CN112662199B - Black dye compound and preparation method and dyeing application thereof - Google Patents
Black dye compound and preparation method and dyeing application thereof Download PDFInfo
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Abstract
The invention provides a black dye compound represented by a general formula (I), and a preparation method and dyeing application thereof. The black dye compound has good dyeing performance, has high soaping fastness, water fastness, chlorinated water fastness and water soaking fastness under the conventional washing condition, and can solve the problems of color change, staining and the like of nylon fibers; meanwhile, the light fastness and the rubbing fastness of the metal acid dye can be achieved. The dye compound has good dye lifting performance, good fastness to chlorinated water and good fastness to water in the aspect of dyeing nylon, polyamide and other fibers containing amino or amido, can replace metal acid dye to dye nylon, solves the problem of heavy metal in textiles, and ensures that the product is more environment-friendly.
Description
Technical Field
The invention relates to a black dye compound, a preparation method thereof and dyeing application on fiber materials.
Background
Black dye compounds have been one of the hot spots in the dye community. The nylon has good elasticity, excellent abrasion resistance, good moisture absorption and quick drying performance and small clo value, can be blended with other fibers, has plump and smooth hand feeling, is comfortable to wear, has high elasticity and luster, and is a very popular garment fabric at present.
The available dyes for dyeing polyamide fiber include acid dye, acid mordant dye, metal complex salt acid dye, reactive dye for wool, etc. Because of the environmental problems of heavy metals (chromium and the like) in dyeing drainage and dye waste (incineration), the reactive dye tends to replace acid mordant dye and metal complex salt acid dye, and the reactive dye is used for dyeing nylon fabric to bring a new problem, namely the promotion of the dye on the fabric is poor.
For many years, textile brands and dye factories suffer from poor washing fastness of nylon dyes due to fading, staining, bleeding and the like, and the problem causes customer complaints and limits the application of nylon.
The root of the nylon fiber washing fastness problem lies in: (1) all dyes currently used for nylon fibers are only bonded to nylon fibers in a relatively weak physical connection. (2) The glass transition temperature of nylon fibers is low. Therefore, even under the conditions of conventional home washing (40-60 ℃), dye molecules are thermally migrated from the inside of the fiber to the surface of the fiber, adjacent fibers are stained upon repeated water washing, color change and reduction of color intensity are gradually caused, and the color fastness of the fabric dyed with the reactive dye is better.
In order to solve the problems, the inventor develops a black dye compound containing active groups such as vinylsulfonyl, monochlorotriazine, carboxylic acid and the like, which is specially designed for nylon and blended fibers thereof and has the advantages of good promotion, high level-dyeing property and good dyeing reproducibility.
The inventors have conducted extensive experiments to confirm that the choice of the dye reactive group is a crucial factor in the present invention.
In the process of research and practice, the inventor surprisingly finds that the dye has a unique structure, can effectively improve the fastness of the dye, and improves the deep dyeing property of the dye.
The inventors do not find patents and articles that are the same or similar to the content of the present invention.
Disclosure of Invention
Through a large number of experiments, the black reactive dye compound represented by the general formula (I) is found to have very excellent dyeing performance and various fastnesses.
Compared with the conventional acid dye, the black reactive dye compound has obviously improved dyeing promotion, washing fastness, light fastness, water soaking fastness and chlorine fastness.
The black dye compound provided by the invention is represented by a general formula (I):
in the general formula (I):
y is selected from-CH = CH 2 、-CH＝CHCH 3 、-CH＝CHCH 2 CH 3 、-CH＝CHCH 2 CH 2 CH 3 、-CH＝CHCHCH 3 CH 3 ；
R is selected from hydrogen atom and C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, sulfo, or-OH;
R 1 and R 3 Each independently selected from hydrogen atom, C 1 ～C 4 Alkyl of (C) 1 ～C 4 An alkoxy group or a sulfonic acid group of (a);
R 2 is selected from-CH 2 COOM、-CH 2 CH 2 COOM、-CH 2 CH 2 OH、-CHCH 3 COOM、-CH 2 CH 2 CH 2 COOM、-CH 2 CHCH 3 COOM、-CH 2 CH 2 CH 2 CH 2 COOM, or-CH 2 CHCH 3 CH 2 COOM；
X 1 Selected from-Cl, -F, -NHCN, or
M is selected from hydrogen, or alkali metal cations, such as lithium, sodium, potassium ions;
R 4 selected from hydrogen, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, or sulfonic acid groups;
R 5 is selected from-NH 2 or-OH.
The invention also provides a preparation method of the black dye compound, which comprises the following steps:
a) Reacting a compound represented by formula 1 with a compound represented by formula 2 to obtain a primary condensation product represented by the following formula a:
in the formula, X 1 Selected from-Cl, -F, -NHCN, or
R 5 Is selected from-NH 2 or-OH;
b) Diazotizing a compound of formula 3 and then reacting the resulting diazonium salt with the primary condensation product prepared in step a) to obtain a primary coupling product of formula B:
wherein R is selected from a hydrogen atom and C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, sulfo, or-OH; r 1 Selected from hydrogen atoms, C 1 ～C 4 Alkyl of (C) 1 ～C 4 Alkoxy or sulfonic acid group of (2);
c) Diazotizing a compound shown as a general formula 4, and then carrying out secondary coupling reaction on the obtained diazonium salt and a compound shown as a general formula 5 to obtain a secondary coupling product shown as a general formula C:
in the formula, R 2 Is selected from-CH 2 COOM、-CH 2 CH 2 COOM、-CH 2 CH 2 OH、-CHCH 3 COOM、-CH 2 CH 2 CH 2 COOM、-CH 2 CHCH 3 COOM、-CH 2 CH 2 CH 2 CH 2 COOM, or-CH 2 CHCH 3 CH 2 COOM；R 3 Selected from hydrogen atom, C 1 ～C 4 Alkyl of (C) 1 ～C 4 An alkoxy group or a sulfonic acid group of (a); r 4 Selected from hydrogen, C 1 ～C 4 Alkyl radical, C 1 ～C 4 Alkoxy, or sulfonic acid groups; r 6 Is selected from-H, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CHCH 3 CH 3 ；
d) Reacting the secondary coupling product obtained in step c) with the primary coupling product obtained in step b) to obtain a compound of the general formula D:
e) Degreasing the secondary condensation product to obtain a target product shown in a general formula (I):
wherein Y is selected from-CH = CH 2 、-CH＝CHCH 3 、-CH＝CHCH 2 CH 3 、-CH＝CHCH 2 CH 2 CH 3 or-CHCHCHCH 3 CH 3 。
The invention also provides a black reactive dye composition which contains the black dye compound shown in the formula (I) and dyeing additives commonly used in the field.
The invention also provides the application of the black reactive dye compound in dyeing hydroxyl-and/or formamide-containing materials, particularly fiber materials.
Under the conventional washing condition, the black dye compound has high soaping fastness, water fastness, chlorinated water fastness and water soaking fastness, and can solve the problems of color change, staining and the like of nylon fibers; meanwhile, the light fastness and the rubbing fastness of the metal acid dye can be achieved. The metal acid dye can be replaced to dye nylon, so that the heavy metal problem of textiles is solved, and the product is more environment-friendly.
Description of the drawings:
FIG. 1 shows a one bath dyeing process step.
FIG. 2 shows the difference in reflectance of dye compound A compared to reference dye 3 at different reflectance wavelengths.
Detailed Description
The black reactive dye compound provided by the invention comprises one or more dye compounds represented by a general formula (I).
In a good priorityIn selected embodiments, the general formula (I) -SO 2 The Y group is in the meta or para position of the-N = N-group on the phenyl ring, R 3 The groups are located on the phenyl ring ortho, meta or para to the-N = N-group.
In a preferred embodiment, the R group in formula (I) is located in the ortho or para position of the-NH-group on the phenyl ring, R 2 The group is selected from-CH 2 COOM、-CH 2 CH 2 COOM、-CH 2 CH 2 OH、-CHCH 3 COOM、-CH 2 CH 2 CH 2 COOM、-CH 2 CHCH 3 COOM、-CH 2 CH 2 CH 2 CH 2 COOM, or-CH 2 CHCH 3 CH 2 COOM。R 2 The radical is preferably attached directly to the phenyl ring-NH-group.
In a preferred embodiment, X in formula (I) 1 Selected from-Cl, -F, -NHCN, or
Wherein R is 5 Is selected from-NH 2 or-OH.
In the present invention, the dye compound represented by the general formula (I) includes, for example, the following examples:
in a preferred embodiment, the process for the preparation of the black dye compound according to the present invention, step a) is carried out at a temperature of 0-5 ℃ and a pH of 6.5-7.0, step b) is carried out at a temperature of 5-15 ℃ and a pH of 6.5-7.0, step c) is carried out at a temperature of 5-15 ℃ and a pH of 3.0-3.5, step d) is carried out at a temperature of 40-60 ℃ and a pH of 6.0-7.0, and step e) is carried out at a temperature of 25-30 ℃ and a pH of 8.0-9.0.
The dye compounds according to the invention may also contain various dye additives conventionally used in dyeing processes and dye preparations, the amount of which may be selected according to the actual requirements, is not particularly restricted, and generally does not exceed 15% by weight. For example, electrolyte salts such as sodium sulfate, sodium chloride, potassium chloride, in an amount of 0 to 8% by weight, preferably 2 to 5% by weight; pH regulators, such as sodium dihydrogen phosphate or disodium hydrogen phosphate, sodium borate, sodium acetate, etc., in an amount of 0 to 5% by weight, preferably 0.5 to 2% by weight; and the auxiliary agents such as a dispersing agent, a leveling agent and the like are also included, or when the auxiliary agents exist in a liquid form, other auxiliary solvents and the like are also needed.
The black dye compound is suitable for dyeing cellulose fiber, polyamide fiber, protein fiber and various blended and interwoven textile materials thereof. The black dye compound is particularly suitable for dyeing nylon fiber materials.
The black dye compound can be effectively blended with other orange, yellow, blue and red dyes to form dyes with different colors, so that the practical application value of the black dye compound is improved.
The dye compounds of the invention can be applied to the fibre material and fixed to the fibre in a number of ways known in the art, for example they can be coloured by a padding process, a pad dyeing process or printing process.
The dye compound has good dyeing performance, and compared with a single dye, the color fastness such as light fastness, sweat stain fastness, water soaking fastness, washing fastness and the like, the dye compound is remarkably improved, beautiful in color, capable of meeting the current printing and dyeing requirements, and wide in application prospect.
Examples
This example includes examples of the synthesis of the dye compounds of the present invention and the preparation of dye preparations and dyeing applications thereof.
The synthesis of the dye compound and the preparation of the dye product of the invention are as follows:
example1 (dye compound i-1):
adding 31.9 g of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid into 100 g of water, adjusting the pH value to 6.5-7.0 by using a 30 wt% NaOH aqueous solution to dissolve the materials, cooling to 5 ℃, then adding the materials into 19 g of cyanuric chloride suspension which is completely dispersed in 70 g of ice water, stirring for 2 hours at the temperature of 0-5 ℃, and filtering out insoluble substances to obtain 45.3 g of a primary condensation product shown in the following formula A1.
Adding 27.8 g of 5-amino-2- (p-toluidino) benzenesulfonic acid into 139 ml of water, adding 30.42 g of 30% hydrochloric acid, stirring, cooling to below 5 ℃, maintaining the temperature at 0-5 ℃, slowly dripping 23 g of 30% sodium nitrite aqueous solution for diazotization reaction, wherein the reaction takes 2 hours, and removing excessive sodium nitrite by a small amount of sulfamic acid to obtain diazotization solution; the diazotised solution is then poured into the primary condensation product obtained above and admixed with 15% by weight of Na 2 CO 3 The pH of the aqueous solution was adjusted to 6.5 to 7.0, and a primary coupling reaction was carried out for 2 hours while maintaining the temperature at 5 to 15 ℃ to obtain 75.6 g of a primary coupling product represented by the following formula B1.
Adding 31.1 g of 2- ((4-amino-3-methoxyphenyl) sulfonyl) hydroxyethyl sulfate into 155.5 ml of water, adding 30.42 g of 30 percent hydrochloric acid, stirring, cooling to below 5 ℃, maintaining the temperature at 0-5 ℃, slowly dripping 23 g of 30 percent sodium nitrite aqueous solution for diazotization reaction, wherein the reaction takes about 2 hours, and a small amount of ammoniaEliminating excessive sodium nitrite by using sulfamic acid to obtain diazotization solution; the diazotised solution is then poured into a solution consisting of 16.6 g of 2- ((3-aminophenyl) glycine and 100 g of water, and washed with 15% by weight of Na 2 CO 3 Adjusting the pH value of the aqueous solution to 3.0-3.5, and maintaining the temperature at 5-15 ℃ to perform secondary coupling reaction for 2 hours to obtain a secondary coupling product shown as the following formula C1.
The secondary coupling product obtained above was added to the primary coupling product with 15 wt% Na 2 CO 3 Adjusting the pH value of the aqueous solution to 6.0-7.0, simultaneously heating to 40-60 ℃, and maintaining the reaction condition until HPLC analysis shows that the secondary condensation reaction is completed. 125.05 g of the compound of formula (D1) are obtained.
Heating the secondary condensation product to 25-30 deg.C, adding 15 wt% Na 2 CO 3 The pH was adjusted to 8.0-8.5 with aqueous solution and the reaction was incubated for 2 hours at pH =8.8-9.0 until HPLC analysis showed the degreasing reaction was complete and neutralized to pH =5.5-6.5 with 30 wt% aqueous HCl. The target product shown in the formula (I-1) is obtained.
The dye I-1 obtained by synthesis is subjected to recrystallization refining, high performance liquid chromatography separation and purification, and then elemental analysis is carried out, and the elemental analysis results are shown in Table 1.
TABLE 1
The resultant dye I-1 was used for the following various dyeing property tests.
Example 2 (dye compound i-2):
adding 31.9 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid into 100 g of water, adjusting the pH value to 6.5-7.0 by using a 30 wt% NaOH aqueous solution to dissolve the materials, cooling to 5 ℃, then adding the materials into 19 g of cyanuric chloride suspension which is completely dispersed in 70 g of ice water, stirring for 2 hours at the temperature of 0-5 ℃, and filtering out insoluble substances to obtain 45.3 g of a primary condensation product shown in the following formula A2.
Adding 26.4 g of 5-amino-2- (phenylamino) benzenesulfonic acid into 132 ml of water, adding 30.42 g of 30% hydrochloric acid, stirring, cooling to below 5 ℃, maintaining the temperature at 0-5 ℃, slowly and dropwise adding 23 g of 30% sodium nitrite aqueous solution for diazotization reaction, wherein the reaction takes about 2 hours, and a small amount of sulfamic acid eliminates excessive sodium nitrite to obtain a diazotization solution; the diazotised solution is then poured onto the primary condensation product obtained above and washed with 15% by weight of Na 2 CO 3 The pH of the aqueous solution was adjusted to 6.5 to 7.0, and a primary coupling reaction was carried out for 2 hours while maintaining the temperature at 5 to 15 ℃ to obtain 74.2 g of a primary coupling product represented by the following formula B2.
Adding 28.1 g of 2- ((4-aminophenyl) sulfonyl) hydroxyethyl sulfate into 140.5 ml of water, adding 30.42 g of 30% hydrochloric acid, stirring, cooling to below 5 ℃, maintaining the temperature at 0-5 ℃, slowly and dropwise adding 23 g of 30% sodium nitrite aqueous solution for diazotization reaction, wherein the reaction takes about 2 hours, and a small amount of sulfamic acid eliminates excessive sodium nitrite to obtain diazotization solution; the diazotised solution is then poured into a solution consisting of 26 g of 2- ((3-aminophenyl) glycine and 100 g of water, and with 15% by weight of Na 2 CO 3 Adjusting pH value of the aqueous solution to 3.0-3.5, maintaining the temperature at 5-15 deg.C, and performing secondary coupling reaction for 2 hr to obtainA secondary coupling product of formula C2.
The secondary coupling product obtained above was added to the primary coupling product and charged with 15 wt.% Na 2 CO 3 Adjusting the pH value of the aqueous solution to 6.0-7.0, simultaneously heating to 40-60 ℃, and maintaining the reaction condition until HPLC analysis shows that the secondary condensation reaction is completed. 127.95 g of the compound of formula (D2) are obtained.
Heating the secondary condensation product to 25-30 deg.C, adding 15 wt% Na 2 CO 3 Adjusting pH to 8.0-8.5 with water solution, maintaining the reaction for 2 hr at pH =8.8-9.0 until the defatting reaction is completed by HPLC analysis, and neutralizing with 30 wt% HCl water solution to pH =5.5-6.5. The target product shown in the formula (I-2) is obtained.
The dye I-2 obtained by synthesis was subjected to recrystallization refining, separation and purification by high performance liquid chromatography, and then elemental analysis was performed, and the elemental analysis results are shown in Table 2.
TABLE 2
The resultant dye I-2 was used for the following various dyeing property tests.
Example 3 (dye compound i-4):
31.9 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is added into 100 g of water, the pH value is adjusted to 6.5-7.0 by using 30 wt% of NaOH aqueous solution to dissolve the materials, the temperature is reduced to 5 ℃, then the materials are added into 13.5 g of the melamine suspension which is completely dispersed in 70 g of ice water, the temperature is maintained at 0-5 ℃, the mixture is stirred for 2 hours, and insoluble substances are filtered out by filtration to obtain 42.1 g of a primary condensation product shown in the following formula A3.
Adding 21.2 g of 2-ethyl- (N-phenyl) -1,4-phenylenediamine into 106 ml of water, adding 30.42 g of 30% hydrochloric acid, stirring, cooling to below 5 ℃, maintaining the temperature at 0-5 ℃, slowly dripping 23 g of 30% sodium nitrite aqueous solution for diazotization reaction, wherein the reaction takes about 2 hours, and removing excessive sodium nitrite by a small amount of sulfamic acid to obtain a diazotization solution; the diazotised solution is then poured into the primary condensation product obtained above and admixed with 15% by weight of Na 2 CO 3 The pH of the aqueous solution was adjusted to 6.5 to 7.0, and a primary coupling reaction was carried out for 2 hours while maintaining the temperature at 0 to 5 ℃ to obtain 65.7 g of a primary coupling product represented by the following formula B3.
Adding 29.5 g of 2- ((4-amino-3-methylphenyl) sulfonyl) hydroxyethyl sulfate into 147.5 ml of water, adding 30.42 g of 30% hydrochloric acid, stirring, cooling to below 5 ℃, maintaining the temperature at 0-5 ℃, slowly dripping 23 g of 30% sodium nitrite aqueous solution for diazotization reaction, wherein the reaction takes about 2 hours, and removing excessive sodium nitrite by a small amount of sulfamic acid to obtain a diazotization solution; the diazotised solution is then poured into a solution consisting of 23.2 g of 2- ((5-amino-2-sulfophenyl) aminoethanol and 100 g of water, and washed with 15% by weight Na 2 CO 3 Adjusting the pH value of the aqueous solution to 3.0-3.5, and maintaining the temperature at 5-15 ℃ to perform secondary coupling reaction for 2 hours to obtain a secondary coupling product shown in the following formula C3.
Mixing the above obtained twoThe coupling product was added to the primary coupling product and washed with 15 wt.% Na 2 CO 3 Adjusting the pH value of the aqueous solution to 6.0-7.0, simultaneously heating to 5-10 ℃, and maintaining the reaction condition until HPLC analysis shows that the secondary condensation reaction is completed. 119.7 g of the compound represented by the formula (D3) were obtained.
Heating the secondary condensation product to 25-30 deg.C, adding 15 wt% Na 2 CO 3 Adjusting pH to 8.0-8.5 with water solution, maintaining the reaction for 2 hr at pH =8.8-9.0 until the defatting reaction is completed by HPLC analysis, and neutralizing with 30 wt% HCl water solution to pH =5.5-6.5. The target product shown in the formula (I-4) is obtained.
The dye I-4 obtained by synthesis was subjected to recrystallization refining, separation and purification by high performance liquid chromatography, and then elemental analysis was performed, and the elemental analysis results are shown in Table 3.
TABLE 3
The resultant dye I-4 was used for the following various dyeing property tests.
The black dye compounds prepared in the examples were tested for their various properties and fastness properties according to the following methods:
1. and (3) testing color light difference:
the method comprises the following steps: the dyed fabric sample prepared by the dyeing process shown in figure 1 is subjected to color measurement by a Datacolor color meter, and the cloth surface reflectivity of the dyed fabric is black when the full-wavelength reflectivity is low at 400-700nm and red when the long-wave part reflectivity is high when the reflection wavelength is read. The second method comprises the following steps: and (3) testing the color difference of the dyed cloth sample by using a Datacolor color measuring instrument, comparing a value, wherein the positive value of a indicates partial red light, and the larger the value is, the more red the value is.
2. And (3) lifting force test:
dyeing nylon or nylon ammonia knitted fabric at room temperature, adding dye, HAC + NaAC buffer solution, NB, leveling agent SET and the like, heating to 80 ℃ (heating at a rate of 1 ℃ per minute) and keeping the temperature for 20 minutes, then heating to 98 ℃ (heating at a rate of 1 ℃ per minute) and keeping the temperature for 60 minutes, then cooling and washing with cold water, adding Na 2 CO 3 1g/L, heating to 80 ℃, and keeping the temperature for 20min for alkali washing; after draining, adding SW-PA 2g/L, heating to 80 ℃, and keeping the temperature for 20min for soaping; after washing with water and clear water, adding Argafix PA 2 and HAC + NaAC buffer solution, adjusting pH =4.5, heating to 70 deg.C, and holding for 20min for fixation.
The apparent depth K/S value of the dyed fabric is measured and recorded by a Datacolor colorimeter under the conditions of constant temperature and constant humidity according to the dye consumption of 1 percent, 2 percent, 3 percent, 4 percent and 6 percent o.w.f (dye is relative to the weight of the fabric).
The dyeing process is shown in figure 1.
The post-treatment process comprises alkali washing, soaping and color fixing, and comprises the following steps:
alkali washing: 1g/L of soda ash, wherein the bath ratio is 1.
Soaping: SW-PA 2g/L, bath ratio 1.
The color fixing process comprises the following steps: argafix PA 2%o.w.f., HAC + NaAC adjusted pH =4.5, warmed to 70 ℃ and incubated for 20min.
3. And (3) testing the water soaking fastness:
adding hot water at the temperature of 70 ℃/90 ℃ into 2g/L tide washing powder at a bath ratio of 50. Two identical liquid portions are prepared and placed in a C, D flask, no cloth sample is placed in a C beaker, and the liquid in the beaker is taken as a reference standard; and D, placing a cloth sample in the beaker, wherein the liquid in the beaker is a sample to be evaluated. The rating standard takes the undistributed clear liquid as grade 5, and the foam fastness of the fabric sample is rated according to AATCC gray color card, the foam fastness is rated at grade 1-5, and the grade can be half.
4. Testing color fastness to light: and (3) after the nylon ammonia knitted fabric is dyed and fixed, determining according to international standard ISO 105B 02.
5. Soaping color fastness test: and (3) after the nylon ammonia knitted fabric is dyed and fixed, determining according to international standard ISO 105C 10.
6. Testing water color fastness: and (3) after the nylon ammonia knitted fabric is dyed and color-fixed, determining according to the international standard ISO 105E 01.
7. Testing color fastness to perspiration: and after the nylon ammonia knitted fabric is dyed and dyed with a yarn fabric and fixed, determining according to the international standard ISO 105E 04.
8. Color fastness to chlorinated water test: and (3) after the nylon ammonia knitted fabric is dyed and color-fixed, determining according to international standard ISO 105E 03.
9. Color fastness to rubbing test: and (3) after the nylon ammonia knitted fabric is dyed and fixed, determining according to international standard ISO105X 12.
The dye compounds used in the examples of the present invention and the comparative examples and their contents are shown in Table 1. The black dye compound of the embodiment of the invention is prepared by mechanical grinding.
TABLE 4 dye Compounds
Note: reference dye 2 (25% C.I. acid blue 194+35% C.I. acid yellow 220+40% C.I. acid Red 405)
As can be seen from FIG. 2, the low reflectance at full wavelength of 400-700nm indicates black, the high reflectance at long wavelength indicates red, and the color is different, indicating that although dye A (100% dye I-1) has monochlorotriazine and naphthalenesulfonic acid structures in the parent structure and the reference dye 3 (dye example10 mentioned in patent US4667022 (1987)), the other structural units are different, so that the synthesized dye A (100% dye I-1) has dyeing difference and novelty.
Dyeing with dye A (100% dye I-1) and reference dye 3 (dye example10 from patent US4667022 (1987)) according to the dyeing process described herein, and measuring the data of the color difference after dyeing with a Datacolor colorimeter as follows:
table 5: color difference data for different dye compounds
It can also be seen from the data of the color difference that the cloth sample dyed with the dye A (100% dye I-1) is taken as a standard sample, and the cloth sample dyed with the test reference dye 3 (dye example10 proposed in patent US4667022 (1987)) has very large color difference, a is very large in positive value, and the colored light is red, which indicates that the dye has very different structures and great performance difference. The general formula of the dye structure selected by us and the prepared dye structure are greatly different from the dye structure mentioned in the prior similar patent, and the product with larger performance difference is synthesized by utilizing the prior patent.
Test example 1: promotion test
The lifting properties of the black reactive dye compound A-I and the reference dye 1 and the reference dye 2 are respectively tested according to the test method, the dyeing depth is respectively 1%, 2%, 3%, 4% and 6% (o.w.f), the dyeing method is dyeing at 98 ℃, and the dyeing process related to the lifting property test method is shown. K/S values of the dyed swatches of the respective components were measured, and the results are shown in Table 2.
TABLE 6 dyeing K/S values of different dye compounds
As can be seen from Table 6, the improvement of the dye compound of the present invention, compared with the reference dye 1, the component dyes thereof are obviously improved and enhanced, the structural differentiation of the dyes is fully embodied, and the product performance is more excellent. The dye of the invention also has a certain improvement in the lifting compared to the reference dye 2.
Test example 2: various color fastness
In the application of reactive dyes, most of the reactive dyes are used for dyeing cellulose fibers, and the black reactive dyes can be used for dyeing fibers containing amino and amido groups, such as nylon, polyamide, wool and the like, under an acidic condition, people have higher and higher requirements on various fastness of the dyes, and the fastness to light, perspiration, soaping, water and chlorine water and the fastness of soaking water measured by the industry for attaching customers become very important fastness indexes.
The black reactive dye compound of the present invention was tested for soaping fastness, perspiration stain fastness, color fastness to chlorinated water, rubbing color fastness, light color fastness, and water-soaking color fastness according to the above-mentioned test methods. The results are shown in tables 3, 4, 5, 6, 7 and 8. The color fastness is tested to 1/1 standard depth of dyeing.
TABLE 7 color fastness to soaping
As can be seen from table 7: the black dye compound has excellent soaping fastness.
TABLE 8 color fastness to water
As can be seen from table 8: the black dye compound has excellent water color fastness.
TABLE 9 color fastness to perspiration
As can be seen from table 9: the black dye compound has excellent color fastness to perspiration.
TABLE 10 color fastness to rubbing
| Name of dye | Dry friction | Wet friction |
| Dye compound A | 4-5 | 3-4 |
| Dye compound B | 4-5 | 3-4 |
| Dye compound E | 4-5 | 3-4 |
| Dye compound F | 4-5 | 3-4 |
| Dye compound H | 4-5 | 3-4 |
| Dye compounds I | 4-5 | 3 |
| |
4 | 3 |
| Reference dye 2 | 4 | 2～3 |
As can be seen from table 10: the black dye compound has excellent color fastness to rubbing.
TABLE 11 light and Water fastnesses
| Name of dye | Color fastness to light (6 level) | Fastness to soaking (5 level) |
| Dye compound A | ＞5 | 4～5 |
| Dye compound B | ＞5 | 4～5 |
| Dye compound E | ＞5 | 4 |
| Dye compound F | ＞5 | 4 |
| Dye compound H | ＞5 | 4～5 |
| Dye compounds I | ＞4 | 4 |
| |
＞5 | 3～4 |
| Reference dye 2 | ＞4 | 3 |
As can be seen from table 11: the black dye compound has excellent light fastness and water fastness.
TABLE 12 color fastness to chlorinated water
| Name of dye | Chlorine water 20PPM | Chlorine water 50PPM |
| Dye compound A | 4-5 | 4 |
| Dye compound B | 4-5 | 4 |
| Dye compound E | 4-5 | 4 |
| Dye compound F | 4-5 | 4 |
| Dye compound H | 4-5 | 4 |
| Dye compounds I | 4 | 3-4 |
| |
4 | 3-4 |
| Reference dye 2 | 4 | 3-4 |
As can be seen from table 12: the black dye compound has excellent fastness to chlorinated water.
The dye compound has excellent light fastness, sweat stain fastness and chlorinated water fastness, and has excellent water soaking fastness, soaping fastness and water fastness, and can reach or exceed that of reference dye 1, and is obviously improved compared with reference dye 2, so that the dye compound has wider application prospect.
Claims (9)
1. A black dye compound represented by the general formula (I):
in the general formula (I):
y is selected from-CH = CH 2 、-CH＝CHCH 3 、-CH＝CHCH 2 CH 3 、-CH＝CHCH 2 CH 2 CH 3 or-CHCHCHCH 3 CH 3 ；
R is selected from hydrogen atom and C 1 ～C 4 Alkyl, sulfonic acid, or-OH;
R 1 is selected from C 1 ～C 4 Alkyl of (C) 1 ～C 4 An alkoxy group or a sulfonic acid group of (a);
R 3 selected from hydrogen atoms, C 1 ～C 4 Alkyl of (C) 1 ～C 4 An alkoxy group or a sulfonic acid group of (a);
R 2 is selected from-CH 2 COOM、-CH 2 CH 2 COOM、-CH 2 CH 2 OH、-CHCH 3 COOM、-CH 2 CH 2 CH 2 COOM、-CH 2 CHCH 3 COOM、-CH 2 CH 2 CH 2 CH 2 COOM, or-CH 2 CHCH 3 CH 2 COOM；
X 1 Selected from-Cl, -F, -NHCN, or
M is selected from hydrogen, lithium, sodium or potassium;
R 4 selected from hydrogen or sulfonic acid groups;
R 5 is selected from-NH 2 。
2. The black dye compound according to claim 1, wherein the general formula (I) -SO 2 The Y group being meta or para to the-N = N-group on the phenyl ring, R 3 The groups are located on the phenyl ring ortho, meta or para to the-N = N-group.
3. The black dye compound according to claim 1, wherein R is in ortho-or para-position to-NH-group on benzene ring, R is 2 The group is attached to a phenyl ring-NH-group.
4. A black dye compound, which is selected from any one of the following compounds:
5. a method for preparing a black dye compound according to claim 1, comprising the steps of:
a) Reacting a compound represented by formula 1 with a compound represented by formula 2 to obtain a primary condensation product represented by the following formula a:
in the formula, X 1 Selected from-Cl, -F, -NHCN, or
R 5 Is selected from-NH 2 ；
b) Diazotizing a compound of formula 3 and then reacting the resulting diazonium salt with the primary condensation product prepared in step a) to obtain a primary coupling product of formula B:
wherein R is selected from a hydrogen atom, C 1 ～C 4 Alkyl, sulfonic acid or-OH; r 1 Is selected from C 1 ～C 4 Alkyl of (C) 1 ～C 4 An alkoxy group or a sulfonic acid group of (a);
c) Diazotizing a compound shown as a general formula 4, and then carrying out secondary coupling reaction on the obtained diazonium salt and a compound shown as a general formula 5 to obtain a secondary coupling product shown as a general formula C:
in the formula, R 2 Is selected from-CH 2 COOM、-CH 2 CH 2 COOM、-CH 2 CH 2 OH、-CHCH 3 COOM、-CH 2 CH 2 CH 2 COOM、-CH 2 CHCH 3 COOM、-CH 2 CH 2 CH 2 CH 2 COOM, or-CH 2 CHCH 3 CH 2 COOM, wherein M is selected from hydrogen, lithium, sodium or potassium; r is 3 Selected from hydrogen atoms, C 1 ～C 4 Alkyl of (C) 1 ～C 4 An alkoxy group or a sulfonic acid group of (a); r 4 Selected from hydrogen or sulfonic acid groups; r 6 Is selected from-H, -CH 3 、-CH 2 CH 3 、-CH 2 CH 2 CH 3 、-CHCH 3 CH 3 ；
d) Reacting the secondary coupling product obtained in step c) with the primary coupling product obtained in step b) to obtain a compound of the general formula D:
e) Degreasing the secondary condensation product to obtain a target product shown in a general formula (I):
wherein Y is selected from-CH = CH 2 、-CH＝CHCH 3 、-CH＝CHCH 2 CH 3 、-CH＝CHCH 2 CH 2 CH 3 or-CHCHCHCH 3 CH 3 。
6. The process according to claim 5, wherein step a) is carried out at a temperature of 0 to 5 ℃ and a pH of 6.5 to 7.0, step b) is carried out at a temperature of 5 to 15 ℃ and a pH of 6.5 to 7.0, step c) is carried out at a temperature of 5 to 15 ℃ and a pH of 3.0 to 3.5, step d) is carried out at a temperature of 40 to 60 ℃ and a pH of 6.0 to 7.0, and step e) is carried out at a temperature of 25 to 30 ℃ and a pH of 8.0 to 9.0.
7. A black reactive dye composition comprising the black dye compound according to any one of claims 1 to 4 and a dyeing additive.
8. Use of a black dye compound according to any of claims 1 to 4 for dyeing hydroxyl-and/or carboxamido-containing material.
9. Use of a black dye compound according to any one of claims 1 to 4 for dyeing a fibrous material.
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