CN114958026B - Improved trisazo red acid dye and preparation method thereof - Google Patents
Improved trisazo red acid dye and preparation method thereof Download PDFInfo
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- CN114958026B CN114958026B CN202210595467.XA CN202210595467A CN114958026B CN 114958026 B CN114958026 B CN 114958026B CN 202210595467 A CN202210595467 A CN 202210595467A CN 114958026 B CN114958026 B CN 114958026B
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- 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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/35—Trisazo dyes in which the tetrazo component is a diamino-azo-aryl compound
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
- D06P3/16—Wool using acid dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid dyes
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Abstract
The invention discloses an improved trisazo red acid dye, which has the following structural general formula:
r1 and R2 are-C 2 H 5 A group; r3 and R4 are H or-CH 3 A group; m is H or an alkali metal cation. The invention also provides a preparation method thereof. The improved trisazo red acid dye disclosed by the invention does not contain any carcinogenic dye or heavy metal dye, and belongs to safe and environment-friendly dyes. The dye has good water solubility, smooth dyeing in a dyeing system and good leveling property, can be combined with protein and polyamide fibers with high efficiency, has high dyeing rate, has excellent color fastness after dyeing, and is an ideal substitute of metal complex dye.
Description
Technical Field
The invention belongs to the field of chemical industry; in particular to a novel red acid dye (trisazo red acid dye) and a preparation method and application thereof.
Background
The acid dye is that the dye molecule contains acid group, also called anion dye, which can combine with amino group in protein fiber and polyamide molecule by ionic bond, and is suitable for acid, weak acid or neutral condition. Acid dyes are the primary dyes used for dyeing wool and polyamide fibers.
Purplish red is an important species in red, which provides a dark blue-red shade, and more purplish red acid dyes are currently used in the market: acid purplish red MB (c.i. acid violet 90), neutral purplish red GRL (c.i. acid red 213), acid red SB (c.i. acid red 405). Since it is a metal complex dye, it is not environment-friendly and has many application restrictions.
Patent CN201911362874.0, "trisazo red acid dye and preparation method thereof," already mentions a new red acid dye, but because of its darker color, it is difficult to blend some more vivid formulas in many color matching applications, and many are more to blend some darker color tones, and the application is greatly limited.
Disclosure of Invention
The invention aims to provide a novel red acid dye, namely an improved trisazo red acid dye, and a preparation method and application thereof.
In order to solve the technical problems, the invention provides an improved trisazo red acid dye, which has the following structural general formula:
r1 and R2 are-C 2 H 5 A group;
r3 and R4 are H or-CH 3 A group;
m is H or an alkali metal cation.
As an improvement of the improved trisazo red acid dye, the structural formula of the dye is any one of the following:
dye II-1:
the structural formula of the dye II-1 is as follows:
r1 is-C 2 H 5 A group R2 is-C 2 H 5 A group, R3 is an H group, R4 is an H group, and M is H or an alkali metal cation.
Dye II-2:
the structural formula of the dye II-2 is as follows:
r1 is-C 2 H 5 A group R2 is-C 2 H 5 A group R3 is-CH 3 A group R4 is-CH 3 And M is H or an alkali metal cation.
The dye II-1 specifically comprises:
the dye II-2 is specifically as follows:
the invention also provides a preparation method of the improved trisazo red acid dye, which comprises the following steps:
1) Adding hydrochloric acid (31% by mass) and paranitroaniline into water, cooling to 0-5 ℃, dropwise adding sodium nitrite solution (30% by mass) to form a reaction system I, controlling the temperature of the reaction system I not to exceed 5 ℃ in the dropwise adding process, stirring and reacting for 1-2 hours at 0-5 ℃ after the dropwise adding is finished, and then eliminating residual nitrous acid after the reaction to obtain a diazonium salt solution;
p-nitroaniline: hydrochloric acid = 1:3.7 molar ratio;
p-nitroaniline: sodium nitrite = 1: a molar ratio of 1.05;
description: in the reaction process, the non-chromogenic reaction can be detected by an ehrling reagent to be a reaction end point;
the excess nitrous acid is destroyed by sulfamic acid, and the starch potassium iodide test paper is not changed into blue;
2) Adding the reaction raw materials into water, uniformly stirring, adjusting the pH value to be 7.0-8.0 (adjustable by sodium carbonate), cooling to 0-5 ℃, dropwise adding the diazonium salt solution obtained in the step 1) to form a reaction system II, controlling the temperature of the reaction system II to be not more than 10 ℃ in the dropwise adding process, always adjusting the pH value of the reaction system II to be 7.0-8.0 in the dropwise adding process, and reacting for 3+/-0.3 hours at 5-10 ℃ after the dropwise adding is finished; the reaction raw materials are as follows: p-nitroaniline=1 to 1.05:1.0 in step 1) (preferably 1.02:1.0 Molar ratio of (c);
the reaction raw materials are N-ethyl-N-benzyl aniline-3 '-sulfonic acid (CAS No. 101-11-1) and N-ethyl-N-benzyl m-toluidine-3' -sulfonic acid.
3) Adding liquid alkali into the reaction product obtained in the step 2) to adjust the pH value to be 11.0-13.0, heating to 75-80 ℃, adding saccharides, and then preserving the temperature at 75-85 ℃ for 2 hours;
the saccharides are glucose, maltose and beta-cyclodextrin;
the saccharides: reactant = 1 to 1.5:1.0 (preferably 1.2 to 1.4:1.0) molar ratio (calculated as glucose monomer to molecular weight);
4) Adding sodium chloride into the reaction product obtained in the step 3) to generate precipitate, filtering, and drying a filter cake to obtain a product;
when the reaction raw material is N-ethyl-N-benzyl aniline-3' -sulfonic acid (CAS No.: 101-11-1), the obtained product is dye II-1;
when the reaction raw material is N-ethyl-N-benzyl m-toluidine-3' -sulfonic acid, the obtained product is dye II-2.
As an improvement of the preparation method of the improved trisazo red acid dye, the invention:
in the step 1), water (60+ -10) g was used per 0.1mol of p-nitroaniline.
As a further improvement of the process for the preparation of the improved trisazo red acid dye of the present invention:
in the step 2), 150-200 g of water is added to every 0.1-0.105 mol of reaction raw materials;
in the step 4), the drying is carried out for 24 hours at the temperature of 80-90 ℃.
The improved trisazo red acid dye is judged to be a red dye according to the Pantong international standard color card as a reference.
Based on a large number of experiments, the inventor discovers that the trisazo red acid dye has more excellent color fastness, does not contain heavy metal structures or cancerogenic structures, can replace the red acid dye in the prior art, and also makes up for the condition that the dye in the patent CN201911362874.0 is darker in color.
In conclusion, the improved trisazo red acid dye disclosed by the invention does not contain any carcinogenic dye or heavy metal dye, and belongs to safe and environment-friendly dyes. The dye has good water solubility, smooth dyeing in a dyeing system and good leveling property, can be combined with protein and polyamide fibers with high efficiency, has high dyeing rate, has excellent color fastness after dyeing, and is an ideal substitute of metal complex dye. The color tone of the dye is more vivid than that of the dye in CN201911362874.0, and the application range is wider when the dye is applied to more vivid products.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a graph showing the dye-uptake curves of the dyes II-1 according to the invention and the corresponding dyes I-1 in CN 201911362874.0;
FIG. 2 is a graph showing the dye-uptake curves of the dye II-2 according to the invention and the corresponding dye I-2 in CN201911362874.0.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
in the following cases, the stirring speed was 50 to 300 rpm.
Example 1, preparation method of trisazo red acid dye II-1, the following steps are sequentially carried out:
1) In a reactor with stirring, 60g of water is started, 0.1mol (about 13.8 g) of paranitroaniline is added, 0.37mol of hydrochloric acid (31% of hydrochloric acid by mass) is added, the mixture is cooled to 0 to 5 ℃, a sodium nitrite solution containing 0.105mol of sodium nitrite (30% of sodium nitrite solution by mass) is dropwise added, the temperature of a reaction system is controlled to be not more than 5 ℃ in the dropwise adding process, at this time, a starch potassium iodide test paper turns blue, the reaction is carried out at 0 to 5 ℃ for 2 hours (the end point of no color development is detected by an ehrling reagent), and then nitrous acid remained after the sulfamic acid is used for destroying the reaction (based on the starch potassium iodide test paper does not turn blue); a diazonium salt solution was obtained (all directly used in the next step).
2) In a reactor with stirring, 150g of water is added, 0.102mol of N-ethyl-N-benzylaniline-3 '-sulfonic acid is added, sodium carbonate is added to adjust the pH value to 7.0-8.0, and stirring is carried out until the N-ethyl-N-benzylaniline-3' -sulfonic acid is dissolved.
Cooling to 0-5 ℃, slowly dropwise adding all the products (diazonium salt solution) obtained in the step 1), controlling the temperature of a reaction system not to exceed 10 ℃ in the dropwise adding process, adjusting the pH value to be 7.0-8.0 by sodium carbonate in the dropwise adding process, and reacting for 3 hours at 5-10 ℃ after the dropwise adding is finished.
3) Adding liquid alkali into the reaction product obtained in the step 2) to adjust the pH value to be 12.0 (the dosage of the liquid alkali is about 90 g), heating to 75-80 ℃, adding 25g (about 0.135 mol) of industrial glucose, and preserving the temperature at 75-85 ℃ for 2 hours after the addition;
4) Adding sodium chloride (about 30 g) into the reaction product obtained in the step 3) to precipitate the dye, filtering to obtain a filter cake, and drying the filter cake at 80-90 ℃ for 24 hours to obtain about 52g of dye II-1.
Dye II-1 is:
1 H NMR(400MHz,DMSO-d6)：δ9.16(d,2H),8.41(d,4H),7.93-7.70(m,10H),7.59(d,2H), 7.44(d,2H),6.95(d,4H),4.81(s,4H),3.42(q,4H),1.12(t,6H)；ESI MS(m/z,％):853.3([M-Na] - , 100)。
example 2, preparation method of trisazo red acid dye II-2, the following steps are sequentially carried out:
1) Step 1) of example 1;
2) In a reactor with stirring, 200g of water is added, 0.102mol of N-ethyl-N-benzyl m-toluidine-3 '-sulfonic acid is added, sodium carbonate is added to adjust the pH value to 7.0-8.0, and stirring is carried out until the N-ethyl-N-benzyl m-toluidine-3' -sulfonic acid is dissolved.
Cooling to 0-5 ℃, slowly dropwise adding all the products (diazonium salt solution) obtained in the step 1), controlling the temperature of a reaction system not to exceed 10 ℃ in the dropwise adding process, and adjusting the pH value to be 7.0-8.0 by sodium carbonate in the dropwise adding process, wherein the reaction is completed for 3 hours at 5-10 ℃.
3) Adding liquid alkali into the reaction product obtained in the step 2) to adjust the pH value to be 12.0, heating to 75-80 ℃, adding 25g of glucose, and preserving the temperature at 75-85 ℃ for 2 hours after the addition.
4) Adding sodium chloride (about 20 g) into the reaction product obtained in the step 3) to precipitate the dye, carrying out suction filtration to obtain a filter cake, and drying the filter cake at 80-90 ℃ for 24h to obtain about 59g of dye II-2.
Dye II-2 is:
1 H NMR(400MHz,DMSO-d6)：δ9.15(d,2H),8.03(d,2H),7.91-7.70(m,10H),7.66-7.59 (m,4H),7.44(d,2H),6.88(d,2H),4.80(s,4H),3.41(q,4H),2.12(s,6H),1.12(t,6H)；ESI MS(m/z,％):881.2([M-Na] - ,100)。
the application embodiment and the various performances of the embodiment are detected according to the method described by CN 201911362874.0;
52g of dye II-1 prepared in example 1 is added with 60g of maltodextrin, standardized into commercial dye, and dyed to obtain dyed cloth sample:
a fabric: polyamide fiber, dyeing depth: 2% (weight ratio of commercial dye to fabric), bath ratio: 1:25, acetic acid: 1%, rate of temperature rise: heating to 95 ℃ at 1 ℃/min, preserving heat for 30 minutes, cooling to 60 ℃, washing cleanly, and drying at 60 ℃.
Description: the filler used in the above normalization may be sodium sulfate, sodium chloride, soluble starch, sodium lignin sulfonate, ammonium lignin sulfonate, or glucose instead of maltodextrin.
The dye II-2 obtained in example 2 was also used to obtain a dyed fabric sample by the same standardized and dyed method as described above.
The test method for the fastness to washing on polyamide fibres was carried out according to ISO105-C10 and the results are given in Table 1 below:
TABLE 1
The test method for perspiration (alkali) resistance fastness on polyamide fibres was carried out according to ISO105-E04 and the results are given in Table 2 below:
TABLE 2
As can be seen from the data in tables 1 and 2, the dye II-1 and the dye II-2 are excellent in color fastness, and the color fastness of the original fabric is slightly improved compared with that of the corresponding dye in CN201911362874.0.
The solubility of the standardized dyes II-1 and II-2 was measured (measurement method is GB/T3671.1,90 ℃), and the results are shown in Table 3 below:
TABLE 3 Table 3
| Dye | Solubility (g/L) |
| Ⅱ-1 | 120 |
| Ⅱ-2 | 100 |
The solubility of the dye obtained by the invention is the same as CN201911362874.0.
(3) And (3) carrying out dyeing process performance measurement on the standardized dye II-1 and dye II-2:
a fabric: polyamide fiber, dyeing depth: 1%, bath ratio: 1:50, acetic acid: 0.2g/L, leveling agent: 0.2g/L, temperature rising rate: heating to 95 ℃ at 1 ℃/min, preserving heat for 45 minutes, taking out the fabric at different time in the heating process, washing the fabric cleanly with water, and drying at 60 ℃. Adding the residual liquid after the fabric is taken out into a blank fabric with equal weight, continuously heating and dyeing, cooling to 60 ℃ after heat preservation is finished, washing cleanly, drying at 60 ℃, and taking out the dyed fabric at different time to obtain the K/S value as shown in the following table 4:
TABLE 4 Table 4
The K/S values of the fabric after the fabric was taken out at different temperatures and then put into an equal weight blank fabric to be dyed continuously are shown in the following table 5:
TABLE 5
The dye uptake curves of the dyes according to the invention are calculated from the fabric K/S values/total K/S (Table 4+Table 5K/S values for the corresponding conditions) by combining the data from tables 4 and 5 as shown in Table 6:
TABLE 6
The basic data of the dye uptake curves for the corresponding dyes I-1, I-2 in CN201911362874.0 were calculated in the same manner as in Table 7.
TABLE 7
The dye II-1 and II-2 of the invention are respectively compared with the dye I-1 and I-2 of CN201911362874.0 in dye uptake curves, and the obtained dye is shown in figures 1 and 2.
It can be seen from the above that: the dye II-1 and dye II-2 dye-uptake curves are very gentle, the leveling property is good, and the dye-uptake is high. And compared with CN201911362874.0, the invention has the advantages that: the dye-uptake curve is more gentle.
Color difference data of the dye II-1 of the invention relative to the dye I-1 of CN201911362874.0 were measured.
The detection process is that the fabric: polyamide fiber, dyeing depth: 0.5%, bath ratio: 1:50, acetic acid: 0.2g/L, leveling agent: 0.2g/L, temperature rising rate: 1 ℃/min, heating to 95 ℃, preserving heat for 45 minutes, taking out the fabric, washing the fabric cleanly, drying at 60 ℃, taking out and cooling back, detecting a cloth sample by using a Datacolor 850 color meter manufactured by American Deltay company, so as to obtain a Lab value of II-1 and a Lab value of I-1 in CN201911362874.0 respectively, and automatically calculating DC and DH values by software of a color meter system according to a CIE color difference calculation formula, wherein the DC and DH values are shown in the following table 8.
TABLE 8
| Dye | CIE L | CIE a | CIE b |
| Ⅱ-1 | 41.58 | 42.56 | 6.60 |
| CN201911362874.0-Ⅰ-1 | 40.02 | 38.76 | 3.00 |
The data for II-1 are shown in Table 9, with CN 201911362874.0-I-1 as a standard.
TABLE 9
| CIE DL | CIE Da | CIE Db | CIE DC | CIE DH |
| 1.56 | 3.80 | 3.60 | 4.12 | 1.78 |
From table 9, it can be seen that: the detection dye II-1 of the invention is reddish, yellowish and gorgeous relative to the color light of I-1 in CN201911362874.0.
Color difference data of dye II-2 of the present invention relative to dye I-2 of CN201911362874.0 were measured.
The detection process is the same as that described above, so that the Lab value of II-2 and the Lab value of I-2 in CN201911362874.0 are obtained respectively, and then the DC and DH values are obtained according to the calculation formula; the method comprises the following steps:
table 10
| Dye | CIE L | CIE a | CIE b |
| Ⅱ-2 | 37.71 | 37.82 | -5.65 |
| CN201911362874.0-Ⅰ-2 | 35.75 | 33.24 | -9.65 |
The data for II-2 are shown in Table 11, with CN 201911362874.0-I-2 as a standard.
TABLE 11
| CIE DL | CIE Da | CIE Db | CIE DC | CIE DH |
| 1.96 | 4.58 | 4.00 | 4.26 | 1.95 |
From table 11, it can be seen that: the detection dye II-2 of the invention is reddish, yellowish and gorgeous relative to the color light of I-2 in CN201911362874.0.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (4)
1. An improved trisazo red acid dye, which is characterized in that: is dye II-1 or dye II-2;
dye II-1:
dye II-2:
m is Na ion.
2. The method for preparing the improved trisazo red acid dye according to claim 1, which comprises the following steps:
1) Adding hydrochloric acid and paranitroaniline into water, cooling to 0-5 ℃, dropwise adding sodium nitrite solution to form a reaction system I, controlling the temperature of the reaction system I not to exceed 5 ℃ in the dropwise adding process, stirring and reacting for 1-2 hours at 0-5 ℃ after the dropwise adding is finished, and then eliminating residual nitrous acid after the reaction to obtain a diazonium salt solution;
p-nitroaniline: hydrochloric acid = 1:3.7 molar ratio;
p-nitroaniline: sodium nitrite = 1: a molar ratio of 1.05;
2) Adding reaction raw materials into water, uniformly stirring, adjusting pH=7.0-8.0, cooling to 0-5 ℃, dropwise adding the diazonium salt solution obtained in the step 1) to form a reaction system II, controlling the temperature of the reaction system II not to exceed 10 ℃ in the dropwise adding process, always adjusting the pH=7.0-8.0 of the reaction system II in the dropwise adding process, and reacting for 3+/-0.3 hours at 5-10 ℃ after the dropwise adding is finished; the reaction raw materials are as follows: the molar ratio of paranitroaniline=1-1.05:1.0 in the step 1);
the reaction raw material is N-ethyl-N-benzyl aniline-3 '-sulfonic acid or N-ethyl-N-benzyl m-toluidine-3' -sulfonic acid;
3) Adding liquid alkali into the obtained product after the step 2) to adjust the pH value to be 11.0-13.0, heating to 75-80 ℃, adding sugar, and then preserving the temperature at 75-85 ℃ for 2 hours;
the saccharide is glucose;
the saccharides: p-nitroaniline=1 to 1.5:1.0 molar ratio as reactant;
4) Adding sodium chloride into the obtained product after the step 3) to generate precipitate, filtering, and drying a filter cake to obtain a product;
when the reaction raw material is N-ethyl-N-benzyl aniline-3' -sulfonic acid, the obtained product is dye II-1;
when the reaction raw material is N-ethyl-N-benzyl m-toluidine-3' -sulfonic acid, the obtained product is dye II-2.
3. The method for preparing the improved trisazo red acid dye according to claim 2, which is characterized in that:
in the step 1), 60+/-10 g of water is added to each 0.1mol of paranitroaniline.
4. A process for the preparation of an improved trisazo red acid dye according to claim 3, characterized in that:
in the step 2), 150-200 g of water is added to every 0.1-0.105 mol of reaction raw materials;
in the step 4), the drying is carried out for 24 hours at the temperature of 80-90 ℃.
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| GB414483A (en) * | 1932-05-15 | 1934-08-09 | Chem Ind Basel | Manufacture of new azo-dyestuffs |
| GB557842A (en) * | 1942-05-06 | 1943-12-08 | Arthur Howard Knight | New disazo dyestuffs |
| DE2951061A1 (en) * | 1979-12-19 | 1981-07-02 | Hoechst Ag, 6230 Frankfurt | WATER-SOLUBLE AZO COMPOUNDS AND THEIR COPPER COMPLEXES, METHODS FOR THEIR PRODUCTION AND THEIR USE AS DYES |
| CN1189521C (en) * | 2002-12-06 | 2005-02-16 | 华东理工大学 | Monoazo acid blue dye without carcinogenicity and its application |
| MXPA06013141A (en) * | 2004-05-19 | 2007-02-28 | Clariant Finance Bvi Ltd | Bridged monoazo dyes. |
| EP2016135B1 (en) * | 2006-04-07 | 2009-07-15 | Clariant Finance (BVI) Limited | Acid dyes |
| MX2008015256A (en) * | 2006-06-25 | 2008-12-15 | Clariant Finance Bvi Ltd | Acid dyes. |
| CN101705013B (en) * | 2009-11-16 | 2012-12-19 | 天津德凯化工股份有限公司 | Dark blue dye for dyeing nylon and preparation method thereof |
| TWI561588B (en) * | 2011-10-22 | 2016-12-11 | Archroma Ip Gmbh | Trisazo acid dyes |
| CN102660134B (en) * | 2012-05-10 | 2014-02-05 | 金华恒利康化工有限公司 | Acidic green-light black dye and preparation method thereof |
| JP5987102B1 (en) * | 2015-11-27 | 2016-09-06 | 株式会社ヘリオス | Triarylmethane composition, staining composition for ophthalmic staining |
| CN107721887A (en) * | 2017-10-18 | 2018-02-23 | 恒升化工有限公司 | A kind of preparation method of highly acid blue dyes |
| JP7288665B2 (en) * | 2019-08-02 | 2023-06-08 | 株式会社デ・ウエスタン・セラピテクス研究所 | Method for producing ethylanilinotoluenesulfonic acid derivative |
| CN111040466B (en) * | 2019-12-26 | 2021-02-23 | 金华双宏化工有限公司 | Trisazo red acid dye and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR754798A (en) * | 1932-04-28 | 1933-11-14 | Ste Ind Chim Bale | Production of new azo dyestuffs |
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