DE2914260A1 - Textile dyeing and printing comprising dye re-oxidn. - in aq. bath contg. soluble vanadate, tungstate or molybdate accelerator and peroxide - Google Patents

Abstract

In dyeing and printing textiles with S-, S vat- and vat dyes, by applying the dye in reduced form on textile and treating the textile in an aq. bath contg. H2O2, peroxydisulphuric acid or peroxydisulphate and an accelerator, to re-oxidate the dye, the accelerator consists of 0.1-0.2 g/l soluble vanadate (prefd.), tungstenate or molybdate. The textiles include polyamide, modified acrylic but esp. cellulose and cellulose fibre blends. Re-oxidn. time and temp. are reduced. Fastness of dyeing is improved, e.g. by comparison with re-oxidn. using H2O2 and Cu salts. Over-dosage leading to "bronzing" is minimised. No H2O2-stabilisers are needed.

Description

Process for coloring and printing textile materials

with sulfur, sulfur pebbles or vat dyes. The invention relates to a process for dyeing and printing textile materials with sulfur, Sulfur vats or vat dyes, the textile material after dyeing or the printing process is treated with an aqueous hydrogen peroxide solution, the catalytic amounts of the alkali, ammonium or alkylammonium salts of the vanadium, Contains molybdiic or tungstic acid.

Sulfur, sulfur vat and vat dyes are used in reduced, soluble form applied to the substrates to be colored or printed. Then the painted or printed substrate must be treated with an oxidizing agent treated to restore the reduced dye to the original, water-insoluble convert back oxidized form. Carrying out the reoxidation is crucial for the nuance and above all for the light gliding, especially for the wet and the rubbing fastness of the dyeings and prints. The ones used for reoxidation Oxidizing agents are alkali dichromate acetic acid, hydrogen peroxide and the like Per connections, e.g.

Sodium perborate, sodium percarbonate or ammonium peroxydisulfate, furthermore Sodium hypochlorite, alkali chlorites and alkali bromites, alkali iodate and sodium tetrathionate. In the case of stacked items in particular, it is also common practice to only rinse the staining complete, with the oxygen in the air reoxidation during this operation causes.

The previous oxidation processes have various disadvantages. In the case of oxidation with bichromate tacetic acid, bichromate / copper sulphate, one must very much often accept clouding of the color tone. Furthermore has the oxidation process with bichromate in addition to the water repellency that occurs with a number of dyes The main disadvantage of the colored materials is that the waste water become contaminated with toxic Cr-VI compounds, making these very common Oxidation method carried out on a large scale, increasingly due to legal wastewater requirements is restricted or ceases to exist. The use of alkali hypochlorite as Oxidizing agents are dyes because of the insufficient chlorine fastness of sulfur associated with problems because the dosage of the oxidizing agent is very precise need. The Sinwendullg the Alkalichlorite is to the observance of certain oxidation temperatures bound. isesollders in the continuous dyeing process can therefore be too technical riiclit easily solvable problems come. Not achieved with the alkali bromites Often there is no complete oxidation and the wet fastness properties of the dyeings obtained stand noticeably behind the colorations produced by oxidation with bichromate return. Alkali iodates give good oxidation effects with wash fastness in the acidic range, as can also be obtained by oxidation with bichromate. The usage of However, like the oxidation with sodium tetrathionate, alkali iodate is too expensive. The oxidation by atmospheric oxygen by "hanging" the goods or equivalent Extensive rinsing processes are relatively slow or require a lot of water connected, and also the oxidation process is under these conditions in vat dyes incomplete. In the case of an oxidation with alkali nitrite it can become acidic form unwanted nitrous gases. When using: hydrogen peroxide is produced no toxic reaction products, but the rate of oxidation is good for that most sulfur dyes insufficient. In particular the brown, red and maroon Sulfur dyes can only be insufficiently oxidized with hydrogen peroxide.

To overcome this problem it is known (US-PS 4,036,586), add water-soluble copper salts to the oxidation bath containing hydrogen peroxide. However, many 4th water regulations contain restrictions for soluble copper compounds Provisions. Also, when using copper salts, there must be a certain cloudiness of the shade can be expected. There is also some of the copper cations from the fiber is bound by secondary valences, there is a deterioration in the wet fastness properties the dyeings, especially the peroxide wash fastness. Because copper ions cause decay catalyze the hydrogen peroxide, stabilizers for the hydrogen peroxide must be added be admitted.

It is also known (US-PS 3,278,254) containing hydrogen peroxide Oxidation bath acetates, chlorides and nitrates of magnesium; Calcium, strontium and Add barium and magnesium sulfate in amounts of 0.5 to 7%. Disadvantages This method is that the dyeings can have a red tint and in the case of calcium and magnesium salts, the water hardness is increased. There Sulphate ions are often present in the dye baths when using Calcium, rtrontium and barium salts lead to unwanted precipitation of poorly soluble Sulfates. By increasing the hardness of the water and / or precipitating heavy soluble sulfates, the rubbing fastness of the dyeings is reduced.

It has now been found that acidic hydrogen peroxide is contained Solutions are then excellent for the reoxidation of reduced sulfur, sulfur vat and vat dye are suitable if the solutions contain soluble salts of the vanadium, tungsten and molybdenum acid in catalytic amounts.

The invention relates to an experienced dyeing and printing textile materials with sulfur, sulfur vat and vat dyes, the dye in reduced Form applied to the textile material and the textile material for reoxidation of the dye is treated in a bath, the hydrogen peroxide, peroxydisulfuric acid or contains peroxydisulfate and an accelerator. The inventive procedure is characterized in that a soluble salt of the vanadium, Tungstic or molybdic acid is used. Soluble salts of vanadic acid are made especially preferred. Soluble salts of tungstic acid are also preferred.

Usually the hydrogen peroxide comes in the form of a commercial one 30 to 35% aqueous solution in amounts of 1 to 5 ml / l, preferably 1 to 3 ml / l, added to the reoxidation bath. The reoxidation takes place at a y value less than 7, preferably at pEI values of 3 to 6, at temperatures of 15 to 700C, preferably from 30 to 400C. Be used to adjust the pH mainly carboxylic acids, especially formic, acetic and propionic acids are used.

Instead of hydrogen peroxide, a solution of peroxydisulfuric acid can also be used or a peroxydisulfate can be used. In particular, the peroxydisulfate solution is used a solution of ammonium peroxydisulfate into consideration. Peroxydisulfuric acid or the peroxydisulfate is used in amounts of 1 to 12 g / l, preferably 1 to 3 g / l.

A soluble salt of the vanadium-tungsten or molybdic acid or a mixture of such salts. Normally it is sufficient to add 0.1 to 0.2 g / l of such a salt or salt mixture. The vanadic, tungstic and molybdic acids can be in different forms as so-called Polyacids occur, of which salts also exist. For example, orthovanadates, Divanadate, Tetravanadate and Pentavanadate are known. Similar are monotungstates, Hexa-tungstates, paratungstates, and metatungstates are known. The designations are however not always used in a uniform manner. Which of the various aforementioned Forms of vanadium, tungsten or molybdic acid in salt form in the reoxidation bath is added, is irrelevant, since in the re-oxidation bath after the existing pH value forms the most stable form of the polyacids in each case. Suitable salts are e.g. the alkali salts (lithium, sodium, potassium, rubidium, cesium salts), furthermore the Ammonium and alkylammonium salts, provided the solubility of the salt used is so great that it is in the reoxidation bath at the concentration used completely dissolves. The sodium salts, especially the sodium salts of vanadic acid, are preferred. Sodium tungstate (Na2W04) and ammonium tungstate, for example, are suitable ((NH4) 2Mo04), sodium molybdate (Na2MoO4), sodium paratungstate (Na10W12O41), sodium orthovandate (Na3VO4), sodium pyrovanadate (Na4V207), but preferably sodium metavanadate (NaVO3). The salts can also be added to the reoxidation bath together with others Auxiliaries, such as oxidation-stable dispersants, can be added.

ie acceleration of the oxidation process among those according to the invention Conditions is great. As a rule, a color change occurs after 10 to 20 seconds observed from the reduced to the oxidized form of the dye, so that Yur Generation of level colorations in normal color strength and times for the Sent oxidation from 30 to 60 S @ customers are possible.

: In the process according to the invention, all fibers can be dyed and are printed, if they are usually with sulfur, sulfur vat or Dye vat dyes or have them printed, so z.n. Modified polyamide fibers Acrylic fibers, but especially cellulose fibers or cellulose fiber-containing mixtures. The process according to the invention can be used both for dyeing piece goods and yarns and loose material as well as for printing piece goods according to discontinuous, semi-continuous and continuous dyeing process can be used. The dyes are like Usually reduced and applied in reduced form to the textile material. at Sulfur dyes can be used instead of the usual reducing agents sodium sulfide and sodium hydrogen sulfide in the context of the present invention also other reducing agents are used for the reduction of the dyes, for example sodium hydroxide / glucose, Sodium hydroxide / hydrosulphite or sodium hydroxide / hydrosulphitaldehyde compounds, such as sodium formaldehyde sulfoxylate.

The method according to the invention can be discontinuous or preferably be carried out continuously. In the case of a discontinuous dyeing process, e.g. in apparatus dyeing, dyeing in cinern @igger, a reel vat, a Jet or the like. The dyed textile material is then used in the dyeing process Rücko =; ydation according to the invention with hydrogen peroxide in the presence of a soluble Subject to the salt of vanadium, tungsten or molybdic acid. With the preferred continuous dyeing process, a distinction is made between win- and double-bath processes. at In the one-bath process, the padding liquor contains the reduced dye, in the two-bath process the first pad bath contains the dispersed and dissolved dye, and the second The required reducing agent is then available in the pad bath. Both in the single bath as well as with two-bath continuous processing, the dyed goods are first rinsed and then subjected to the reoxidation according to the invention. In any case the goods are rinsed after the reoxidation according to the invention and finished as usual.

The process according to the invention can be carried out with sulfur, sulfur vat, Vat dyes, but preferably with soluble and insoluble sulfur dyes be performed. More aromatic, more nitrogen-containing due to sulfur melt Compounds with elemental sulfur or more aromatic through sulfuric boiling melt Compounds with polysulfides and aliphatic alcohols and / or water is obtained one insoluble sulfur dyes, the structure of which is not precisely known in detail is. The insoluble sulfur dyes can be soluble in water with sulfite or bisulfite Sulfur dyes, that is, in the water-soluble derivatives of thiosulfuric acid or their sodium salts, the so-called Buntesalzen, are transferred.

In addition to the water-soluble and water-insoluble sulfur dyes There are also preparations of sulfur dyes on the market that already have the contain the amount of reducing agent necessary for dyeing. All known modifications the Sulfur dyes can be used for the process according to the invention. Suitable Sulfur dyes are, for example, the following: C.I. Sulphur Blue 1, C.I. Leuco Sulfur Blue 1, C.I. Sulfur Blue 3, C.I. Leuco Sulfur Blue 3, C.I. Sulfur Blue 4, C.I. Solubilized Sulfur Blue 4, C.I. Sulfur Blue 5, C.I. Leuco Sulfur Blue 5, C.I. Solubilized Sulfur Blue 5, C.I. Sulfur Blue 7, C.I. Leuco Sulfur Blue 7, C.I. Solubilized Sulfur Bluc 7, C.I. Sulfur Blue 10, C.I. Solubiliscd Sulfur Blue 10, C.I. Sulfur Blue 15, C.I. Leuco Sulfur Blue 15, C.I. Solubilized Sulfur Blue 15, C.I. Sulfur Yellow 2, C.I. Leuco Sulfur Yellow 2, C.I.

Solubilized Sulfur Yellow 2, C.L. Sulfur Yellow 4, C.I.

Leuco Sulfur Yellow 4, C.I. Solubilized Sulfur Yellow 4, C.I. Leuco Sulfur Yellow 7, C. Ie Sulfur Yellow 9, C.I.

Leuco Sulfur Yellow 9, C.I. Sulfur Green 2, C.I. Leuco Sulfur Green 2, C.I. Solubilized Sulfur Green 2, C.I.

Sulfur Green 3, C.I. Leuco Sulfur Green 3, C.I. Solubilized Sulfur Green 3, C.I. Sulfur Green 5, C.I. Sulfur Brown 5, C.I. Leuco Sulfur Brown 5, C.I. Solubilized Sulfur Brown 5, C.I. Sulfur Brown 10, C.I. Leuco Sulfur Brown 10, C.I. Sulfur Brown 16, C.I. Solubilized Sulfur Brown 16, C.I. Sulfur Brown 5t, C.I. Solubilized Sulfur Brown 51, C.I. Sulfur Black 8, C.I. Sulfur Red 3, C.I.

SolubiliscSulphur Red 3, C.I. Sulfur Red 7, C.I. Solubilized Sulfur Red 7.

Sulfur vat dyes suitable for the process according to the invention are e.g. C.I. Vat Blue 42, C.I. Reduced Vat Blue 42, C.I. Vat Blue 43, C.I. Reduced Vat Blue 43, C.I. Vat Blue 14, C.I. Vat Blue 45, C.I. Vat Blue 47, C.I. Vat Blue 49, C.I. Vat Blue 50, C.I. Sulfur Black 10, C.I. Leuco Sulfur Black 10.

The method according to the invention is simple, safe and quick to carry out. Above all, there is a significant reduction in the time for reoxidation and thus also the time for the entire process and a lowering of the temperature for determine the reoxidation. In addition to the energy savings resulting from the lowering of the temperature faces the well-known reoxidation with hydrogen peroxide in the alkaline pH range or against reoxidation with hydrogen peroxide a significant improvement in the fastness properties in the presence of copper salts of the colorations obtained. The dangers of overdosing and thus bronzing the coloration is extremely slight. The addition of stabilizers for the hydrogen peroxide not necessary.

Example 1 5 g hydrosol light brown GGL (C. I. Solubilized Sulfur Brown 51, C.I. 53 32S), 34 g sodium hydrogen sulfide (30% NaHS) and 15 g soda dissolved in water and made up to a volume of 1000 ml with water. In this A cotton twill is padded with a liquor pick-up of approx. 80% Steamed for 1 minute at 102 to 1050C. It is then rinsed and then in a 400 ml liquor containing 3 ml / l hydrogen peroxide 30%, 4 ml / l acetic acid 60% and 0.2 g / l sodium metavanadate and has a pH of 4-5, 30 seconds oxidized at 400C. Then it is rinsed and finished.

The dyeing process corresponds to a continuous manufacturing process, in which, depending on the speed of the goods, very short oxidation times (approx. 30 to 60 seconds) are the rule. By adding sodium metavanadate the oxidation is greatly accelerated so that a color change occurs after just 15 seconds takes place from the reduced to the oxidized form of the dye. You get one level dyeing in normal color strength with fastness properties like after oxidation with Na dichromate. The oxidation with hydrogen peroxide in the acidic range without additives of sodium netavanadate, sodium molybdate or sodium tungstate is for continuous Only partially suitable for coloring, as the oxidation process of most sulfur dyes runs too slowly.

Example 2 to 4 The dye listed under 2 to 4 were after dyed using the same procedure as in example 1: 2. 50 g / l hydrosol light olive BBN (Solubilized Sulfur Green 9, C.I. 53006) 3. 50 g / l hydrosol light brown; 3T (Solubil i sed Sulfur Brown 16, C.I. 53 286) 4. 50 g / l Hydrosol Yellow 3RT (Solubilised Sulfur Brown 21, C.I. 53 066) In all cases, colorations were obtained which are similar to those in The depth of color and the fastness properties corresponded to the colorations as they were after oxidation Sodium dichromate can be obtained.

Example 5 50 g Immedial-Lichtbordo 3BL (C.I. Sulfur Red 7, C.I.

53 810) are mixed with 25 g of sodium sulfide (60% technical @@ ukt) dissolved in @ a @ ser and made up to a volume of 100 ml with water. In this A cotton fabric is padded and steamed at 102 to 105 ° C. for 1 minute. It is then rinsed and then in a liquor of 400 ml, the 3 ml / l hydrogen peroxide Contains 30%, 4 ml / l acetic acid 60 ¼, 0.2 g / l sodium metavanadate and has a rapid pH value of 4-5, oxidized for 30 seconds at 40 ° C.

It is then rinsed and dried.

1) the dye is difficult to oxidize and is readily available standing time at 400C without addition of sodium metavanadate not sufficiently oxidized, so that a coloring of less depth of color results. The addition of sodium metavanadate causes a normal color yield with good egalitlite with normal fastness properties.

Example 6 50 g Hydrosol-Licht @ raun uSL (C.I. Solubilized Sulfur Brown 51, C.I. 53 328), 34 g of sodium hydrogen sulfide (30% sodium sulfhydrate solution) and 15 g of soda are dissolved in water and made up to a volume of 1000 ml with water. In this liquor, a cotton twill is padded with a liquor pick-up of approx. 80% and steamed for one minute at 102 to 1050C.

It is then rinsed and then in a liquor of 400 ml, the 3 g / l ammonium peroxydisulfate, 4 ml / l acetic acid 60% and 0.2 contains g / l sodium metavanadate and has a pH of 3 to 4, 30 seconds oxidized at 400C.

Then it is rinsed and finished.

It becomes a dyeing with normal color yield and normal fastness properties obtain.

Claims (10)

PATENT CLAIMS 1. Process for dyeing and printing textile materials with sulfur, sulfur vat and vat dyes, with the dye in reduced Form applied to the textile material and the textile material for reoxidation of the dye is treated in a bath, the hydrogen peroxide or peroxydisulfuric acid or contains peroxydisulfate and an accelerator, characterized in that a soluble salt of vanadium, tungsten or molybdic acid is used as an accelerator will. 2. The method according to claim 1, characterized in that a soluble Vanadic acid salt is used. 3. The method according to claim 1, characterized in that a soluble Tungstic acid salt is used. 4. The method according to claims 1 to 3, characterized in that that the reoxidation is carried out at pfI values below 7. 5. The method according to claims 1 to 4, characterized gekennzeichnot, that the reoxidation is carried out at pIl values of 3 to 6. 6. The method according to claims 1 to 5, characterized in that that reoxidation is carried out at temperatures of 20 to 70 ° C. 7. The method according to claims 1 to 6, characterized in that that the reoxidation is carried out at temperatures of 30 to 400C. 8. The method according to claims 1 to 7, characterized in that that the accelerator is added to the reoxidation bath in amounts of 0.1 to 0.2 g / l will. 9. The method according to claims 1 to 8, characterized gekennzeichnot, that it is carried out continuously. 10. The method according to claims 1 to 9, characterized in that that the accelerator together with an oxidation-stable dispersant dem Oxidation bath is added.