DE2434095A1 - Oxidn. of sulphur dyes on cellulose fibres - using oxygen-contg. gas and opt. substd. 1-3 ring quinones as catalysts - Google Patents

Abstract

Cellulose textiles dyed or printed with sulphur dyes are oxidised by oxygen-contg. gas in presence of catalysts consisting of 1-3 ring quinones and/or their leuco forms, which may be substd. by one or two methyl, ethyl or Cl gps., and by one or two anionic salt-forming gps. Poor wash fastness caused by oxidn. with H2O2 is avoided. The treatment does not cause dulling of the shades, hardening of the textiles by metal residues, hydrophobic effects of effluent problems, as occurs with bichromate or bichromate/copper sulphate treatments.

Description

Oxidative aftertreatment of mft sulfur dyes colored resp. printed cellulosic textile materials. The present invention relates to: fft a process for the oxidative aftertreatment of dyed with sulfur dyes respectively.

printed cellulosic textile materials in which the oxidation with oxygen or (in an oxygen-containing gas in the presence of oxidation catalysts is carried out and wherein as Oxydationskatalysatoj mononuclear to trinuclear quinene and / or their leukofo-m, which are mono- or twofold by methyl, ethyl or chlorine and independently substituted by one or two anionic salt-forming groups can be, as well as preparations which are particularly advantageous for carrying out the process the catalysts to be used according to the invention.

Dyeings or prints with sulphurous dyes are done after mounting of the dye and subsequent rinsing for the final fixation of the dye oxidized. It is assumed that the mercapto groups here are zl disulfide groups are oxidized. In the case of chironimine dyes, the leuco compound is also used converted into the quinonimine group by oxidation, similar to the Eüpen dyes. The common oxidizing agents are alkali dichromate / acetic acid, Hydrogen peroxide and peroxide compounds such as sodium perborate or sodium percarbonate.

Recently proposed oxidizing agents are: sodium bromite, Potassium iodate, sodium tetrathionate, ammonium persulfate and other compounds. In particular In the case of stackable items, it is also common practice to only finish the coloring by rinsing. In this case, the oxygen in the air acts as an oxidizing agent.

Oxidation with the chemicals mentioned has various disadvantages, in particular, water-off peroxide and its derivatives reduce in most cases - l the washfastness of the dyeings is clear. It is assumed that this is the process of oxidation does not stop at the disulfide mare, but until sulfonate groups are formed, which make the dye more soluble and cause poorer wet fastness, goes on. In other cases, especially in the case of green coloring, the B-> treatment with hydrogen peroxide or perborate the color tone is much more bluish, emptier and weaker. When working with bichromate or bichromate / copper sulfate, there are two In general, there is no deterioration in the fastness to washing, but you have to accept a considerable clouding of the color tone. In addition, through the metal salt residue hardens the textile material, so that difficulties are encountered when sewing may occur. Another disadvantage is the occurrence of hydrophobic effects, whereby difficulties arise in the finishing and other post-treatments. The use of metal salts is also undesirable in terms of wastewater.

The oxidation of dyeings and prints with air, i. H. with the oxygen the air is cheap and completely problem-free in view of the sewage; Unfortunately the oxidation process may take several days and weeks. This makes through a relocation, d. H. by changing the hue, clarity and the color strength of the coloration is also noticeable.

It has now been found that there is a considerable improvement in the oxidation can be achieved if the dyeings and prints, ideally after rinsing, with Treated oxidation catalysts and simultaneously or subsequently oxygen or an oxygen-containing gas, such as. B. allows air to act as oxidation catalysts for the oxidative post-treatment of those dyed or printed with sulfur dyes ceilulose-containing textile materials with oxygen or an oxygen-containing one Gas, according to the invention, mononuclear to trinuclear quinones and / or their leuco forms, one or two times by methyl, ethyl or chlorine and independently of them by one or two anionic salt-forming groups can be substituted, are used. Anionic salt-forming groups are, for example, the carboxyl group and the sulfonic acid group or the thiosulfonic acid group. The oxidation catalysts according to the invention preferably contain as anionic salt-forming groups sulfonic or thiosulfonic acid groups.

Examples of one- to three-ring quinones, which as such or their According to the invention, leuco forms can be used as oxidation catalysts are: p-Benzoquinone, p-Benzo ch inonsulfonsalee, 1,4-NapNthoquinone, 1,4-Naphthoquinone-2-sulfonic acid, 1,4-naphthoquinone-2-thiosulfonic acid, 2,3-dichloro-1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone disulfonic acid, Anthraquinone (lS4) anthraquinone (9, 10), 2-ethyl-9,10-anthraquinone, 9,10-anthraquinone-2-sulfonic acid, Acenaphthenquinone, acenaphthencainone-5-sulfonic acid, benzoehinonecarboxylic acid, phenanthrenequinone, Phenanthrenequinone-3-sulfonic acid, phenanthrenequinone-2-sulfonic acid, phenanthrenequinone-5-thiosulfonic acid.

Oxidation catalysts have particular application advantages Naphthoquinone-1,4), acenaphthenquinone or phenanthrenequinone, the single or double by chlorine and independently of it by one or two sulfonic or thiosulfonic acid groups can be substituted, in particular the leuco forms of these quinones. The unsubstituted naphthoquinone- (i, 4), acenaphthenquinone are particularly preferred or phenanthrenequinone and in particular their leuco forms.

The quinones used according to the invention as oxidation catalysts have long been known and some are commercial products. The leuco forms of these quinones used according to the invention, preferably as oxidation catalysts, can be obtained in a simple manner by the action of reducing agents on the quinones mentioned reducing medium, such as. B. a reducing agent en-containing dye liquor are soaked. The leuco forms of quinones which are substituted by chlorine sulfo or thiosulfo groups. can also by adding, hinone will be obtained.

Applying the oxidation catalysts to the ones to be oxidized Materials are generally made by treating these materials with? Katalyaüorflotten ' the catalysts to be used according to the invention in a suitable liquid, preferably dissolved or dispersed in water. It is also possible that Adding an oxidation catalyst to the dye liquor or a sulfur dye for dyeing to use, which contains the oxidation catalyst. In this case, the Operation of the aftertreatment of the dyeing with the catalyst liquor. Preferential rate However, the oxidation catalysts are in the form of aqueous solutions after dyeing applied. aqueous solutions containing sulfonic acid or thiosulfonic acid group Quinones or their leuco compounds can be obtained by the Dissolves compounds in an equivalent amount of an aqueous, inorganic base.

Aqueous solutions of the leuco compounds of quinones can be obtained be by placing them in an aqueous solution of a preferably inorganic Base dissolving or by placing the corresponding quinones in an aqueous medium in the presence one inorganic base reduced to the leuco form; The manufacture of the catalyst liquors by reducing the quinones is expediently carried out in such a way that the required Amount of the quinone with the 2 to 50 equivalents, preferably 5 to 25 equivalents of reducing agent and 4 to 60 equivalents, preferably 10 to 30 equivalents Alkali in water at 50 to 100 ° C, preferably at 40 to 80 ° C in per se known Way converted into the leuco form, whereby the amounts of quinone and water are measured be that the resulting liquors 0.001 to 3.2 percent by weight, preferably Contain 0.002 to 0.1 percent by weight of the oxidation catalysts.

The inorganic base is preferably alkali metal hydroxides, such as. ü. Sodium or potassium hydroxide used.

When using easily reducible quinones, especially if the quinone Contains anionic salt-forming groups, alkali carbonates, such as. B. Soda or potash can be used as a base.

Inorganic reducing agents 31 are preferably sodium dithionite, Sodium sulfoxylate "ormaldchyd- or acetaldehyde adducts or complex alkali hydrides, such as B. sodium boronate is used.

There is one possible embodiment of the method according to the invention in that the dyed textiles in a liquor containing the catalyst 1lm pulled, d. h repeated through the catalyst liquor and through air space be guided. However, it is also possible to first immerse the textiles, Impregnate padding, paddling or spraying with the catalyst liquor, if necessary Squeeze to a certain degree of the liquor uptake and then to bring into contact with an oxygen-containing gas, preferably with air. The oxidative aftertreatment can be carried out at temperatures between 25 and 1300C be0 The oxygen-containing gas used for the oxidation can be heated or combined can be used with wet or high pressure steam.

To simplify the preparation of the catalyst liquors, it is expedient to Use preparations which contain the oxidation catalysts to be used according to the invention Contained as active ingredients and which are soluble in water or dilute aqueous bases or can be diluted with water. Preference is given to those preparations which are used as active ingredients Ohinones containing sulfonic acid or thiosulfonic acid groups, but in particular those which have the leuco forms of the above-mentioned substituted or unsubstituted Contain quinones. In addition to the active ingredients, the preparations preferably contain one inorganic reducing agent and optionally also a preferably inorganic reducing agent Base "The task of reducing agents is to counteract the action of the leuco compounds to stabilize the oxygen in the air. Based on i mole of the oxidation catalyst the preparations contain 2 to 50, preferably 5 to 25 equivalents of the reducing agent and optionally 4 to 60, preferably 10 to 30 equivalents of the base.

Also in the preparation of the catalyst preparations are used as inorganic base, preferably alkali hydroxides, such as

Sodium or potassium hydroxide is used.

The oxidation catalyst used contains anionic salt-forming Groups, so could also alkali carbonates, such as.

B. soda or potash can be used as a base.

The preferred inorganic reducing agents are sodium dithionite, Sodium sulfoxylate formaldehyde or acetaldehyde adducts or complex alkali hycrides, such as 13. Sodium borate used.

Preferred catalyst preparations consist of an inorganic one Reducing agent, optionally an inorganic base and the Leukofcrm one mononuclear to trinuclear quinones, preferably 1,4-naphthoquinone of acenaphthenquinone or of phenanthrenequinone1 which is once or twice by methyl, ethyl or chlorine, preferably by chlorine and additionally by one or two anionic salt-forming Groups, preferably one or two sulfonic or thiosulfonic acid groups substituted can be. Oxidation catalysts are used with particular advantage the leuco form of naphthoquinone (1,4), A.cenaphthenchinons or phenanthrenequinones contain.

It is also possible to use one of the above instead of the leuco form Quinones a quinone substituted by a sulfonic acid or thiosulfonic acid group to use for the production of preferred catalyst preparations.

Solid, powdery catalyst preparations are preferably free of inorganic bases and can be obtained by mixing the solid components will. The leuco compounds are preferably in the form of the free leuco acid used; However, they can also be in the form of their salts, preferably their alkali, such as B. sodium or potassium salts are present, quinones and / or their leuco compounds used which contain sulfonic or thiosulfonic acid groups in the molecule, so can the anionic salt-forming groups also in the form of salts or acids are present. Such solid preparations give when dissolved in dilute aqueous Bases, if necessary under fJhreu and heating the ready-to-use catalyst liquors.

It is particularly useful for technical use, highly concentrated to use aqueous preparations of the leuco forms of the quinones mentioned, these can can be obtained in that the quinones themselves in the smallest possible amount of water in the presence of an excess of one of the abovementioned bases with an excess one of the above-mentioned reducing agents at 20 to 1000C, expediently below Air exclusion can be reduced to the leuco form, with the excess of the reducing agent for the stabilization of the leuco compounds obtained against the action of the Oxygen from the air ensures that the preparation is stored The amount of water is such that the quinone can be reduced without difficulty takes place when stirring or mixing the reaction mixture. For the special simple Applying the preparation, it may be useful to use enough water that after the reduction all components of the preparation are completely dissolved.

However, you can also use less water, in which case if necessary after the reaction mixture has cooled down, some or all of the components crystallize.

The aqueous preparations deliver when simply diluted with water Catalyst liquors for use according to the invention.

The aqueous catalyst preparations are more convenient to use than the solid powdery; however, the solid preparations can be stored for a longer period of time.

Example 1 10 g of cotton yarn are in a dye bath which is in 200 ccm of water, 0.3 g of hydroxyl blue R powder (C. 1. Vat Blue No. 43), 1.2 ml of 32.5 percent by weight Contains sodium hydroxide solution and 0.8 g of sodium dithionite, for 45 minutes at 600C in the usual way Wise colored and then rinsed clear. Then the coloring is carried out in a catalyst liquor, which was obtained as described below, for 15 minutes-at 700C so moved, that the dye comes into contact with air. It is then rinsed and dried. The catalytic oxidation effect can be recognized by the clearly clearer color compared to dyeings that are carried out in an analogous manner, but without using the inventive Oxidation catalyst have been treated or after rinsing for 15 Minutes have been imposed in the air.

To prepare the catalyst liquor, 200 ml of water, 0.04 g Phenanthrenequinone, 0.32 g of a 32% weight percent sodium hydroxide solution and 0.32 g Sodium dithionite is heated to 60 ° C with gentle stirring until the phenanthrenequinone is completely resolved. After cooling to 30 ° C., the catalyst liquor is ready for use.

Example 2 A cotton package weighing 600 g is in a Bath of 6000 ccm, the 36 g Indocarbon CL conc. (C. 1. Sulfur Black No. 11), 60 ml 32.5 percent strength by weight sodium hydroxide solution, 51 g sodium dithionite and 12 g sodium sulfate contains, colored in the usual way for 60 minutes at 650C and then treated with a catalyst liquor prepared as described below. To brief rinsing is oxidized by suction for 15 minutes. The color is oxidized significantly faster and more complete than a coloration that is not done with the catalyst liquor was treated. A liquor not treated according to the invention bronzes on drying and is therefore completely useless.

A similar acceleration of oxidation is achieved if one 0.12 g of phenanthrenequinone-3-sulfonic acid potassium is added to the dye liquor or if the used Indocarbon CL conc.

Contains 0.3% of the oxidation catalyst. In this way of working there is no post-treatment with the catalyst liquor.

To prepare the catalyst liquor, 1000 ml of water, 0.02 g phenanthrenchino'1-3-sutonic acid potassium, 1 ml of a 32.5 percent strength by weight sodium hydroxide solution and 1 g of sodium dithionite 5 minutes with gentle stirring to 3000 heated, Example 3 Cotton fabric is on the padder with a dye liquor that 100 g of hydrosol light yellow G (C.I. Sol. Sulfur Yellow 5) and 100 g of crystallized per liter Contains sodium sulphide, padded at 3000 and a liquor uptake of approx. 80%, steamed and rinsed air-free for 45 seconds at 110 ° C. The color is squeezed off and through a further padding passage with an aqueous catalyst liquor which contains 0.9 g of phenanthrene-3-sulfonic acid potassium per liter, with an additional Fleet uptake of approx. 10 padded and for 1 minute with a supply of air at 11,000 steamed and then rinsed.

The coloring is considerably greener than a coloring that is analogous Way, but without padding the catalyst liquor by steaming with air supply has been oxidized. It is color-stable, while one is not the oxidation catalyst according to the invention padded, reddish coloration in Lying in the air in the course of days becomes noticeably greener Example 4 Cotton fabric, according to the pad steaming process, analogous to Example 3, with a dye liquor which is in the Liter 30 g hydron blue R f. Sol, (o. I, Vat Blue No. 43), 45 ml 32, weight percent Contains sodium hydroxide solution and 40 g sodium dithionite, colored and then rinsed has been, after intensive squeezing with a catalyst liquor that through Dilute a concentrated prepared according to Example 5 Catalyst solution to 1295 times the volume was obtained, with an additional liquor uptake 10% padded at 250C and with air supply for 1 minute at 110 ° C steamed, rinsed and dried. A coloration is obtained that is consistent with the clarity comes close to oxidation with H202.

Dyeings that are carried out in the same way, but without using the inventive Oxidation catalyst have been treated or oxidized by hardening in the air are bronzed and considerably duller and change their hue strong in storage by post-oxidation.

Example 5 370 ml of water, 4 g of phenanthrenequinone, 32 g of 32.5 percent by weight Sodium hydroxide solution and 32 g of sodium dithionite are heated to 50 ° C. under a nitrogen atmosphere stirred until the phenanthrenequinone is completely dissolved. The solution thus obtained is a concentrated catalyst preparation.

Dilute this concentrated solution with water to the 10- bis 500 times the volume, a ready-to-use catalyst liquor is obtained which is used for Catalysis of the air oxidation of dyeings or prints with sulfur dyes is excellent suitable is. Concentrated catalyst preparations can be obtained in the same way if, instead of phenanthrenequinone, naphthoquinone- (1,4) or acenaphthenchinone begins.

Example 6 100 ml of water, 2 g of phenanthrenequinone-3-sulfonic acid potassium, 10 ml of a 32.5 percent strength by weight sodium hydroxide solution and 10 g Sodium Dithionite are heated to 35 ° C for 5 minutes under a nitrogen atmosphere ready-to-use catalyst liquor, this concentrated solution is diluted with water to 20 to 1000 times the volume. Concentrated catalyst preparations can be used in the same way be obtained if, instead of the phenanthrenequinone-3-sulfonic acid used in this example Potassium equal amounts of phenanthrenequinone-2-sulfonic acid potassium or acenaphthenchinone-5-sulfonic acid rem potassium is used.

Example 7 1000 ml of water, 0.02 g of 1,4-naphthoquinone-2-sulfonic acid Potassium, 1 ml of a 32.5 percent strength by weight sodium hydroxide solution and 1 g of sodium dithionite are heated to 35 ° C. for 5 minutes with gentle stirring. The catalyst liquor thus obtained is ready to use and catalyzes the air oxidation of dyeings or prints with sulfur dyes, in the same way catalyst liquors can be obtained, if instead of the i, 4-naphthoquinone-2-sulfonic acid used in this example Potassium equal amounts of 1,4-naphthoquinone-2-thiosulfonic acid sodium, i, 4-dihydroxynaphthalene-2-thiosulfonic acid Sodium, 2,3-dichloro-1,4-naphthoquinone sulfonic acid sodium, p-benzoquinone sulfonic acid Potassium sets in.

Example 8 20 g of phenanthrenequinone-3-sulfonic acid potassium are ground and intimately mixed with 200 g of sodium dithionite in dry form, for production ready-to-use catalyst liquors become 2 g of this powder in a mixture of 10 ml of a 3.5 weight percent sodium hydroxide solution and 500 bis Sprinkled in 5000 ml of water at 35 to 45 ° C.

Preparations of similar effectiveness can be obtained by taking instead of phenanthrene-3-sulfonic acid potassium otnaphthochinone-2-sulfonic acid potassium, p-benzoquinone-sulfonic acid potassium or the leuco form of phenanthrenequinone is used or instead of sodium dithionite, the aldehyde compounds of the alkali metal salts of sulfoxylic acid begins.

Claims (18)

Claims 1. Process for the oxidative aftertreatment of sulfur dyes dyed or printed cellulosic textile materials with oxygen or an oxygen-containing gas in the presence of oxidation catalysts, characterized in that that as an oxidation catalyst mononuclear to trinuclear quinones and / or their leuco form, the once or twice by methyl, ethyl or chlorine and that regardless of it can be substituted by one or two anionic salt-forming groups are used will. 2. The method according to claim 1, characterized in that the oxidation catalyst 1, 4-naphthoquinone, acenaphthoquinone or phenanthrenequinone and / or their leuco form, one or two times by chlorine and independently by one or two Sulphonic or thiosulphonic acid groups can be substituted, can be used. 3. The method according to claims i and 2, characterized in that that the leuco form of 1,4-naphthoquinone, acenaphthenquinone, is used as an oxidation catalyst or phenanthrenequinones, which are one or two times by chlorine and independently thereof be substituted by one or two sulfonic or thiosulfonic acid groups can be used. 4. The method according to de claims 1 to 3, characterized in that that the oxidation catalyst i, 4-naphthoquinone, acenaphthenquinone or phenanthrenequinone and / or their leuco forms are used. 5. The method according to claims 1 to 4, characterized in that that the leuco form of 1, 4-naphthoquinone is used as the oxidation catalyst will. 6. The method according to claims i to 4, characterized in that that the leuco form of acenaphthenquinone is used as the oxidation catalyst. 7. The method according to claims 1 to 4, characterized in that that the leuco form of phenanthrenequinone is used as the oxidation catalyst. 8. The method according to any one of claims 1 to 7, characterized in that that the textile materials dyed or printed with sulfur dyes a 0.001 to 0.2 weight percent aqueous solution of the oxidation catalyst treated and oxidized simultaneously or subsequently. 9. The method according to any one of claims 1 to 7, characterized in, that the oxidation catalyst is contained in the dye liquor and the resulting Staining is oxidized without further treatment. 10. Catalyst preparation for the oxidative aftertreatment of with Cellulosic textile materials dyed or printed with sulfur dyes with oxygen or an oxygen-containing gas, characterized in that they The active ingredient is the leuco form of a one- to three-ring quinone, one or two times by methyl, ethyl or chlorine and that independently of one or two anionic salt-forming groups can be substituted or a mononuclear to trinuclear group Quinone, which can be substituted one or two times by methyl, ethyl or chlorine can and solidly substituted by one or two anionic salt-forming groups, contains. 11. Catalyst preparation according to claim 10, characterized in that that they use the leuco form of 1, 4-naphthoquinone 'acenaphthenchinons as the active ingredient or phenanthrenequinones which are once or twice by chlorine and which are independent of it be substituted by one or two sulfonic or thiosulfonic acid groups can, contains, 12. Catalyst preparation according to claim 10, characterized in that that they are the active ingredient i, 4-naphthoquinone, acenaphthenquinone or phenantbrenchinone, which can be substituted one or two times by chlorine and by one or two sulfonic or thiosulfonic acid groups are substituted, contains. 13. Catalyst preparation according to claims 10 and ii, characterized characterized in that it is the leuco form of it4-naphthoquinone, des Contains aeenaphthenehinone or phenanthrenequinone, 14. Catalyst Preparation according to claims 10 and 122, characterized in that they contain 1> 4-naphthoquinone as active ingredient Acenaphthenchinon or Phenanthrenohinont which are replaced by one or two sulfonic or Thiosulfonic acid groups are substituted contains. 15. Catalyst preparation according to one of claims 10 to 14, characterized gekennzeiohnet that they contain 2 to 50 equivalents of an inorganic one per mole of the active ingredient Reducing agent and optionally 4 to 60 equivalents of an inorganic base contains. 16. Catalyst preparation according to claim 15, characterized in that that they are used as an inorganic reducing agent c sodium dithi / nit, sodium sulfoxylate-formaldehyde- respectively. Contains aoetaldehyde adducts or sodium boronate. 17. Catalyst preparation according to claim 15, characterized in that that they are the hydroxide or carbonate of sodium or potassium as the inorganic base contains. 18. Cellulosic products dyed or printed with sulphurous substances Textile materials are oxidized according to one of Claims 1 to 9.