MXPA96001653A - New dis colorants - Google Patents

Abstract

The present invention relates to the compounds according to formula I: and their salts characterized in that R1 represents hydrogen or -SO3H, R2 represents hydrogen, methyl, -NHCONH2 or -NHCOCH3, and R3 represents hydrogen, alkyl of 1 to 4 atoms of carbon or alkyl of 1 to 4 carbon atoms substituted. A process for dyeing or printing organic substrates containing hydroxyl groups or containing nitrogen, characterized the process because the dyeing or stamping is carried out with compounds as described above, their salts or mixtures thereof.

Description

REF: 22308 NEW COLORS FOR THE DISASTER DESCRIPTION OF THE INVENTION This invention relates to disazo dyes, to methods for their preparation and to their use as dyes reactive with fibers in processes of teat and stamping. According to the invention, the compounds according to formula (I) are provided and its salts in which it represents hydrogen or -S0 ~ H, R2 represents hydrogen, methyl, -NHC0NH2 or -NHCOCr 3 ' R- represents hydrogen, alkyl of 1 to 4 carbon atoms, preferably methyl or ethyl, or alkyl of 1 to 4 carbon atoms substituted with CN, OH, Cl, F or -S03H.

A more preferred compound according to formula I is represented by the formula The compounds according to formula I can be formed in the form of free acid or salt. When the compound of the formula I is in the salt form, the cations associated with the sulfo groups are not critical, and can be any of those non-chromophoric cations conventional in the field of the fiber-reactive dyes, with the proviso that the corresponding salts are soluble in water. Examples of such cations are cations. of alkali metal and unsubstituted ammonium cations, for example, lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, triethylammonium, and mono-, di-, and tri-ethanolammonium. Preferred cations are the alkali metal cations and the ammonium cation, with the sodium cation being the most preferred. In a compound of the formula I, the cations of the sulfo groups can be the same or different, for example, these can be a mixture of the aforementioned cations or 0 which means that the compound of the formula I can be in the form of mixed salt The invention provides in another of its aspects a method for the formation of compounds of the formula I, their salts or mixtures thereof, which comprises reacting a compound according to the formula with a compound of the general formula This condensation reaction proceeds according to a known method, and is preferably carried out at a temperature of from 20 to 50 ° C, more preferably from 30 to 40 ° C and at a pH of 4-5. An alternative method of preparing the compounds of the formula I is provided by the reaction of a compound having the formula with a compound that has the formula wherein X is the chloride or bromide ion, preferably chloride. This coupling reaction can be carried out according to known methods, and is preferably carried out at a temperature of 0 to 10 ° C, more preferably 0 to 5 ° C and a pH of 0 to 2, preferably 0 a 1. In each of the syntheses referred to above, the initial materials are either readily available or can be synthesized from commonly available raw materials. The compounds of formula I can be isolated according to known methods, for example, by conventional desalting with alkali metal salts, filtration and optionally drying under vacuum and at slightly elevated temperature. Depending on the reaction and isolation conditions, a compound of the formula I can be formed in free acid form or preferably in salt form, or even in the form of a mixed salt containing, for example, one or more of the cations previously mentioned. The compounds of the formula I can be converted from the free acid form to a salt form or mixture of salt forms, or vice versa, or from one salt form to another by conventional means. The compounds of the formula I, their salts and mixtures thereof are reactive dyes. These are suitable for dyeing and printing substrates containing hydroxyl groups or containing nitrogen. These can produce colorations or patterns of a red hue. According to yet another aspect of the invention, a process for dyeing or printing organic substrates containing hydroxyl or nitrogen-containing groups is provided., wherein the dyeing or stamping is performed with compounds as described above, their salts or mixtures thereof. Preferred substrates which may be mentioned are leather and fibrous materials, which consist or contain natural or synthetic polyamides, and in particular natural or regenerated cellulose such as cut cotton, viscose or rayon fibers. The substrate that is usually preferred is the textile material consisting of or containing cotton.

• • • The compounds of the formula I, their salts or mixtures thereof can be used in dyeing baths or in stamp pastes or according to all the dyeing or printing processes that are common in the field of reactive dyes. The dyeing is preferably carried out by the Exhaustive Process from an aqueous medium and at a temperature in the range of 30 to 80 ° C, more preferably 50 to 60 ° C and a salt content of 10 to 80 g / 1, preferably from 10 to 50 g / 1, more preferably from 10 to 30 g / 1. An article-to-liquor ratio (i.e. substrate to liquor ratio) is from 4: 1 to 30: 1, preferably 6: 1 to 20: 1. In still another aspect of the invention there is provided the use of compounds as defined hereinabove, their salts or mixtures thereof, in the dyeing or stamping of substrates as described above. The compounds of this invention and their salts have good compatibility with known fiber-reactive dyes. Accordingly, the compounds of the invention, their salts or mixtures thereof can be used individually in a dyeing or stamping process, or as a component in a composition in combination of dyeing or printing comprising other reactive dyes of the same kind, ie reactive dyes having comparable coloring properties, for example, fastness properties and the degree of ability to consume from a dye bath on a substrate. In particular, the dyes of the invention can be used in a trichromatic dye bath, in conjunction with certain appropriate yellow and blue dyes, which have the same or another appropriate reactive group, in suitable proportions to produce a wide range of shades or tones. The dyeings or prints in combination, obtained have strength properties that are comparable to those dyed and printed made with individual dyes according to the invention. The compounds of the formula I, their salts or mixtures thereof give good exhaustion and fixation yields when used as dyes. In addition, any unfixed dye is easily washed off the substrates. The dyes and prints formed show good shine fastness properties and good wet fastness properties, such as fastness in washing, in water, in sea water and in sweat. They also show good resistance to oxidizing agents such as chlorinated water, hypochlorite bleach, peroxide bleach and washing detergents containing perborate. The following examples are illustrative of the invention. In the examples, all parts and percentages are expressed by weight unless otherwise indicated, all temperatures are given in degrees Celsius.

Example 1 47. 8 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid were stirred in 500 parts of water at 25 ° C, and dissolved by the addition of 22 parts of a 30% by weight solution of sodium hydroxide. To this solution was added 26.8 parts of 2,4,6-trifluo-ropyrimidine, drop to drop in a period of 30 minutes. At the same time, a 20% solution of sodium carbonate was added to this mixture, continuously, in order to maintain the pH of the mixture at 4-5. The reaction temperature was increased to 40-45 ° C. The end point of the reaction was determined using chromatographic techniques. The resulting suspension was cooled to 20-25 ° C and emptied onto a diazonium salt solution which was formed of 71.5 parts of 4-amino-1, 1'-azobenzene-3, '-disulfonic acid and 50 parts of volume of 4N sodium nitrite solution at 0-5 ° C, and at a pH of 1. The resulting coupling reaction mixture was maintained at a pH of 7-7.5 by continuous addition of sodium carbonate solution at Z0% . The disazo compound formed in this way was desalted using conventional methods, filtered and dried at 50 ° C under vacuum. The product had the formula X max 515 nm in H.O This product dyed cotton to a red hue. The resulting dyeing showed excellent luminosity and wet fastness properties, and was resistant to oxidative influences.

Example 2 A solution of 28.1 parts of 2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid in 200 parts of water at 25 ° C, was mixed with a diazonium salt solution formed at 0-5 ° C, and at a pH from 1, from a mixture of 35.8 parts of 4-amino-1, 1'-azobenzene-3, '-disulfonic acid and 25 parts by volume of 4N sodium nitrite solution. The resulting mixture of coupling reaction was maintained at a pH of 8-8.5 by continuous addition of a 20% sodium carbonate solution. At the end of the reaction the obtained product was filtered and dried by suction. The still wet residue after the suction filtration was dissolved in 300 parts of 4% by weight sodium hydroxide solution, and the resulting solution was heated to 90-100 ° C, until the saponification of the acetyl group was completed, as determined by thin layer chromatography. The solution of the compound obtained in this way, which has the formula it was cooled to 20 ° C and by the addition of 30% hydrochloric acid the pH was adjusted to 5-6. At this pH, 26.8 parts of 2,4,6-trifluoropyrimidine were added dropwise over a period of 30 minutes. The pH of this solution was maintained by the continuous addition of 20% sodium carbonate solution, and the temperature of the reaction mixture was maintained at 40-45 ° C. Upon completion of the reaction the resulting dye was desalted, filtered and dried at 50 ° C in vacuo. The resulting dye had the following formula This dye stained and stamped cotton to a red hue. The dyeings and prints obtained in this way showed excellent luminosity and wet fastness properties, and were stable to oxidative influences.

Examples 3-15 Table 1 describes several dyes that were formed according to methods analogous to those described in Examples 1 and 2, and using the corresponding starting materials. In all cases, the dyes obtained stained or printed cotton to a red hue, and the dyes and prints obtained in this way, showed excellent luminosity and wet fastness, and were stable to oxidative influences.

Table 1 Application Example A 0. 3 parts of the dye of Example 1 were dissolved in 100 parts of demineralized water, and 3 g of Glauber's salt (calcined) was added. The staining bath was heated to 50 ° C, then 10 parts of cotton cloth (bleached) were added after 30 minutes at 50 ° C, 0.4 parts of sodium carbonate (calcined) were added to the bath. During the addition of sodium carbonate, the temperature was maintained at 50 ° C. Subsequently, the dye bath was heated to 60 ° C, and the dyeing was carried out for an additional hour at 60 ° C. The dyed fabric was then rinsed with running cold water for 3 minutes, and then with running hot water for 3 additional minutes. The dyeing was washed at boiling for 15 minutes in 500 parts of demineralized water in the presence of 0.25 parts of Marseille soaps. After being rinsed with running hot water (for 2 minutes) and centrifuged, the dyeing was dried in a cabinet dryer at about 70 ° C. A red cotton dyeing was obtained which shows good fastness properties, and particularly high humerus fastness properties, which is stable towards oxidative influences.

Application Example B To a staining bath containing 100 parts of demineralized water and 3 g of Glauber's salt (calcined) was added 10 parts of cotton cloth (bleached). The bath was heated at 50 ° C for 10 minutes, and 0.5 parts of Example 1 were added. After an additional 30 minutes at 50 ° C, one part of sodium carbonate (calcined) was added. The staining bath was then heated to 60 ° C and the staining was continued at 60 ° C for an additional 45 minutes. The dyed fabric was rinsed with running cold water, and then with running hot water, and washed at boiling temperature according to the method of Application Example A. After rinsing and drying a red cotton dyeing was obtained which had the same good solid properties as indicated in Application Example A. Similarly, the chlorins of Examples 2-15 or mixtures of the exemplified dyes were used to dye cotton according to the method described in Application Example A or B. Cotton obtained in this way were red, and show good fastness properties.

Application Example C A stamping paste consisting of 40 parts of the dye of Example 1 100 parts of urea 350 parts of water 500 parts of a thickener of 4% sodium alginate and 10 parts of sodium acid carbonate. 1000 parts in total It was applied to a cotton fabric according to conventional stamping methods. The printed fabric was dried and fixed in steam at 102-104 ° C for 4-8 minutes. This was rinsed in cold water and then hot water, washed at boiling temperature (according to the method described in Application Example A) and dried. A red print was obtained which had good general solid properties. Similarly, the dyes of Examples 2 to 15 or mixtures of the dyes exemplified, were used to print cotton according to the method given in Application Example C. All prints obtained were red and showed good fastness properties It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:

Claims (8)

1. The compounds according to the formula and its salts characterized because. represents hydrogen or -S0 ~ H R. represents hydrogen, methyl, -NHC0NH "or -NHC0CH" R represents hydrogen, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted.

2. The compounds according to claim 1 and their salts, characterized in that R "represents hydrogen, methyl, ethyl or alkyl of 1 to 4 carbon atoms, substituted with OH, CN, Cl, F, -SO H.

3. A compound according to claim 1 or claim 2, characterized in that it has the formula

4. A method for the formation of compounds of formula I, their salts or mixtures thereof, characterized in that it comprises the reaction of a compound according to the formula with a compound of the general formula

5. A process for dyeing or printing organic substrates containing hydroxyl groups or containing nitrogen, characterized the process because the dyeing or stamping is carried out with compounds as described above, their salts or mixtures thereof.

6. The organic substrates containing hydroxyl groups or containing hydrogen, characterized in that they are dyed or stamped with the compounds according to claim 1, with their salts or mixtures thereof.

7. The textile material according to claim 6, characterized in that it consists of cotton dyed or printed with compounds according to claim 1, its salts or mixtures thereof. 5

8. The compounds, characterized in that they are as described hereinabove with reference to any of Examples 1 to 15.