention time=7.900).
2, synthetic example 2-9 (preparation and the cobalt complex reactions thereof of dyestuff 1 and dyestuff 2 mixtures)
According to the same operation method of synthetic example 1, use respectively the dyestuff (1) of the different mol ratio shown in following table and dyestuff (2) mixture warp to carry out complex reaction with rose vitriol, make 1: 2 cobalt complex dyestuff composition of yellow azo-group of different content.Its data are summarized as follows:
Table 1
The structure of the complex dyestuff composition of the synthetic example 2-9 described in table 1 is as follows:
1) structure that respectively forms dyestuff of the complex dyestuff composition of synthetic example 2,3 is with synthetic example 1, and only ratio is different mutually.
2) structure that respectively forms dyestuff of the complex dyestuff composition of synthetic example 4 is as follows:
A, asymmetric cobalt complex dyestuff
Figure BDA0000063733830000181
Dyestuff 3-2
B, symmetric form cobalt complex dyestuff
Figure BDA0000063733830000182
Dyestuff 4-2
C, asymmetric cobalt complex dyestuff
Dyestuff 5-2
3) structure that respectively forms dyestuff of the complex dyestuff composition of synthetic example 5,6 is with synthetic example 4, and only ratio is different mutually.
4) structure that respectively forms dyestuff of the complex dyestuff composition of synthetic example 7 is as follows:
A, asymmetric cobalt complex dyestuff
Figure BDA0000063733830000201
Dyestuff 3-3
B, symmetric form cobalt complex dyestuff
Figure BDA0000063733830000202
Dyestuff 4-3
C, asymmetric cobalt complex dyestuff
Dyestuff 5-3
5) structure that respectively forms dyestuff of the complex dyestuff composition of synthetic example 8 is as follows:
A, asymmetric cobalt complex dyestuff
Figure BDA0000063733830000221
Dyestuff 3-4
B, symmetric form cobalt complex dyestuff
Figure BDA0000063733830000222
Dyestuff 4-4
C, asymmetric cobalt complex dyestuff
Figure BDA0000063733830000231
Dyestuff 5-4
6) structure that respectively forms dyestuff of the complex dyestuff composition of synthetic example 9 is as follows:
A, asymmetric cobalt complex dyestuff
Figure BDA0000063733830000241
Dyestuff 3-5
B, symmetric form cobalt complex dyestuff
Dyestuff 4-5
C, asymmetric cobalt complex dyestuff
Figure BDA0000063733830000251
Dyestuff 5-5.
1: 2 cobalt complex dyestuff composition of yellow azo-group of the present invention can be that powder can be also particulate material, but also can comprise auxiliary, the example of auxiliary be solubilizing agent as urea, weighting agent is as dextrin, saltcake or sodium-chlor, sequestrant is as tetrasodium phosphate, and dispersion agent and dust-proofing agent.Above-mentioned auxiliary can adopt with the dyestuff hygrometric state mode of drying again of mixing and add, and also can adopt the mode of dry state blending, and the dyestuff drying can adopt conventional drying mode, as spraying drying.
Above-mentioned dyestuff also can water prescription form use, its water prescription also can comprise auxiliary.Example for the auxiliary of water prescription is for example hexanolactam or urea of solubilizing agent, and organic solvent for example glycols, polyoxyethylene glycol, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, ethanamide, alkanolamine or polyoxamide.
(2) every testing method of composition embodiment
The properties of the present embodiment is tested by following every testing method
1, enhancing rate test: by polyamide fabric, according to the acid dyeing dyeing, dyeing concentration is 0.5%, 1%, 2%, 4%, 6%o.w.f (dyestuff is to the fabric weight).After dyeing, fabric, after fixed temperature and humidity is processed, is tested its Apparent Depth K/S value record with the Datacolor color measurement instrument.
2, solubleness: take a certain amount of dyestuff, be dissolved in 100ml boiling water, suction filtration while hot, observe dyestuff and have or not and separates out.Acidproof solubleness: take a certain amount of dyestuff, be dissolved in 100ml boiling water, cooling rear adjusting PH=4, then after high temperature boils and boil 10min, suction filtration is observed dyestuff and is had or not and separates out.
3, compatibleness test: the dye liquor preparation, dye the nylon dyeing by matching stain.Test respectively the dye uptake of each time point in dyeing course, observe the synchronism of colouring speed.
Dye uptake=(absorbance of the absorbance of dye liquor after 1-dyeing/front dye liquor of dyeing) * 100%
4, colour fastness to perspiration test: measure by international standard ISO 105-E04.
5, fastness to soaping test: measure by international standard ISO 105-C10.
6, colour fasteness to sunlight test: measure by international standard ISO 105-B02.
Dye type shown according to the form below 2 and consumption thereof evenly mix various dye components by ordinary method in this area, 1: 2 cobalt complex dyestuff composition of various yellow azo-group of the preparation embodiment of the present invention.
" % " in table 2 all means % by weight, and the gross weight of dye composite of take is benchmark.
Table 2
Figure BDA0000063733830000261
Test implementation example 1
Enhancing rate test (the K/S value at absorbing wavelength 450nm place)
Be determined as follows as stated above the enhancing rate of dyestuff, test result is recorded in table 3
Table 3
From table 3:
1: 2 cobalt complex dyestuff composition of the yellow azo-group of the present invention is compared with the reference dyestuff, and its enhancing rate is improved and improves.
Test implementation example 2
Solubleness and the test of acidproof solubleness
Be determined as follows as stated above the acidproof solubleness of dyestuff, test result is recorded in table 4.
Table 4
The dyestuff numbering Solubleness (g/L) Acidproof solubleness (g/L)
A 90 30
B 90 30
C 90 30
D 90 30
E 90 30
F 90 30
Reference X 85 25
Reference Y 85 25
From table 4:
1: 2 cobalt complex dyestuff composition of the yellow azo-group of the present invention, have excellent solubleness and acidproof solubleness, embodies its good level dyeing performance.
Test implementation example 3
Compatibility is measured
Be determined as follows as stated above dyestuff on dye curve, test result is referring to Fig. 1, wherein Line 1 means dyestuff A, No. 2 line means acid blue, No. 3 line means Xylene Red, No. 4 line means comparative dye.
As seen from Figure 5:
1) 1: 2 cobalt complex dyestuff composition of the yellow azo-group of the present invention has improved the slow defect of reference dyestuff dyeing rate greatly, shows compatibleness good while dying together with conventional primary colors red, blue dyestuff;
2) 1: 2 cobalt complex dyestuff composition of the yellow azo-group of the present invention has high exhaustion rate.
Test implementation example 4
Colour fastness to perspiration (MTD is 1/1 standard depth)
Be determined as follows as stated above the colour fastness to perspiration of dyestuff, test result is recorded in table 8
Table 6
Figure BDA0000063733830000281
Figure BDA0000063733830000291
From table 6:
1: 2 cobalt complex dyestuff composition of the yellow azo-group of the present invention is compared with the reference dyestuff, has excellent alkali perspiration fastness.
Test implementation example 5
Sunlight fastness (MTD is 1/1 standard depth)
Be determined as follows as stated above the sunlight fastness of dyestuff, test result is recorded in table 1] in
Table 7
The dyestuff numbering Sunlight fastness
A 6
B 5-6
C 5-6
D 5-6
E 6
Reference X 6
Reference Y 5-6
From table 7:
1: 2 cobalt complex dyestuff composition of the yellow azo-group of the present invention has excellent sunlight fastness.

Claims (13)

1. a yellow azo-group 1:2 cobalt complex dyestuff composition, it contains the symmetric form 1:2 complex dyestuff compound that asymmetric 1:2 cobalt complex dyestuff compound that at least one general formula (3) means, symmetric form 1:2 complex dyestuff compound that at least one general formula (4) means and at least one general formula (5) mean:
Figure FDA0000380513960000011
Figure FDA0000380513960000021
In general formula (3), general formula (4) or general formula (5):
R 1For H or C 1-C 4Alkyl;
R 2For H or C 1-C 4Alkyl;
R 3For H, Cl, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or CN;
R 4For H, Cl, C 1-C 4Alkyl or C 1-C 4Alkoxyl group.
2. yellow azo-group 1:2 cobalt complex dyestuff composition as claimed in claim 1, is characterized in that, in the gross weight of this dye composite,
The content of the asymmetric 1:2 cobalt complex dyestuff compound that general formula (3) means is 40~98%;
The content of the symmetric form 1:2 cobalt complex dyestuff compound that general formula (4) means is 1~30%;
The content of the symmetric form 1:2 cobalt complex dyestuff compound that general formula (5) means is 1~30%.
3. yellow azo-group 1:2 cobalt complex dyestuff composition as claimed in claim 1 or 2, is characterized in that the R in general formula (3), general formula (4) or general formula (5) 3And R 4Contraposition, a position or the ortho position of be separately located in respectively on benzene nucleus-CONH group of group, in general formula (3) or general formula (4)-the COOH group is separately located on benzene nucleus respectively
Figure FDA0000380513960000032
The ortho position of group, contraposition or a position.
4. yellow azo-group 1:2 cobalt complex dyestuff composition as claimed in claim 1 or 2, is characterized in that, the dye composition that general formula (3) means comprises:
Figure FDA0000380513960000051
Figure FDA0000380513960000061
Figure FDA0000380513960000071
Figure FDA0000380513960000081
The dye composition of general formula (4) comprising:
Figure FDA0000380513960000091
The dye composition of general formula (5) comprising:
Figure FDA0000380513960000111
Figure FDA0000380513960000121
Figure FDA0000380513960000131
Figure FDA0000380513960000151
5. yellow azo-group 1:2 cobalt complex dyestuff composition as claimed in claim 2, is characterized in that, in the gross weight of this dye composite,
The content of the asymmetric 1:2 cobalt complex dyestuff compound that general formula (3) means is 70~90%;
The content of the symmetric form 1:2 cobalt complex dyestuff compound that general formula (4) means is 5~25%;
The content of the symmetric form 1:2 cobalt complex dyestuff compound that general formula (5) means is 5~25%.
6. the preparation method of yellow azo-group 1:2 cobalt complex dyestuff composition as claimed in claim 1 or 2, it is characterized in that, the method comprises that the mixture of the dye composition that dye composition that general formula (1) is meaned and general formula (2) mean carries out network with cobalt salt and reacts:
Figure FDA0000380513960000161
In formula:
R 1For H or C 1-C 4Alkyl;
R 3For H, Cl, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or CN;
R 4For H, Cl, C 1-C 4Alkyl or C 1-C 4Alkoxyl group;
In formula:
R 2For H or C 1-C 4Alkyl;
R 3For H, Cl, C 1-C 4Alkyl, C 1-C 4Alkoxyl group or CN;
R 4For H, Cl, C 1-C 4Alkyl or C 1-C 4Alkoxyl group.
7. preparation method as claimed in claim 6, is characterized in that, the mol ratio of the dye composition that the dye composition that general formula (1) means and general formula (2) mean is 1~3:3~1.
8. the preparation method described in claim 6 or 7, is characterized in that, the R in general formula (1) 3And R 4Group, contraposition, a position or the ortho position of be separately located in respectively on benzene nucleus-CONH group; R in general formula (2) 3And R 4Group, contraposition, a position or the ortho position of be separately located in respectively on benzene nucleus-CONH group, described cobalt salt is the water-soluble inorganic cobalt salt.
9. the preparation method described in claim 6 or 7, is characterized in that, in general formula (1)-the COOH group, be positioned on benzene nucleus The ortho position of group, contraposition or a position.
10. the described preparation method of claim 6 or 7, its characteristic is, the dye composition that general formula (1) means is:
Figure FDA0000380513960000181
The dye composition that general formula (2) means is:
Figure FDA0000380513960000201
Figure FDA0000380513960000211
11. preparation method as claimed in claim 7, is characterized in that, the mol ratio of the dye composition that the dye composition that general formula (1) means and general formula (2) mean is 1~2:2~1.
12. the preparation method, is characterized in that as described in claim 8, described cobalt salt is rose vitriol, halogenation cobalt, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobaltous phosphate or cobaltous carbonate.
13. the tint applications of the described yellow azo-group 1:2 cobalt complex dyestuff composition of any one on wool, silk, polyamide fibre in claim 1~5.
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