MXPA99002117A - Alkaline aqueous solutions and use of these procedures to dye textiles materials - Google Patents

Abstract

Aqueous solutions are disclosed which comprise sodium hydroxide and potassium carbonate in a molar ratio of 1: 1.7 to 1: 0.5, which are useful for preparing alkaline dye liquors, especially liquors for the application by pads, of dyes reactive to the fibers to produce stains on cellulosic textiles

Description

ALKALINE AQUEOUS SOLUTIONS AND USE OF THEM IN PROCEDURES FOR DYEING CELLULOSE TEXTILE MATERIALS DESCRIPTIVE MEMORY The cellulosic textiles are dyed by such procedures as printing, dye exhaustion and application by pads. The dyes reactive to the fibers, which are capable of forming a covalent bond with the fiber during the dyeing process, are particularly important dyes for cellulosic materials since the dyeings obtainable are also notable for their good firmness to the wet in particular, which is very difficult to impossible to obtain with dyes not reactive to the fiber. However, the covalent bond between • Fiber and fiber reactive dyes generally only arise when the staining procedure is carried out under alkaline conditions. The alkalis used are alkali metal carbonates, alkali metal bicarbonates, and hydroxides of metals, alkalis or mixtures thereof in addition, in the dyeing by "application by pad, alkali metal silicate,! optionally together with a hydroxide or carbonate of the alkali metal, the term "alkali metal" includes, 1 lithium as well as sodium and potassium. It is the mixtures of alkali carbonates and alkali metal hydroxides in particular those which are highly effective and are preferred, although the system alkaline used in a particular case is chosen according to the group of the fiber-reactive dye and the specific dyeing process. An ultra-short liquor staining process, for example the pad-applied process, whereby the treatment liquor is applied to a textile material and the excess liquor in the textile material is then squeezed, it can be carried out according to the procedures both of a stage like two stages. The two-stage process procedures, whereby the textile material is initially impregnated with a dye solution until some moisture absorption, then dried and subsequently over-applied with pads in a subsequent impregnation step with an electrolytic salt liquor, Alkaline has the disadvantage of high t use of machines and of using electrolyte salts in the second phase of the process. In contrast, in the one-stage process, the entire treatment liquor, which contains both the fiber reactive dye and the alkali without additional auxiliaries, is applied to the textile material in an operation which is followed by the step of fix the colorant on the text 1il material. One of these one-step process procedures is the cold batch-pad process, which is mainly used for dyes containing a group i! reactive to fiber; In this case, the alkaline bonding agents used are frequently alkali metal silicates. in the form of liquid glass (Na2 ?: Si? 2 in a ratio of 1: 2 to 1: 3.5), between 60 and 130 g of 38 ° Bé liquid glass and 6 to 40 ml of aqueous solution of 32% by weight aqueous sodium hydroxide are added per liter of the coloring liquor, depending on the depth of water. tone you have in mind. The liquid glass has the advantage that it has a regulating effect of pH and I increases the stability of the liquors for application by pad of the reactive dyes. Another positive effect of using liquid glass in the pad application process is that the edges of the material to be dyed will have the same depth of shade and hue, since the liquid glass forms a protective layer against the carbon dioxide of the air environmental. However, the use of liquid glass is not completely beneficial. Examples of disadvantages are that liquid glass tends to crystallize and therefore tends to soil the equipment; that it is not possible to neutralize the textile material before the washing step; and that the use of steam to fix the pollutants is not always possible; In addition, undesirable manipulative effects may arise. I Literature describes attempts to overcome such disadvantages. By in the U.S. Patent. 4,555,348 an aqueous regulatory system which has a pH between 11 and 13 and which contains various phosphate salts is added to the dyeing liquors.The aqueous regulatory system as such is undoubtedly suitable for dyeing baths of aqueous dyeing processes.

Application procedures by pad. In addition, the regulatory system has the disadvantage that phosphate salts create environmental problems in water treatment plants. 1 The dyeing technique by the cold pad-batch method generally presents the addition to the dyeing liquor (application by pads) of a specific amount of sodium hydroxide solution, calculated on the basis of the amount of dye present in the liquid dyeing, and in addition to about 30 g / 1 of electrolyte salt, such as sodium chloride or sodium sulfate. However, the stability of the liquor for pad application is generally unsatisfactory and leads to losses in the color strength of the dyeings. However, the prior art also teaches that the sodium carbonate by itself or the mixtures of sodium carbonate and sodium hydroxide can be used in the case of fiber systems, for example dichloroquinoxaline, difluoromono-chloropyrimidine and monofluorotriazine dyes. In the case of the pure sodium carbonate method, the lower pH will sometimes lead to non-economic long fixation times, while the sodium hydroxide / sodium carbonate variant will sometimes lead to increased hydrolysis of the sodium hydroxide. reactive dye. These systems are less suitable for vinyl sulfone dyes since the fixing times are significantly longer and compromise the economy of the staining procedure. Furthermore, the technique as it is presently taught teaches in relation to the method of sodium hydroxide / sodium carbonate that the amount of sodium hydroxide used varies with the concentration of the dye, while that of sodium carbonate is always' tf added as a fixed proportion. It is an object of the present invention to provide, in i! the field of staining by ultrashort liquor procedures, for example by pad application procedures, especially by the cold lot pad process, an aqueous alkaline formulation which can be added to the stain liquor without creating the disadvantages I mentioned. It has been especially as a replacement for glass ultra-short procedures with liquor such as pad application processes, an aqueous solution comprising sodium hydroxide and potassium carbonate in a molar ratio of 1: 1.7 to 1: 0.5, preferably 1: 1.5 to 1: 1.1, particularly preferably 1: 1.2 to 1: 0.7, supersely has the advantageous effect,? wanted. In addition, the alkaline formulation of the invention has the particular advantage, in its use that it can be measurable. And the use of urea in the staining procedures can be eliminated. •! Examples of formulations according to the invention which are suitable for production are aqueous solutions of 39.6 Kg of sodium hydroxide and 110 to 163 kg of potassium carbonate in 150 to 1000 liters of solution. The invention therefore provides this solution and also a method of using it -in ultra-short aqueous liquors, such as the liquors for application by pads, which, 1 contain dyes reactive to the fibers. This may include customary staining aids, such as an anionic wetting agent. The alkaline formulation of the invention is used according to the invention by mixing an aqueous solution of one or more dyes reactive to the fibers, optionally including customary dyeing aids, with the alkaline formulation of the invention (generally 100 liters of a aqueous dye solution comprises about 10 to 12,000 which will be mixed with 2 to 17 liters of the alkaline formulation of the invention) and using the ^^ resulting alkali staining liquor to impregnate a cellulosic textile material in a conventional manner, for example by spraying or by application by pads and fixing the colorant or dyes under the process conditions used for dyes reactive to fibers. The invention thus further provides a process for dyeing cellulosic textile material by mixing for example a solution of the aqueous dye which contains per liter about 0.1 to 120 g of one or more of the dyes reactive to the fibers and optionally the auxiliary dyes. staining, ii with the alkaline formulation of the invention, for example with at 170ml, based on 11 of the dye solution, by applying the resulting alkaline dye liquor to the cellulosic textile in an amount of 60 to 100% by weight, based on the weight of the material, for example by spray or by application by pads preferably by means of a customary pads application, and fixing the dye or dyes under the customary process conditions for the dyes reactive to the fibers. Since the alkaline formulation of the invention is easily measurable within the dye solution, even in small amounts and steps, to form the liquid for pad application, the dyeing process is also easily performed continuously; the alkaline liquor for application by pads can therefore be continuously formed which ensures its stability even in the case of critical dyes. better washing, neutralizability (not existing in the case of liquid glass since the treatment in an acidic bath is not possible without the formation of SÍO2) and better handling. A preferred ultra-short staining procedure is that of the cold pad-batch process, in which the alkaline staining liquor (staining solution) is pressed with the pads on the fabric and the pressed fabric is then rolled up in a roller and left at room temperature on the furler for 4 to 24 hours. The fixing phase is followed by a customary washing procedure, in which the material can be acidified. The pBR staining techniques of ultrashort liquor can be developed for example according to the correlations shown in figure 1, between the concentration of the dye and, 1 the amount of alkaline formulation in the liquor for application by pad necessary to effect the fixation. The alkaline formulation, for example, which is an aqueous solution of 39.6g of sodium hydroxide and 163g of potassium carbonate, per lOOOml, of which 49ml is used for the lowest usual dye concentration. , requires that I use 0.1 to O.llml additional of it by 0.1 parts! by weight of the dye. • of the alkaline formulation B, which 146 g of sodium hydroxide and 390 g of potassium carbonate per 1000 ml, the alkaline stain liquor requires an additional 0.04 to 0.045 ml of the alkaline solution B per 0.1 parts by weight of the dye 'i as well as 20 ml of this alkaline formulation B required for the lowest usual concentration of the dye. The alkali-forming liquor obtainable by the mixing of the alkaline formulation of the invention with an aqueous solution of dye, reagents to the fiber has a high liquor stability, for application by pad and f! It can be used in all ultra-short liquor procedures such as the application procedures by means of pads, hitherto customary using alkali metal silicates (liquid glass) as alkaline donors and / or pH regulating agents and replace the latter in the Reactive dyes to fibers should be given special emphasis to those, which have a radical reactive to the fiber of the series of vinyl sulfone, for example vinylsulfonyl or an ethylsulfonyl, which is β-substituted by an alkali removable substituent , such as β-sulfatoethylsulfonyl, β-acetoxyethyl-sulfonyl, β-chloroethyl-sulfonyl or β-thiosulfatoethylsulfonyl, furthermore fiber-reactive radicals of the series "chlorotriazinyl, fluorotrazinyl, dichloroquinoxalinyl, <; fluoropyrimidinyl and chlorofluoro-pyrimidinyl, and in addition dyes possessing combinations of such 1 reactive groups to the fibers. The following examples illustrate the invention. The parts and percentages are by weight, unless otherwise indicated. The parts ,! in weight they are related to the parts in volume like the kg to the liter.

EXAMPLE 1 parts of a woven cotton fabric bleached at 20 ° C are applied by padding to obtain a moisture absorption of 70%, based on the weight of the fabric, an aqueous solution containing (per 1000 parts by volume) 10 parts of the dye of the formula indicated below (A) which has an electrolyte salt content of about 50%, 10 parts of the dye of the formula indicated below (B), which has an electrolyte salt content from about 50%, - 10 parts of the dye of the indicated formula i (C), which has an electrolyte salt content of about 50%, and 33 'parts of an alkaline formulation which < ! It contains about 4-87 parts of sodium hydroxide and 1 about 13 parts of potassium carbonate (the liquor is obtained by the addition of 33 parts of an original alkaline formulation which contains (per 1000 parts) ) about 331 parts by volume of 32% sodium hydroxide solution and about 390 parts of potassium carbonate, to an aqueous solution of the aforementioned dyes thereafter • The fabric impregnated in this way with the tinting liquor is rolled or braided in a reel and left for 12 hours in that state at 20 ° C, then subjected to the procedure of washing customary for dyes reactive to the fibers. A brown stain is obtained with the same depth of ^^ tone and firmness than in the antecedent staining technique .1 (obtained using liquid glass and sodium hydroxide solution) and with the edges of the fabric completely penetrated. H 'I II EXAMPLE 2 Example 1 is repeated using an aqueous staining liquor which (for every 1000 parts by volume) contains 16 parts of the dye, of the formula set forth below (D), which has an electrolyte salt content of about 50%, 12.6 parts of the dye of formula (E), which has an electrolyte content of about i.l.l.l%, 13.3 parts of the dye of the formula (B), which has a electrolyte content of approximately 50%, and 58.5:! parts of the dye? of the formula (C) which has an electrolyte content of about 50%, plus 24 parts of sodium carbonate and 9.1 parts of sodium hydroxide (corresponding to approximately 62 parts of the new alkaline formulation which was mentioned in Example 1 and added to the dyeing solution).

S CH, CH2-OS03Na A dark gray stain is obtained with the same hue and level of firmness as the dyeing produced by the standard procedure customary in the prior art, wherein the dyeing liquor contained liquid glass, sodium carbonate and urea.

A mercerized fabric that had a weight close to it is applied, through pads on a press machine with pads, up example one and adding an anionic wetting agent). The fabric Soaked is then passed, at a speed of 20 m / min, to a fixing unit at 120 ° C and a relative humidity of 25% and kept there in (up to a wet bulb temperature of 70 ° C for 2.5 minutes, fixing the dye in the fabric. The dyed material leaving the fixing unit still has a residual moisture content of 15% and is then subjected to a continuous washing procedure customary for reactive and finished dyes. *,! 1 The yellow stain has a very uniform appearance and a smooth surface. The hue is 5% deeper than the dye produced by a traditional pad-drying-pad-steam application procedure using a dye pad, a dryer and a chemical pad} | It comprises 900 ml / 1 of liquid glass and 100 ml / 1 of sodium hydroxide solution at i32% as alkaline donor.

EXAMPLE 4 A press machine with pads is used to impregnate a woven viscose fiber fabric having a weight weight of about 100 g / pr with an aqueous dye liquor which (per 1000 parts by volume) contains 50 parts of the dye the formula (F) which has an electrolyte content of about 50%, 6.1 parts of sodium hydroxide, 16.1 parts of potassium carbonate parts of a commercially available anionic wetting agent (obtainable similarly to example 3) until obtaining a moisture absorption of 90% , based on the weight of the fabric, at 20 ° C. The fabric so soaked is braided or entangled in a production arm and left on it to ° C for 12 hours to fix the dye. The dyed fabric is then conventionally rinsed, washed and finished. A strong red tint is obtained with the same depth of tone ij I as the dyeing obtained by the pad-drying-pad-steam application process.

'' EXAMPLE 5 To 10 parts of a linen cloth bleached at 20 ° C, it is applied by means of pads, until obtaining an absorption of! humidity of 70% based on [the weight of the cloth, an aqueous solution] i which (for every 1000 parts by volume) contain 90 parts of a dye powder of the formula (G) with 50% strength, which contains electrolyte salts, 16 parts of a 50% powder! strength of the dye of the formula (H), which contains electrolytes, 1.6 parts of a powder of 50% strength of the dye of the formula (F), which contains electrolyte salts, and 66 parts of a new aqueous solution which includes 9.8 parts of sodium hydroxide and 26 parts of potassium carbonate.

The fabric thus impregnated is then rolled or braided onto a reel and left at 20 ° C for 12 hours. The dyeing obtained is then finished in a manner customary for reactive dyes _k the fibers, by rinsing and washing. A black dyeing is obtained with the same depth of tone and dyeing obtained by the liquid technique and hydroxide solution of sodium. if EXAMPLE 6 A 10-part woven cotton cloth bleached at 20 ° C is applied by pads, until a moisture absorption of 80% is obtained, based on the weight of the cloth, an aqueous solution which (for every 1000 parts in volume) contains 30 parts of a powder at 50% strength of the dye of the formula j (A), which contains electrolytes, 9 parts of a 50% strength powder of the dye of the formula (J), which contains electrolyte salt, 10.5, parts of a 50% strength dye of the formula (C), which contains electrolytes, 4.5 parts of a 50% powder of the dye of the formula (G), which contains electrolyte salt, and 43 parts of a new aqueous solution that,? It comprises 6.2 parts of sodium hydroxide and 16.5 parts of potassium carbonate. > The fabric thus impregnated is then rolled or braided i into a reel and left at 20 ° C for 12 hours. The dyeing obtained is then finished in a manner customary for dyes reactive to the fibers, by rinsing and washing. A dyeing of mud color is obtained with the same depth of tone and level of firmness as the dyeing obtained by the prior art process using liquid glass and sodium hydroxide solution.

EXAMPLE 7) A 10 parts '' of a woven cotton fabric bleached at 20 ° C is applied by pads to obtain a moisture absorption of 70%, based on the weight of the fabric, an aqueous solution which (for every 1000 parts in volume) 1 contains 100 parts of a powder at 50% dye strength Copper phthalocyanine of the formula indicated below (K), which contains electrolyte salt, and 61 parts of a new aqueous solution comprising 9.1 parts of sodium hydroxide and 24 parts of potassium carbonate.

The fabric thus impregnated is then rolled up in a reel II and left at 20 ° C for 12 hours. Is the dye obtained? then finished on t > a customary way for tj dyes reactive to the fibers, by rinsing and washing. A turquoise dye is obtained with the same depth of tone and level of ; 2 I i firmness that the dyeing obtained by the procedure of the prior art, using liquid glass and sodium hydroxide solution.

! EXAMPLE 8 parts of a mercerized and 1 bleached cotton fabric at 20 ° C are applied by padding to obtain a moisture absorption of 70%, based on the weight of the cloth, an aqueous solution which (for each 1000 parts by volume) contains 3 parts of a 50% strength powder of the dye of the formula (D), which contains electrolyte salt, 3 parts of a powder at 50% force of the dye of the formula I ( E), which contains electrolyte salt, 3 parts of a powder of jj 50% strength of the dye of the formula (C), which contains I electrolyte salt, and 58 parts of a new aqueous solution comprising 2.3 parts of hydroxide of sodium and 9.5 parts of I! potassium carbonate.1 The fabric is then rolled or braided in a furler and 20 ° C for 12 hours. The dyeing obtained is then finished in a manner customary for the reactive dyes, the fibers, by rinsing and washing. A light brown dye is obtained with the same depth of shade and level of firmness as the dyeing obtained by the procedure of the prior art using liquid glass and sodium hydroxide solution.

EXAMPLE 9 To 10 parts of a bleached woven cotton fabric ° C is applied t | using pads until obtaining a II absorption to solution) contains B-RF (Col a new 5.1 parts, sodium hydroxide and 21 parts of potassium carbonate. The fabric thus impregnated is then rolled up on a reel and left at 20 ° C for 12 hours. The dyeing obtained is then finished in a manner customary for the dyes reactive to the fibers, by rinsing and washing. A dark blue dye is obtained with the same depth of tone and level of firmness as the dye obtained by a prior art process using liquid glass and sodium hydroxide solution. 1 EXAMPLE 10 To 10 parts of a woven cotton fabric bleached ° C is applied by padding until a moisture absorption of 70% is obtained, based on the weight of the cloth, an aqueous solution which (per 1000 parts by volume) Contains 110 parts of a powder at 50% dye strength of the formula (G), which contains electrolytic salts, 40 jj parts of a powder at 50% strength of the dye of the formula indicated below (L), which contains electrolyte, and 90 parts of a novel aqueous solution, of 13 parts of sodium hydroxide The fabric thus impregnated is then rolled up on a reel and left at 20 ° C for 12 hours. The dyeing obtained is then finished in a manner customary for the dyes reactive to the fibers, by rinsing and washing. A deep dark black dye is obtained with the same depth of tone and level of firmness as that obtained by a prior art process using liquid glass and sodium hydroxide solution.

Claims (5)

NOVELTY OF THE INVENTION CLAIMS

1. An aqueous solution comprising sodium hydroxide and potassium carbonate in a molar ratio of 1: 1.7 to 1: 0.5.

2. - An alkaline formulation according to claim 1, which comprises sodium hydroxide and carbonate. ^ of potassium in a molar ratio 1: 1.5 to 1: 1.1. the fibers, using the resulting alkaline dye liquor to impregnate a cellulosic fabric into a conventional form and fixing the dye or dyes under the customary process conditions for the reactive dyes to the fibers, . 5. A process for dyeing cellulosic textiles, which comprises mixing an aqueous alkaline formulation according to at least one of claims 1 to 3 with an aqueous solution of one or more dyes reactive to II. the fibers, resulting util to impregnate fix the dye or dyes under the staining conditions