DE2156675A1 - Process for dyeing and / or finishing textiles - Google Patents

Description

Process for dyeing and / or finishing textiles

(Addition to patent 2 021 110 - patent application P 20 21 110.3-43)

The invention relates to a method of dyeing or any other finishing of fibers and textiles by exhausting the dye or finishing agent of the fleet. ■

In the Hauptanmeidung a process for dyeing of basic textile fibers and products produced therefrom is described by exhaustion of the dye from a fleet to be a small part of polar organic solvents in which the dyes are soluble and contains _r to a main part of a non-polar organic solvent, in which the dyes are little or not soluble. A mixture of methanol and isopropanol is specified as the preferred polar solvent and a halogenated hydrocarbon such as perchlorethylene is specified as the preferred non-polar solvent or diluent. The polar solvents mentioned can be wholly or partially replaced by a halo-

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substituted aliphatic alcohol, such as 2-chloroethanol be that with the perchlorethylene an azeotropic mixture forms. According to a particularly advantageous embodiment is continuously from the color apparatus the or, the polar (n) Solvent drawn off in the liquid phase or in the vapor phase.

The present invention relates to an advantageous modification and further development of the method according to the Main patent. . .

After the .Verfahren of the main patent can be the dyeing process Under atmospheric pressure or under increased pressure carry out; the polar solvent is drawn off in the vapor phase when dyeing is carried out under normal pressure Part of the liquid phase is drawn off when dyeing under increased pressure. It has now been shown that the solvent can be removed very well in the vapor phase even if not under normal pressure, but under is colored increased or under reduced pressure. It then only needs to set the temperature of the liquor that · these under the applied pressure or vacuum conditions boils. It has also been shown that the liquid phase can also be removed if the liquor is under normal pressure or even under vacuum provided that their temperature is always below their boiling point is maintained.

In the main patent it is further described that the the liquid phase withdrawn from the liquor can be passed into an expander or evaporator, which is usually "flash" vapor he is called and in which the separation occurs between polar and non-polar solvent.

The polar solvent is preferably withdrawn as an overhead product in vapor form which is condensed thereon during.

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the non-polar solvent as a bottom product in the evaporator "remains, - It has been shown that the operation of this device easily and very well adapt to the most varied of conditions of application of the dyeing process according to the invention adjusted. So you can use the evaporator both under atmospheric pressure and under overpressure or Let the negative pressure work. Is the pressure in the dyeing machine the same or less than that for the relaxer? selected pressure, the withdrawn liquid phase is sufficiently heated when it leaves the dyeing apparatus, so that their more volatile components can be separated off in the expander. On the other hand, is the pressure in the dyeing machine higher than the pressure in the expander, the temperature in the dyeing machine is increased sufficiently to remove the volatile component the withdrawn liquid phase is then separated off by simply letting down the pressure. Regarding the separation the liquid phase withdrawn from the liquor in its components has been shown to be that described in the main patent System can be replaced by any other mode of operation, in which of the different physical Properties of the components are made use of, such as crystallization, azeotropic distillation, ge

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Adsorption, especially with the help of molecular sieves, passage through semipermeable membranes, etc.

It has also been shown that the method of the main patent can be applied not only to basic fibers and textiles made from them, but also to Textiles made from natural fibers, synthetic fibers and synthetic fibers of all kinds and in particular made from fibers and fabrics Cellulose esters, polyesters, and acrylic polymers and copolymers and from polyvinyl alcohol.

The combination of polar solution, described in the main patent

209834/1142 O _{R) G / NA1} _

The medium and non-polar solvent can also be replaced by a number of other combinations while maintaining the advantages of the procedure described in the main patent, ie homogeneous and permanent dyeing of the textiles and practically complete extraction of the dyes from the liquor. ^{v In} principle, this procedure requires the simultaneous use of a solvent that can dissolve the dyes used and another solvent, hereinafter referred to as diluent, in which the dyes are insoluble or sparingly soluble, regardless of the type and nature of the solvents and diluents, provided that these can be separated by any means, in particular by the various methods mentioned above. A polar solvent can therefore be combined with a polar diluent or a non-polar solvent with a non-polar diluent or a non-polar solvent with a polar diluent with very good success. Furthermore, in this combination of solvent and diluent, the one polar organic component can be replaced by water. Finally, all combinations of solvent and diluent which form an azeotropic mixture, whose.-.- boiling point preferably -below .des -boiling point- des-Vex = -,. _ thinning agent so that it can be separated by evaporation.

The new options just defined for the composition of the fleet include, for example, the combination von'Trichlortrifluoräthan (solvent) with an inert fluorinated diluent, for example a perfluorinated trialkylamine, etc., or the combination Methanol, pyridine or acetonitrile (solvent) and water (diluent).

'The procedure described in the main patent can ultimately not only be applied to dyeing by pulling out a To apply the fleet, but also to the different ones

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ORIGINAL! Ν8ΡέζΠΒ>

2156875

Finishing and finishing treatments of fibers and textiles, e.g. optical brightening, insecticidal equipment etc. The bath used then consists of a solvent for the finishing or finishing agent and a diluent in which this finishing agent is insoluble or is sparingly soluble. This treatment can be used along with or can be carried out independently of the dyeing process. Apart from the modification and improvement described the process is followed by dyeing or pre- and post-treatment and rinsing the fibers and textiles expediently under the same working conditions as for Main patent; this concerns the possible addition of glacial acetic acid or a stronger acid, the gradual increase of the Temperature, # 4e the amount to be taken from the "liquor Proportion, working at constant volume by adding of diluent (which can be recovered from the portion withdrawn from the liquor) etc. The quantitative ratio from solvent to diluent as well as the duration of treatment is not critical and can vary within a very long time further limits can be varied. The maximum working temperature depends on the boiling points of the new, according to the invention

solvents and thinners to be used and of the _

"" treated fibers and textiles. Can be used as a dye of course one of the known, with the textile material in question and the solvent and diluent used contractual dyes are chosen; Also come with other TüTorte, besides the anionic colors cationic dyes, plastic-soluble dyes, etc. in question i

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The following * examples serve to explain the; ErfiriciÄigr SXf ^ tz ^ preferflfen * on the various possibilities the removal of the fleet, on the application of the procedure on non-basic fibers, on the new combinations of solvents and thinners, and on the apprecia-

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door and finishing procedures.
Example A_

Two 400 g swatches of a jersey made of polyamide 6.6 were dyed with, based on the weight of the fabric:

. 0.5% by weight Acid Red CI, £ 7 and 0.5% by weight acid yellow CI. 25th

Composition of the liquor: Methanol '75' parts by volume

Perchlorethylene ■ 925 parts by volume

• Total amount of the fleet: 39 1.

The first pattern was dyed at atmospheric pressure; the Anfängstemperatur of 37 ⁰ C was placed over ih to 60 0 and then 4 $ held min, corresponding to h a Gesamtfärbedauer of 1 45 min. The withdrawal of a portion of the liquid liquor was 1 Ir after the dyeing begun, and this removal to continued towards the end of the staining process.

The liquid phase was first in a preheater Heated to boiling temperature and then passed into a "flash" evaporator. The volume of condensed vapors was

"7 Γ05 i ~;" the condensate contained all of the methanol used. The non-evaporated perchlorethylene was passed into the dyeing apparatus and fresh diluent was added in order to keep the bath or the liquor at a constant volume. The extract of the dyestuff from the fleet warde photocolorimetrisch evaluated and the trigger was after 1 hour, ie, before the start of a part of the fleet, and 24% at the end of the dyeing 100%. A very uniform, lightfast and washable red color was obtained.

The second sample was dyed under the same conditions as above for a total of 1 hour 45 minutes, but without deducting part of the liquor. The extraction of the dye from the liquor was after. 1 h 45 min only 24 %.

ι o-- '-;. - / 209834/1142 original inspected

example

It was the same textile material as in Example 1 with the same dyes and the same liquor with the same Dyed dye concentration and the same liquor ratio.

The dyeing was carried out under a pressure of 4 bar absolute at one. Initial temperature of 30 ^{° C., which is brought to 100 °} C. in the course of 50 min and then 1 hour at this

Value was held. ■. ". -

The withdrawal of the liquid from the liquor began for 1 hour 10 minutes after the start of dyeing and was up to the end of the dyeing process continued. The liquid phase was immediately in the below Atmospheric pressure working evaporator directed; the condensed vapors had a volume of 7 * 20 l and contained all of the methanol originally added.

The dye extraction from the liquor was at the beginning of the removal of the liquid, after 1 hour 10 minutes _; 4-0 % and at the end of the dyeing process 100%.

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Withdrawal of liquid phase worked, so in the end \

the dyeing process only 40 ° / o of the extracted dye.

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This example illustrates the removal of solvent in the vapor phase. The same textile material as in the previous examples was dyed with the same dyes and the same liquor ratio, and the temperature of the liquor was initially 30 ^° C. under atmospheric pressure. Based on these common conditions were

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treated three patterns as follows:

a) It was dyed in an open apparatus and the liquor was brought to 65 ° C. in 1 h 15 min, then removal began of the fumes and was after the end of the dyeing process continued for a total of 2 hours 10 minutes.

b) It was colored in a closed apparatus, and the bath in the course of 1 h 25 min 73 ⁰ O heated. The pressure was then x 1.4 bar absolute. They started with the withdrawal of vapors and put it to the end of the dyeing of 1 h 4-5 min continued, the temperature rose to 90 ⁰ C.

c) The fleet was gradually heated to 60 ⁰ C. After 1 hour a slight vacuum was applied so that the pressure in the dyeing machine was 600 ml Hg. The vapors then began to be withdrawn. The total duration of the dyeing process was 2 hours 30 minutes.

In all three different procedures, the dye was completely exhausted at the end of the dyeing process.

Example 4

-Es -w * r-den — 3-5Q g -P-el-yes-ter tissue-ait · Θ; _r 5 - & ewr- ^, - related =

on the fabric, dyed with a plastic-soluble dye namely with dispersion blue CI. 40. Composition of the liquor: 2 ~ chloroethanol 25 parts by volume

Trichlorethylene 50 " ^le Perchlorethylene 925"

Total volume of the fleet: 100 1.

The dyeing took place under a pressure of 4.5 bar absolute at an initial temperature of 20 ° C, which in the course of 55 min rose to 130 ° C and then held at this value for 1 h became. The removal of a liquid portion of the liquor began 1 hour 25 minutes after the start of dyeing. The liquid phase was immediately

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ORlGlNALlNSPECTEb

■ - 9 -

bar passed into the evaporator operating at atmospheric pressure; the condensed vapors had a volume of 40 l and contained the total amount of trichlorethylene and chloroethanol. The dye separation was 80 %.

The dyed material was rinsed with cold perchlorethylene and dried. A uniform lightfast was obtained and washable medium blue shade.

If the same conditions were used, but no liquid was withdrawn, only 10% of the dye was removed from the Fleet moved out.

Example 5

900 g of fabric made of polyacrylonitrile (Crylor) were dyed with 1% by weight, based on the fabric, of blue dye and although Lyrcamin-Blau 2 BLL. -

Composition of the liquor: methanol · 100 parts by volume * ~ Isopropanol 10 "

Glacial acetic acid 5 "

Perchlorethylene 885 "

"Total volume" of the "FIoTTte:

Dyeing was carried out under a pressure of +, 5 bar absolute. Initial temperature 25 ° C; Temperature increase to 110 ⁰ G within 30 minj total duration of the dyeing process 1 h 50 min; Start of removal of the liquid phase 1 hour 15 minutes after the start of dyeing. Separation of the solvent from the withdrawn liquid fraction directly by evaporation under atmospheric pressure.

Liquid recovered by condensation of the vapors Volume 4- 1, after 10 min 9 1 at the end of the dyeing process.

The dye extraction was 100 %.

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The polyacrylonitrile material was uniform, lightfast and washable in a medium blue shade.

If the same conditions were used, but no liquid was withdrawn , the dye was only extracted to the extent of 45%.

Example 6.

400 g of cellulose triacetate fabric were dyed with 1% by weight dispersion blue CI. 40.

Composition of the liquor: methanol 100 parts by volume

Isopropanol 10 parts by volume, perchlorethylene 890 parts by volume

Total volume of the fleet: 40.50 1st.

Dyeing was carried out under a pressure of 4.5 bar absolute; Initial temperature of 40 ⁰ C, increase in temperature to 11O ⁰ C in the course of 20 min, total time of the dyeing transition before it 1 h 25 min, the beginning of the extraction liquid 50 minutes after the start of dyeing; Separation x of the solvent from the liquid drawn off by evaporation under atmospheric pressure; liquid volume recovered by condensing the vapors 2.6 liters after 10 minutes and 8.3 liters at the end of the dyeing process.

At the beginning of the removal of the liquid, only 2 % of the dye had been drawn out of the liquor, and at the end of the dyeing process, 80% of the dye had been drawn out.

Example 7

500 g of cellulose diacetate fabric were dyed with 1% by weight acidic dye acid red CI. 57 · Composition of the liquor: methanol 100 parts by volume

Isopropanol 10 parts by volume • Perchlorethylene 890 parts by volume Total amount of the fleet: 40.5 1.

2 0 98 34/1142 originally inspected

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Dyeing was carried out under a pressure of 3 bar; Initial temperature 30 ° C; Temperature rise to 52 ° C. within 35 minutes low temperature was chosen with regard to the material to be dyed, which tends to deform when exposed to heat. Total duration of the dyeing process: 1 hour 20 minutes.

The start of the withdrawal of the liquid phase 35 ^m i ⁿ after the start of dyeing; Separation of the solvent by heating the withdrawn liquid phase to 80 ° C. and subsequent evaporation or relaxation under normal pressure. Amount of liquid recovered by condensing the vapors 2.20 after 10 min, 4.10 1 after 20 min and 8.80 1 at the end of the λ

Dyeing process.

Of the. Dye extraction was 24 % before the beginning of the liquid withdrawal and reached 100% at the end of the dyeing process.

The material was in a vivid red, washable and dyed lightfast color.

If the work was carried out under the same conditions, but without withdrawing liquid, the fleet only turned 2j? J ^ _Farbstof f _ aus.ge_zpg.eiij _t __ _ ". —.- ----- - - —— = · -

Example 8 ■

Two spools of textured yarn made of polyamide 6.6 were dyed, Total weight 1.5 kg, with 0.8 wt .- ^ o, based on the Textile weight, dispersion blue CI. 40. The dye was not blended and therefore insoluble in water.

Composition of the liquor: methanol 375 parts by volume

demineralized

Water .625 "· ■

Total volume of the fleet: 40 1.

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ORfQlNAt fhiSPECTEO

The dyeing was carried out under a pressure of 4 bar absolute; Initial temperature 22 ° C; Temperature rise to 80 ° G within 4-5 min; Total duration of the dyeing process 2 h; begin the Liquid withdrawal 1 h after the start of dyeing; Separation of the Solvent from the withdrawn liquid fraction by evaporation under atmospheric pressure. ■.

- Volume of liquid recovered by condensing the vapors, 3.50 liters after 10 minutes, 8 liters after 30 minutes and 14-1 at the end of the staining process

The dye was completely exhausted. Example 9

• Two spools of wool with a total weight of 1.5 kg using the method according to the invention. equipped with a solution of 3,3 ', 4 -'- $ richlor- (2-sulfo-4-chlorophenoxy) -6-diphenylurea (Commercial product Mittin FF) in methanol and isopropanol, diluted with perchlorethylene.

Composition of the bath: methanol 100 parts by volume. "Isopropanol 10 parts by volume

Perchlorethylene 890 parts by volume

Total volume of the bath: 4-0.5 1 · ■ The treatments were carried out under a pressure of 4 bar absolute. Initial temperature 4-0 C; The solvent from the withdrawn liquid phase separation by evaporation under atmospheric pressure by condensing the vapors recovered liquid amount 6.80 1 by; "temperature rise to 1OQ ⁰ C in 30 min; total duration of treatment 1 h 20 min, the start of the removal of liquid 50 minutes after the start of treatment. 30 min and 1 9.50 at the end of treatment.

The insecticide was neither noticeable in the treatment bath the surface of the treated textile material. The treatment for Kottenecht equipment can also be carried out at the same time a dyeing process can be carried out.

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Example 10

100 g of polyester fabric were dyed with 0.3%, based on the weight of the fabric, of a ruby-red plastic-soluble, unblended and water-insoluble dye that did not contain a dispersant.

Composition of the bath: pyridine 100 YoI. Parts

Water 900 parts by volume total volume of the tape 1,500 1.

The treatment was carried out under a pressure of 3 bar. Initial temperature 40 ⁰ G; Temperature rise to 110 ^° C. in 30 min; Total duration of the process 1 hour 45 minutes after the start of dyeing. The solvent was separated from the withdrawn liquid phase by evaporation under atmospheric pressure. Amount of liquid recovered 0.30 1. The dye bath has been completely depleted. ''

The fabric was completely uniform and strong colored ruby red; the color was lightfast and washable.

72XXIV claims

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Claims (6)

Claims 1. Modification of the process for dyeing textiles in the fiber by drawing out the dye from a Liquor containing a polar solvent for the dye and a non-polar diluent in which the dye is insoluble or only very soluble, the solvent from the liquor in liquid Phase or vapor phase is withdrawn and, if necessary, the diluent is returned to the liquor, according to main patent 2 021 110 (P 20 21 110.3), characterized in that instead of the combination polar solvent and non-polar diluent the combination of non-polar solvent and polar diluent, polar solvent and polar diluent or non-polar solvent and non-polar diluent used. 2. Modification of the method of the main patent according to claim 1, characterized in that one under increased or reduced pressure from boiling The liquor is colored and the solvent is drawn off in the vapor phase. 209834/1142 ORiQ / fNJAL INSPECTED ir 3. Modification of the process of the main patent according to. Claim 1, characterized in that one colors at atmospheric pressure or under reduced pressure, the liquor keeps below its boiling point and part of the liquid phase containing the mixture of solvent and diluent) withdraws, the solvent is separated off and the diluent is fed back into the liquor. 4. Modification of the method of the main patent according to i claim 3 ,. characterized in that the solvent is separated off from the withdrawn liquid phase by means of flash evaporation, 5. Modification of the process of the main patent according to Claim 3, characterized in that the solvent can be used in any other way than flash evaporation, in particular by crystallization, azeotropic distillation with a third substance, selective absorption or passing it through a semipermeable membrane from the withdrawn liquid phase. 6. "Application of the procedure according to the main patent and" according to claim 1 to 5 for dyeing »optionally and / or for finishing or finishing non-basic natural, artificial or synthetic textile fibers. . 209834 / 1U2 ORIGINAL INSPECTED