Patent Application
20050148764
The present invention is situated within the field of fiber-reactive dyes. EP-A 785 237 discloses reactive dyes comprising the structural element
The present invention now provides dyes of the general formula (I)
where
In the compound of the general formula (I) an alkali metal M can be in particular lithium, sodium or potassium, while calcium is a particularly suitable alkaline earth metal. Preferably M is hydrogen or sodium.
Preferred compounds of the general formula (I) meet the condition p+r=1, while paricularly preferred compounds of the general formula (I) meet the condition p+r=2. If m=1 then preferably p+r=1.
X2 is preferably C1-C4 alkyl, C1-C4 alkoxy or SO3M and more preferably methyl, ethyl, methoxy, ethoxy or SO3M, in which M is hydrogen or sodium.
If r is 2 then the radicals X3 may have identical or different meanings. Similarly, the radicals X2 may have identical or different meanings if q is 2 or 3 and the radicals X1 may have identical or different meanings if p is 2.
Particularly preferred dyes of the general formula (I) correspond to the general formula (Ia)
where X1 to X3, A, L, L′, M, m, r, p and q are as defined above.
Particularly preferred dyes of the general formula (I) correspond, moreover, to the general formula (Ib)
where X1 to X3, A, L, L′, M, r, p and q are as defined above.
Particularly preferred dyes of the general formula (I) correspond, furthermore, to the general formula (Ic)
where M, X2 and q are as defined above and V is X3-NH-L- or X1—O2S-L′-, where X1, X3, A, L and L′ are as defined above.
Especially preferred dyes of the general formula (I) correspond to the following general formulae (Id) to (Iq)
where in each case
The dyes of the general formula (I) according to the invention are generally in the form of preparations in solid or liquid (dissolved) form. In solid form they generally include the electrolyte salts which are customary for water-soluble and especially fiber-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and may further include the assistants customary in commercial dyes, such as buffer substances with the capacity to set a pH in aqueous solution of between 3 and 7, such as sodium acetate, sodium borate, sodium hydrogen carbonate, sodium dihydrogen phosphate, sodium tricitrate, and disodium hydrogen phosphate, small amounts of siccatives or, if they are in liquid, aqueous solution (including the thickener content customary in the case of printing pastes), substances which ensure the durability of said preparations, such as mold preventatives, for example. The dyes of the general formula (I) according to the invention are preferably in the form of dye powders or dye granules containing from 10 to 80% by weight, based on the powder or granules, of an electrolyte salt, also referred to as a standardizer. Granules have grain sizes in particular of from 50 to 500 μm. These solid preparations may further comprise the abovementioned buffer substances in a total amount of up to 10% by weight, based on the preparation. Where the dyes are in aqueous solution, the total dye content of such aqueous solutions is up to about 50% by weight, such as between 5 and 50% by weight, for example, with the electrolyte salt content of these aqueous solutions being preferably below 10% by weight, based on the aqueous solution. The aqueous solutions (liquid preparations) may comprise the abovementioned buffer substances, in general, in an amount of up to 10% by weight, preferably up to 2% by weight.
Dyes of the general formula (I) where p≠0 and/or those containing a group of the formula (IIb) in which X8 is a group of the formula (III), while having the same chromophore, may possess a different structure in respect of the fiber-reactive group SO2X1 and/or R2. In particular, with the same chromophore, SO2X1 and R2 may on the one hand be —SO2CH═CH2 and on the other —SO2CH2CH2Z, with particular preference β-sulfatoethylsulfonyl. The fraction of the dye in vinylsulfonyl form may be up to about 30 mol %, based on the respective dye chromophore. The molar ratio between the vinylsulfonyl dye fraction and the β-ethyl-substituted dye fraction is preferably between 5:95 and 30:70.
The dyes of the general formula I according to the invention may be prepared, for example, by diazotizing an aromatic amine of the general formula (V)
where p, q, r, A, L, X1, X2 and X3 are as defined above and coupling the diazonium compound with a compound of the general formula (VI)
Using one equivalent of compound of the general formula (V) in this preparation process per equivalent of compound of the general formula (VI) produces dyes of the general formula (I) according to the invention in which m is 1. Alternatively, using two equivalents of compound of the general formula (V) per equivalent of compound of the general formula (VI) produces dyes of the general formula (I) according to the invention in which m is 2.
In one preferred embodiment of the preparation process according to the invention first one equivalent of aromatic amine of the general formula (V) is diazotized and the diazonium compound is coupled with one equivalent of a compound of the general formula (VIa)
where M is as defined above in the pH range between 0 and 6, preferably between 1 and 4. The resultant monoazo dyes correspond to the general formula (Ir)
where p, q, r, A, L, X1, X2, X3 and M are as defined above.
The dyes of the general formula (Ir) can then if desired be reacted with a second equivalent of the aromatic amine of the general formula (V), diazotized beforehand by known methods, to give disazo dyes of the general formula (Ia) or (Ib).
In the preparation according to the invention of compounds of the general formula (I) in which m is 2 the two equivalents of aromatic amine may be the same or different in respect of the variables p, q, r, L, L′, X1, X2 and X3.
If the two equivalents of aromatic amine are the same in respect of the variables p, q, r, L, L′, X1, X2 and X3 then it is particularly preferred to perform the reaction in a one-pot process (“one-pot coupling”). In this case two equivalents of the aromatic amine of the general formula (V) are diazotized and the diazonium compound is coupled with one equivalent of the compound of the general formula (VI).
Dyes of the general formula (I) according to the invention in which m is 2 and p+r=1 may be prepared by diazotizing an aromatic amine of the general formula (V) in which p+r=0 and reacting the diazonium compound with a compound of the general formula (VI) to give a compound of the general formula (VII)
where q, n, A, X2 and M are as defined above. Then, in a second step, an aromatic amine of the general formula (V) in which p+r=1 is diazotized and the diazonium compound is coupled further with the compound of the general formula (VII) to give the disazo dye according to the invention.
The diazotization and coupling reactions needed to prepare the dyes of the general formula (I) are known per se to the skilled worker and can be performed in conventional manner as described thoroughly in the relevant literature. In the case of the preparation processes-indicated the dyes of the general formula (I) according to the invention are obtained as solutions or suspensions and can be isolated by salting out, for example. The dyes can also be spray dried, although evaporative concentration of the solution or suspension is a further possibility.
The aromatic amines of the general formula (V) are known per se and can be prepared by methods familiar to the skilled worker.
The reactive dyes of the general formula (I) according to the invention possess useful application properties. They are used for dying and printing hydroxyl—and/or carboxamido-containing materials, in the form for example of sheetlike structures, such as paper and leather, or of films, of polyamide, for example, or in bulk, as for example polyamide and polyurethane, but especially in the form of fibers of the materials mentioned. Preferably they are used for dyeing and printing cellulosic fiber materials of any kind. They are additionally suitable for dyeing or printing hydroxyl-containing fibers present in blend fabrics; for example, blends of cotton with polyester fibers or polyamide fibers. It is also possible to use them to print textiles or paper by the inkjet process.
The present invention accordingly also provides for the use of the reactive dyes of the general formula (I) according to the invention for dyeing or printing the materials mentioned and, respectively, provides methods of dyeing or printing such materials in a conventional manner using as colorants one or more reactive dyes of the general formula (I) according to the invention.
Advantageously the as-synthesized solutions of the reactives dyes of the general formula (I) according to the invention may be used directly as a liquid preparation for dyeing, where appropriate following addition of a buffer substance and similarly where appropriate following concentration or dilution.
The materials mentioned are used preferably in the form of fiber materials, particularly in the form of textile fibers, such as wovens or yarns, as in the form of hanks or wound packages.
Carboxamido-containing materials are, for example, synthetic and natural polyamides and polyurethanes, particularly in fiber form, examples being wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-1 1 and nylon-4.
The reactive dyes of the general formula (I) according to the invention may be applied to and fixed on the substrates mentioned, particularly the fiber materials mentioned, by the application techniques that are known for water-soluble dyes and in particular by the techniques known for fiber-reactive dyes.
The padding process likewise provides excellent color yields and very good color build on cellulose fibers, in which case fixing can be accomplished conventionally by batching at room temperature or elevated temperature, at up to about 60° C., for example, by steaming or using dry heat.
Similarly, the customary printing processes for cellulose fibers, which can be carried out either in one phase, by printing for example with a print paste comprising sodium bicarbonate or another acid-binding agent and by subsequent steaming at 100 to 103° C., or in two phases, by for example printing with a neutral or weakly acidic print color and by subsequent fixation either by passing the printed material through a hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor with subsequent batching or steaming or dry heat treatment of the alkali-overpadded material, produce strong prints having well-defined contours and a clear white ground. The outcome of the prints is largely independent of variations in the fixing conditions.
When fixing by means of dry heat in accordance with the customary thermofix processes use is made of hot air and from 120 to 200° C. Besides the customary steam at 101 to 103° C. it is also possible to use superheated steam and pressurized steam at temperatures of up to 160° C.
The acid-binding agents which bring about the fixation of the dyes on the cellulose fibers include for example water-soluble basic salts of the alkali metals and likewise alkaline earth metals of organic or inorganic acids or compounds which release alkali in the heat. Mention may be made in particular of the alkali metal hydroxides and alkali metal salts of weak to medium-strength organic or inorganic acids, the preferred alkali metal compounds being the sodium and potassium compounds. Examples of such acid-binding agents include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate, waterglass or trisodiumphosphate. The reactive dyes of the general formula (I) according to the invention are notable for high reactivity, good fixability, very good build, and a high level of fastness to light and to light coupled with perspiration. They can therefore be used in accordance with the exhaust dyeing process at low dyeing temperatures and require only short steaming times in pad-steam processes. The degrees of fixation are high, and the unfixed portions are easily washed off, the difference between the degree of exhaustion and the degree of fixation being remarkably small—that is, the soaping losses being very small. They are also particularly suitable for printing, especially on cotton, but also for printing nitrogenous fibers, such as wool or silk or blend fabrics containing wool or silk.
The reactive dyes of the general formula (I) according to the invention have the further feature that, following the dyeing operation, unfixed dye portions on the fiber material are very easily washed off without whites in the same wash being stained by the dye that becomes detached. This brings advantages of the dyeing operation by saving on wash cycles and hence on costs.
The dyeings and prints produced with the reactive dyes of the general formula (I) according to the invention, especially on cellulose fiber materials, possess high color strength and a high fiber-dye bond stability both in the acidic and in the alkaline range, as well as good light fastness and very good wet fastness properties, such as wash, water, seawater, cross-dyeing, and perspiration fastnesses, and also good fastness to dry heat setting, pleating, and crocking.
The examples below serve to illustrate the invention. The parts and percentages are by weight unless noted otherwise. Parts by weight relate to parts by volume as the kilogram relates to the liter.
The absorption maxima (λmax) in the visible range reported for the dyes according to the invention were measured on aqueous solutions of their alkali metal salts.
Synthesis of a Compound of the Formula (VI) (Precursor)
18.8 parts of 2,4-diaminobenzenesulfonic acid are suspended in 150 parts of water and converted to a neutral solution by adding 20% strength sodium hydroxide solution. At 20° C., 14.7 g of formaldehyde bisulfite (Na salt) are added and the mixture is heated to 50° C. It is subsequently stirred for 4 hours at a pH from 5.0 to 5.5. The solution obtained is concentrated by evaporation or reacted further directly.
1H-NMR (400 MHz, d6-DMSO): δ (ppm)=3.77 (d, 2 H, 3J=6.6 Hz, CH2), 5.28 (s, 2 H, NH2), 5.54 (t, 1 H, 3J=6.6 Hz, NH), 5.82 (dd, 1 H, 3J=8.1 Hz, 4J=2.2 Hz, Har), 5.86 (d, 1 H, 4J=2.2 Hz, Har), 7.08 (d, 1 H, 3J=8.1 Hz, Har).
A suspension of 28.1 g of 4-(2′-sulfatoethylsulfonyl)aniline in 200 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 21 parts of 31% strength hydrochloric acid and the mixture is stirred for 15 minutes thereafter. Then 13.2 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is stirred for 60 minutes more with nitrite in excess. Excess nitrite is then destroyed by adding 10% strength amidosulfuric acid. The suspension of the diazonium salt is then admixed with the solution of the compound of the formula (Via) prepared in Example 1. The pH is then adjusted to 5-6 by adding 15% strength sodium carbonate solution and coupling is completed at 20° C.
The dyes of Examples (3) to (17) are obtained analogously by diazotizing amines R-NH2 as described in Example 2 and coupling the diazonium compounds with the compound (VIa).
18.8 parts of 2,4-diaminobenzenesulfonic acid are suspended in 150 parts of water and converted to a neutral solution by adding lithium hydroxide solution. This solution is cooled to 10° C. and admixed dropwise over one hour with 17.4 parts of 2,4,6-trifluoropyrimidine, a pH of 5.5 being maintained using 15% strength sodium carbonate solution. When the addition is complete the mixture is warmed to 20-25° C. and stirred for an hour thereafter. It is then filtered and 6.9 parts of sodium nitrite are added.
The dyes of Examples (19) to (32) are obtained analogously by diazotizing and subsequently coupling the amino compounds R-NH2 indicated in the table below by the method indicated in Example 18.
28.1 parts of 4-(2′-sulfatoethylsulfonyl)aniline are dissolved in 250 parts of water by neutralization of solid sodium bicarbonate. 4.2 parts of sodium fluoride are added to the solution, which is subsequently cooled to 0-5° C. by adding ice. Then, over the course of 5 minutes, 13.5 parts of trifluorotriazine are added dropwise, the pH initially falling rapidly and then leveling out at 4.5 to 5.0.
When the addition is complete, stirring is continued for 15 minutes. Subsequently, a neutralized solution of 18.8 parts of 2,4-diaminobenzenesulfonic acid in water is added dropwise and the pH is adjusted to 6.0-6.5. The reaction is completed by heating at from 30 to 35° C. followed by 60 minutes of stirring. The resulting solution is filtered and 6.9 parts of sodium nitrite are added.
The dyes of Examples (35) to (47) are obtained analogously by diazotizing and subsequently coupling the amino compounds R-NH2 indicated in the table below 25 by the method indicated in Example 33.
A suspension of 33.7 g of 4-(2′-sulfatoethylsulfonyl)aniline in 250 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 25 parts of 31% strength hydrochloric acid and the mixture is stirred for 15 minutes thereafter. Then 16 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is subsequently stirred for 60 minutes with the nitrite in excess.
The dyes of the general formula
set out in the table below are obtained by reacting the compound prepared as in Example 1 first as described in Example 2 with an amine A1-NH2 and then as described in Example 48 with an amine A2-NH2.
17.3 parts of aniline-4-sulfonic acid are dissolved in 200 parts of water and acidified by adding 21 parts of 31% strength hydrochloric acid. Ice cooling to 10-15° C. is followed by dropwise addition of 13.2 parts of 40% strength sodium nitrite solution. With an excess of nitrite, stirring is conducted for 60 minutes. The excess is then reduced by adding a few drops of 10% strength amidosulfuric acid solution.
A suspension of 33.7 g of 4-(2′-sulfatoethylsulfonyl)aniline in 250 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 25 parts of 31% strength hydrochloric acid and subsequently stirred for 15 minutes. Then 16 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is subsequently stirred for 60 minutes with an excess of nitrite.
Dull orange dyes of the formula
are obtained in analogy to the procedure described in Example 92 by diazotizing a reactive amine A1-NH2 in accordance with Examples 49 to 91 instead of 4-(2′-sulfatoethylsulfonyl)aniline and carrying out coupling in the second stage.
19.1 parts of aniline-4-sulfonic acid are dissolved in 220 parts of water and acidified by adding 23 parts of 31% strength hydrochloric acid. Ice cooling to 10-15° C. is followed by dropwise addition of 14.5 parts of 40% strength sodium nitrite solution. With an excess of nitrite, stirring is conducted for 60 minutes. The excess is then reduced by adding a few drops of 10% strength amidosulfuric acid solution.
Dull orange dyes of the formula
are obtained in analogy to the procedure described in Example 136 by using a solution of a dye according to Examples 3 to 47 instead of the dye solution described in Example 2.
30.3 parts of 2-naphthylamine-4,8-disulfonic acid are dissolved in 300 parts of water and acidified by adding 21 parts of 31% strength hydrochloric acid. Ice cooling to 10-15° C. is followed by dropwise addition of 13.2 parts of 40% strength sodium nitrite solution. With an excess of nitrite, stirring is conducted for 60 minutes. The excess is then reduced by adding a few drops of 10% strength amidosulfuric acid solution.
A suspension of 33.7 g of 4-(2′-sulfatoethylsulfonyl)aniline in 250 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 25 parts of 31% strength hydrochloric acid and subsequently stirred for 15 minutes. Then 16 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is subsequently stirred for 60 minutes with an excess of nitrite.
Dull orange dyes of the formula
are obtained in analogy to the procedure described in Example 182 by diazotizing a reactive amine A1-NH2 in accordance with Examples 49 to 91 instead of 4-(2′-sulfatoethylsulfonyl)aniline and carrying out coupling in the second stage.
33.3 parts of 2-naphthylamine-4,8-disulfonic acid are dissolved in 350 parts of water and acidified by adding 25 parts of 31% strength hydrochloric acid. Ice cooling to 10-15° C. is followed by dropwise addition of 14.5 parts of 40% strength sodium nitrite solution. With an excess of nitrite, stirring is conducted for 60 minutes. The excess is then reduced by adding a few drops of 10% strength amidosulfuric acid solution.
Dull orange dyes of the formula
are obtained in analogy to the procedure described in Example 226 by using a solution of a dye according to Examples 3 to 47 instead of the dye solution described in Example 2.
A suspension of 61.8 g of 4-(2′-sulfatoethylsulfonyl)aniline in 500 parts of water is admixed at 15° C. in succession with 0.5 g of a commercial dispersant and 50 parts of 31% strength hydrochloric acid and subsequently stirred for 15 minutes. Then 32 parts of 40% strength aqueous sodium nitrite solution are added dropwise and the mixture is subsequently stirred for 60 minutes with an excess of nitrite.
Dull orange dyes of the formula
are obtained in analogy to the procedure described in Example 272 by diazotizing 2.2 equivalents of a reactive amine A1-NH2 in accordance with Examples 49 to 91 instead of 4-(2′-sulfatoethylsulfonyl)aniline and reacting the diazonium compound with one equivalent of the coupler from Example 1.
| Number | Date | Country | Kind |
|---|---|---|---|
| 102 12 771.9 | Mar 2002 | DE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP03/02794 | 3/18/2003 | WO |
