DK142587B - Method for dyeing basic textile fibers and material by de-dyeing in an anhydrous dye bath. - Google Patents

Description

(11) FRENCH LIBRARY MANAGEMENT 1 ^ 1-2587 DENMARK (δ1), nt C | 3 0 06 p 1 ^ 0 • (21) Application No. 219 ^ / γθ (22) Filed on JQ. April 19? ° (24) Race day JO. April 1970 (44) The application made and the application for the petition filed 24 HOV. 19 ^ 0

DIRECTORATE OF

PATENT AND TRADE MARKET (30) Priority baked Fri.

JO. April 1969,% 12J5J, FR

Nov 26 1969 # 6§4θβ84, FR

Mar 20 1970, 70115J7, FR

OD GROUP INTERNET ECONOMIftUE 5TX, 5 bis, rue de Berri, Paris 8e, FR.

F2) Inventor: Remy Blanc, 19, Rue des Chartreux, 69 I ^ yon, FR: Willy Hess, 28, Chemin du Marfcelet, 69 Limas, FR: Georges Ramler, Montee St Koch, 69 Villefranche Sur Saone, ER.

(74) Plenipotentiary;

The engineering firm Lehmann & Ree._ (54) Procedure for dyeing basic textile fibers and material by discharge dyeing 1 in an anhydrous dye bath.

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a process for dyeing basic textile fibers and material for depletion dyeing in an anhydrous dye bath containing at least St polar organic solvent in the form of one or more optionally halogenated alcohols having up to 4 carbon atoms, wherein the dyes are soluble -polar solvent in the form of a halogenated ear hydride in which the dyes are insoluble or soluble, and optionally a small amount of acid.

The process according to the invention is characterized in that a bath containing, on the basis of 1000 volume units, contains 20-150 volume units of polar organic solvent and optionally up to 10 volume units of acid, the remainder of which is the non-polar solvent and that during the dyeing is continuous a removal from the bath of the polar solvent (s) in liquid or vapor form.

In the specification of German Patent No. 239,193, a color method is described, using as a colorant an alcohol solution acidified with aliphatic acids containing carbon tetrachloride, wherein the amount of polar solvent is approx. 300 volume units, the amount of non-polar solvent approx. 665 volume units and the amount of acid approx. 35 volume units per 1000 volume units color bath.

In the disclosure of French Patent No. 1,483,030, a staining method is generally described, whereby baths consisting of mixtures of various solvents including mixtures of non-polar solvents and polar solvents are used instead of aqueous color baths.

By the method according to the invention, a strong fixation of the dye is achieved and thereby a good staining of the treated material. This is due to the progressive removal of polar solvent from a bath, of which the polar solvent constitutes a relatively limited portion. By this continuous elimination of the polar solvent in which the dye is soluble, the dye is deprived of its carrier medium, thereby obtaining the desired good fixation on the textile fibers or material.

A particularly preferred embodiment of the process is characterized in that the dyeing is initiated at ambient temperature and the temperature of the bath is gradually increased for a period of between 30 and 60 minutes, until it reaches between 85 and 120 C, the latter being maintained at a period of time between 15 and 45 minutes. The use of this relatively high staining temperature favors a faster and more efficient removal of the polar solvent, thereby speeding up the staining operation.

In a further preferred embodiment of the process according to the invention, the dyeing is carried out under normal pressure and the polar solvent (s) are removed in the vapor phase and optionally partially recycled to the dye bath after condensation. This results in reduced consumption of polar solvent.

A further preferred embodiment of the process is characterized in that the dyeing is carried out under a pressure higher than atmospheric pressure, that a liquid fraction is withdrawn from the bath comprising a mixture of the polar organic solvent (s) and the non-polar solvent. from this mixture, partially or completely, the polar organic solvent (s) is separated, and the remaining liquid fraction is continuously recirculated to the bath.

By performing the dyeing under over-atmospheric pressure, a further improvement of the dye's fixation to the textile fibers or material is obtained, but the said precautions are taken to recover the non-polar solvent before it is recycled.

Preferably, a bath consisting of several polar solvents is used together with the non-polar solvent. It has e.g. It has been found that to obtain good staining conditions it is particularly advantageous to use as a polar solvent a mixture of methanol and isopropanol and as a non-polar solvent per-chloroethylene.

It may also be convenient to use as a polar solvent at least one compound capable of forming an azeotrope with the nonpolar solvent. In particular, a bath consisting of a halogenated aliphatic alcohol capable of forming an azeotrope with perchlorethylene is used. Among the halogenated alcohols that may be mentioned are chloro-2-ethanol, bromo-2-ethanol, chloro-1-propanol and chloro-2-propanol.

As mentioned, the amounts of polar solvents vary between 20 and 150 parts by volume. 1000 parts of the color bath. When using a mixture of polar solvents, especially methanol and isopropanol, the respective weight amounts of the alcohols are the same.

In addition, small amounts of acid, such as acetic acid, may be added to the dye bath. Usually, the amount of acid is up to 5 parts of the bath. When using a halogenated aliphatic alcohol, as explained above, the amount can be increased to 10 parts per liter. 1000 parts.

It is also possible to replace the whole or part of the acetic acid with a stronger acid such as e.g. mcaa.

The method of the present invention is particularly useful for dyeing yarns composed of continuous or discontinuous fibers of all shapes, as well as fibers present in flocks, ribbons, cotton wool, curds, and the like. The method can also be used in conjunction with woven fabrics, knitwear, nonwoven fabrics, provided that the fabric is loosely wound on a perforated weave bar which forms a kind of coil and the staining is done by a circulation pump. In another embodiment, said substances may be arranged together either in a circulating apparatus or in a rotating perforated drum. It is also possible to perform the coloring in tanks provided that they are tanks which are dense with respect to the solution used in filling with filling means, so that the loss of solvent by evaporation during introduction of the substances to be stained is reduced to a minimum.

Among the basic and treatable fibers are the polyamides 6,6-6 and 11, wool, fibers which have been "animalized" by grafting or otherwise and more generally all fibers which can be dyed with anionic colorants in some form, especially acidic and premetallized acidic colorants.

If there is a danger that the water, which can be extracted from the fibers by the solvents in the dye bath, may cause a separation in this bath, it is advantageous and even necessary to carry out a preliminary treatment for the substance to be dyed, removing the extractable water by a water-sucking solvent, e.g. hot perchlorethylene. Furthermore, in some cases, this pretreatment has the advantage of simultaneously removing dirt and other ingredients (such as grease) which are soluble in the solvent from the fibers.

The colorants are used without additives, i.e. that they contain only a minimal amount of impurities resulting from the manufacture of the coloring agents. Thus, these are, in fact, colorants having a maximum concentration, which is why it is unnecessary to purify by extraction and crystallization or by other methods.

In practice, the staining operation is preferably carried out as follows: In the case where a mixture of methanol, isopropanol and perchlorethylene is used, the powdered colorant is first dissolved at ambient temperature in methanol. Then isopropanol is added to the solution and the mixture is introduced into polychlorethylene. Finally, if necessary, glacial acetic acid is added.

With regard to the use of a polar solvent capable of forming an azeotrope with the nonpolar solvent, it has been found that a mixture of chloro-2-ethanol and perchloroethylene and in particular the azeotropic composition of 24.3 parts by weight of the former component and 75.7% by weight of the second component (boiling point: 110-111 ° C at 760 mm Hg) represents a good solvent for most of the coloring agents. Thus, it is easy to use this mixture, e.g. a mixture obtained by distilling a pre-used dye bath to dissolve the coloring agents and then adding additional amounts of perchlorethylene to obtain the desired conditions and optionally organic acid. However, for certain colorants, it may be necessary to maintain a small amount of methanol, isopropanol or a mixture thereof together with the azeotropic composition during the dissolution step. However, this can also be avoided and instead of adding to the bath greater amounts of acetic acid than mentioned above or a stronger acid, this addition being made in the preparation of the bath or gradually and after a certain staining time.

When the bath has been assembled, it is introduced into the dyeing apparatus in which the textile fabric has been introduced beforehand, which is not subject to any prior degreasing except in the case of fabrics with glued chain threads.

The staining operation begins at ambient temperature. Next, the bath is gradually heated for a period of time which may range from 30 to 60 minutes until reaching a temperature range of between 85 and 12CTC. The selected final temperature is maintained for a period of time which can vary between 15 and 45 minutes. The process is carried out under normal pressure or in an autoclave under pressure.

The total duration is adjusted according to the degree of depletion of the bath judged by the staining of a sample which has been previously introduced into the bath. The same method also makes it possible to set the optimum duration of the gradual heating, referring to systematically performed experiments during the dyeing of samples whose colors are judged by a colorimeter.

The temperatures and duration of the operation used are in principle a function of the boiling points of the selected polar solvents. When working with light aliphatic alcohols, e.g. methanol and isopropanol, the final temperature is of the order of 80-85 ° C and the duration of the gradual heating is about 30 minutes. The time period during which this temperature is maintained is essentially the same. Using a bath consisting of chloro-2-ethanol and per-chloroethylene, the boiling point of the azeotrope (110-111 ° C) formed from these two compounds allows the staining to be carried out at a temperature of up to 100 ° C and that the duration of the gradual heating can be increased up to 45 and even 60 minutes. Of course, the temperatures indicated may vary to some extent as a function of the pressure conditions.

As mentioned, the polar solvent (s) (hereinafter referred to as the polar component) is continuously removed during the staining in liquid or vapor phase.

The result is that, after g evenly distributed in the substance to be dyed after g 142587, the colorants are gradually freed from the component in which they are soluble and, as a result of the energy supplied in the form of heat, they are fixed. even better on the substance due to the fact that at the end of the operation, only one solvent in which they are insoluble is present. This fixation is further aided by the fact that the staining temperature is no longer limited by the boiling point of the polar component and can be increased more than when no removal has been made, however, keeping the temperature within the same general range mentioned above. . In practice, as soon as the dye bath kept under a pressure equal to or above atmospheric pressure has reached at least the theoretical boiling point temperature of the polar component under normal pressure, the said removal is carried out on a regular basis.

Thus, if the dyeing is carried out under normal pressure, the polar component is removed in the vapor phase. Next, it is readily condensed by known means and optionally partially recycled to the dye bath. When operating under a pressure higher than atmospheric pressure, one proceeds by withdrawing a liquid fraction of the bath containing a mixture of the polar component and of the non-polar solvent. For this mixture, the polar component is completely or partially separated and the remaining liquid fraction is continuously recycled to the dye bath. The polar component is separated by known methods. Thus, the liquid fraction withdrawn from the dye autoclave can be fed to an expansion apparatus, commonly referred to as a "flash" in which the separation between polar and non-polar solvents takes place. The polar component rapidly evaporates upon expansion and is collected in the upper part of the apparatus while the non-polar solvent is recovered at the bottom of the apparatus and recycled to the color container.

In this way, the dye bath is progressively freed from the polar constituent which is a solvent for the dye, and thus enables the latter, which is insoluble or poorly soluble in the nonpolar solvent, to be applied to the fibers in a very homogeneous manner.

The dye bath operates at constant volume, compensating for the progressive removal of polar component by the corresponding addition of non-polar solvent.

In general, the removal of the polar component occurs in a controlled manner, whatever separation technique is used. Regardless of whether a part of the separated polar component is reintroduced into the dye bath together with the recovered nonpolar solvent, the rate of removal of the dye depends on the bath, i.e. the application of dye to the fibers to be dyed. Thus, it has been found that the distillation rate must be inversely proportional to the amount of dye in the bath. At the beginning of the staining, where there is a lot of dye in the bath, the distillation rate may be relatively small, whereas the removal of the polar component at the end of the staining is accelerated until this component has been completely eliminated.

After dyeing, a rinse performed in the color device itself at ambient temperature is most often needed in the case of black and dark shades. It is not strictly necessary with the medium shades and the light shades where the extraction of the bath is almost complete. In practice, however, it is often better to rinse in all cases to eliminate the odor of acetic acid, unless the colors are very light, or the amount of acid is negligible, or in cases where the smell of acid is sufficiently eliminated during drying. When very large quantities of acids are included, two successive rinses are made, adding, as needed, a smaller amount of organic base, such as triethanolamine, piperidine and morpholine, to the first rinsing bath. According to a characteristic feature of the invention, the rinsing or rinsing is performed by non-polar solvent.

After the rinses, liquid is squeezed and a drying is done in known appliances.

A particularly significant advantage of the process of the present invention is that the dye bath, when containing the ingredients in the amounts set forth above, does not cause major corrosion and difficult to fire.

Finally, the recovery of the organic solvents presents no particular problems and can be practically complete with respect to the non-polar solvents. One has e.g. It has been found in a number of experiments that by fractional distillation of the dye bath and with the distillation bottoms at a temperature between 70 and 123 ° C, almost the total amount of acetic acid and 91.1% perchlorethylene can be recovered. leafily, a fractional distillation of the bath resulting from a first rinse with perchlorethylene has allowed a recovery of 99, 3 »of this solvent.

142587 o

Finally, the perchlorethylene used in another rinsing operation has been recovered in an amount of 99 s 7 $ by purification at a temperature between 68 and 120 ° C. The solvent fractions recovered by distillation can be reused in new dye baths after a simple bleaching of activated charcoal.

The following examples illustrate embodiments of the method of the present invention. The percentages stated are expressed on a weight basis and the amounts indicated are based on volume.

Following Examples 1-3 illustrate the embodiment in which the liquid component is removed in the liquid phase. Examples 1 and 2 relate to the use of the method of dyeing polyamide 6-6, denier value 1040, for use in the manufacture of blankets in the form of cylindrical coils, with 750 g of each being wound up and stained using a bath ratio of approx. 1: 13 · Example 3 relates to the dyeing of wool under the same conditions. The pressure during the staining is 3 bar.

The light and wash strengths shown in the examples were measured according to, rCode de solidité des teintures et impressions sur textiles - Recueil des normes francaises association francaise de normalization 1973 "·

Example 1.

The staining with 1% of the colorant C.I. Yellow acid 6l relative to the weight of the treated textile material.

The bath:

Denatured technical methanol: 100 parts

Technical perchlorethylene: 899 parts

Glacial acetic acid: 1 part

Initial temperature: 19 ° C

Final temperature: 10 ° C

The temperature gradually increased over 30 minutes to 82 ° C. The removal of polar solvent (by withdrawing liquid phase from the bath, separation of methanol and recirculation of perchlorethylene) was carried out after reaching a temperature of 82 ° C.

The removal of polar solvent is uniformly regulated in such a way that it has been completely removed in 40 minutes. At the end of the staining, the perchlorethylene is practically unstained. A single rinse for safety reasons in perchlorethylene at 40 ° C for a period of 6 minutes is then sufficient.

Duration of staining: 1 hour and 10 minutes.

The depletion of the hatred was total and the fixation was expressed in the following values:

Lightfastness: 6 Authenticity in washing in water: 5 Authenticity in washing in ISO 1: 5

Example 2.

Staining by 1% on the basis of fiber weight C.I. Red acid 57 of polyamide 6-6 fibers having a denier value of 1040.

The bath:

Technical methanol: 100 parts

Technical monochlorobenzene: 899 parts

Glacial acetic acid: 1 part

Initial temperature: 20 ° C

Final temperature: 100 ° C.

A temperature of 80 ° C was achieved over 30 minutes. The removal of polar solvent was performed from a temperature of 80 ° C and at uniform speed over 40 minutes.

Duration of staining: 1 hour and 10 minutes.

The depletion of the bath was total and the fixation was expressed in the following values:

Lightfastness: 6 Authenticity in washing in water: 5 Authenticity in washing in ISO 1: 5

Example 5

Staining of wool fibers by $ 1.2 C.I. Blue acid 129 based on the fiber weight.

The bath:

Technical methanol: 100 parts

Technical isopropanol: 40 parts 142587 ίο

Technical perchlorethylene: 857 parts

Glacial acetic acid: 3 parts

Initial temperature: 20 ° C

Final temperature: 102 ° C

The temperature rise was carried out gradually over 30 minutes.

The removal of polar solvents was performed from a temperature of 90 ° C in an amount of 25 parts over 27 minutes. The residue was removed within 33 minutes.

Total duration of surgery: 1 hour and 30 minutes.

Finally, 2 consecutive rinses were performed with perchlorethylene at a temperature of 22UC and over 10 minutes.

The depletion of the bath was total and the fixation was expressed in the following values:

Lightfastness: 6-7.

Authenticity for washing in water: 5 Authenticity for washing in ISO 1: 5

By the methods described in the above three examples, a satisfactory staining was achieved in terms of the color adhesion and yield. To confirm that such good results were obtained by using a completely anhydrous medium, a color test was performed in the laboratory, eliminating the moisture associated with the fibers and that supplied through the air. The operations performed were as follows: Drying a sample of 25 g of polyamide 6-6 filaments for 3 hours at a temperature of 115 ° C. Immediate introduction of the sample to the bottom of a narrow sample glass filled with 250 ml of a color bath at a temperature of 20 ° C and of the following composition:

Denatured technical methanol 21.00 parts

Technical isopropanol 23.00 -

Technical perchlorethylene 952.75 ~

Glacial acetic acid 3.75 -

Canned closure of the test tube with a stopper which is pierced at the center and in which a straight tube is inserted which is open at both ends. One end aligns with the lower end of the plug. The second one opens the free air into a tip of sufficient length to allow the rise of the bath during the heating thereof.

Gradually heating the sample tube in a water bath to a temperature of 74 ° C over 26 minutes and maintaining this temperature for 27 minutes.

The surface of the colored bath rises in the tube as the temperature rises and then stays at a constant level.

It is found that the intensity of the staining of the liquid in the tube decreases as it heats up until it virtually disappears after 53 minutes, which shows an extraction of the bath and transfer of the fibers between 90 and 100¾.

The sample finally removed from the sample tube has a uniform color even in the uninflated state, the strength of which is the same as that obtained under the same conditions by a staining carried out in free air on a non-dried sample. This hue and strength is the same as for the same fibers containing the same amount of dye applied in aqueous medium by known methods.

As a result, the presence of a certain amount of water is not necessary for a staining carried out in a solvent as described above, which is also discussed in connection with the known methods. ·

It should be noted that the apparatus described in connection with said test constitutes an appropriate means of determining the necessary and sufficient temperature and time conditions for each staining in a prior experiment.