DE1202245B - Process for coloring and padding structures made of hydrophobic materials - Google Patents

Description

Process for dyeing and padding structures made of hydrophobic materials It has been found that structures such as threads, fibers, films, tapes and the like made of hydrophobic materials such as aromatic polyesters, in particular polyethylene terephthalates, synthetic polyamides and polyurethanes, polyvinyl chlorides, polyacrylonitrile and the like Copolymers, cellulose esters and polyolefins, such as polyethylenes and polypropylenes, can produce valuable colorations if the structures to be colored are successively combined with azomethines of aromatic amines in any order. which have at least one solubilizing group in the remainder of the aldehyde component, and treated with a) quinones or b) N-haloquinonimines or N, N'-dihaloquinonediimines of preferably substituted quinones or e) with compounds which are in a carbocyclic ring the grouping contain, where X and Y mean carbon-carbon bonds, hydrogen or halogen.

Instead of components a), b) or e) it is also possible to use d) quinonanil-N-haloimides, optionally in a mixture with a), b) or c).

All of the above-mentioned new processes usually give dark-colored, in particular black, dyeings which are distinguished by good general fastness properties, in particular very good sublimation and lightfastness. The processes for dyeing aromatic polyesters (polyethylene terephthalate) are of particular interest. The azomethines to be used according to the process can be z. B. by condensation of the amines described below with the aldehydes mentioned below: 4 - amino - diphenylamine, 4-amino-4'-methoxy-diphenylamine, 1,8-diaminonaphthalene, benzidine, 4-aminonaphthalene-1,1'-azo -4'-aminobenzene, 3-methoxy-4-amino-diphenylamine, 4 - amino - 4'-naphthyl - diphenylamine, 4 - amino-4'-cyclohexyl-diphenylamine, 4-amino-4'-methyldiphenylamine, 2.4 -Diamino-diphenylamine, dianisidine, m-phenylenediamine, 4-amino-2-chloro-4 '- (N-dioxyethyl) - amino - 1, l'- azobenzene, 4 - benzoylamido-2,5 - dimethoxy - 1 - aminobenzene , furthermore the connections Aldehydes: o-benzaldehyde sulfonic acid, p-Benzaldchydsulfonsäure, m-benzaldehyde-sulphonic acid, o-, p-benzaldehyde-disulfonic acid or the corresponding carboxylic acid derivatives, further benzaldehyde - disulfimide and Naphthaldehydsulfonsäuren.

For further treatment of the hydrophobic materials are from the Class of compounds a) z. B. the following quinones are suitable: benzoquinone- (1,4), naphthoquinone- (1,4), 2,5-dichloro-benzoquinone- (1,4), 2,3,5,6-tetrachloro-benzoquinone- (1,4), 1,2-benzo- or. Naphthoquinone or derivatives thereof, 2,6-dichloro-benzoquinone, 2,3,6-trichloro-benzoquinone or the corresponding bromine derivatives, 2-phenyl-1,4-benzoquinone or its substitution products or any mixtures of these products.

As N-chloroquinone imines or N, N # -Dichloroquinonediimines (component b), which can be used in place of component a), can advantageously be used in addition to the unsubstituted chloroimines and those mono- or dichlorodiimines which are further substituted in the quinoid nucleus, e.g. B. by halogen, such as chlorine or bromine, alkyl or alkoxy groups. Particularly suitable components b) are, for example, 2,6-dichloro-4-mono- or 1,4-dichloroimino-benzoquinones of the formula (X = 0 or # N - CI), furthermore 2,5-dichloro-N, N ' - dichloro - p - benzoquinone diimine, 2 - methyl-N, N'-dichloro-p-benzoquinone diimine or naphthoquinone-1,4- dichlorodiimin.

Mixtures of such N-haloimines can also be used with good success of the quinones or mixtures of such compounds with optionally substituted ones Use benzo- or naphthoquinones [component a)].

Suitable compounds of group c) which can be used in place of or in some cases also as a mixture with compounds of groups a) and b) . are inter alia cyclohexenone, cyclohexandienone, heptachlorocyclohexenone, pentachlorotetralone, hexachlorocyclohexadienone.

Compounds d) that can be used include: quinonanil-N-chloro- or bromamide or 2,5-dichloroquinonanil-N-chlorimide.

The processes using components a), b), c) and d) are carried out in detail in such a way that the azomethines of the specified composition and the compounds a), b), c) and d) act on the materials to be treated , e.g. B. fibers or fabrics, from neutral, acidic or alkaline aqueous suspensions or solutions can be applied successively in any order, preferably using dispersants or emulsifiers, from a dyebath or a padding liquor. Depending on the type of material to be dyed, the components are applied to the material at room temperature or at an elevated temperature and the temperature is increased in the course of the dyeing process, the optimum temperature being up to WO'C. At temperatures up to 100 ° C. it is sometimes advantageous to add common carrier substances, such as trichlorobenzene, diphenyl, diphenyl ether or esters of aromatic carboxylic acids, to the dyebath. One proceeds, for example, that the material to be colored, for. B- fabrics or fibers made of polyethylene terephthalate, first introduced into a dye bath at room temperature - or treated with a padding liquor which, in addition to azomethines of the type indicated, contain emulsifiers or dispersants and possibly reducing substances; treatment is then carried out with a slow increase in temperature, depending on the type of material to be treated, preferably to 70 to WO'C until a sufficient amount is absorbed. The dyeing process is expediently interrupted at this stage, the treated material is rinsed, optionally dried and then placed in a fresh bath which contains components a), b), c) or d) in the form of an aqueous solution or dispersion. This second bath is entered at room temperature or at a slightly elevated temperature and the color is dyed until the optimum depth of color has been achieved, if appropriate with an increase in temperature up to, for example, WO'C. The components can sometimes be applied in reverse order, with good results, by applying suitable components a), b), c) or d) or mixtures of such compounds from a dye bath or on a padding device to the material to be treated, the temperature depending depending on the type of material and the starting component used - increases to up to 140 ° C, the treated material is optionally subjected to intermediate drying at a higher temperature and then treated in a fresh bath with the azomethine component, optionally together with reducing substances, preferably below Temperature increase up to 140'C. The rubbing fastness of the dyeings obtainable in this way can be improved by aftertreatment with reducing agents, such as sulfites or formaldehyde-sulfite addition products, often with the addition of an emulsifying agent.

A special AusfUhrungsförrn the above-mentioned process consists in that the material padded in the first phase with the azomethine component in the presence of hydrazine is dried in a continuous operation, then briefly thermoset at a higher temperature, preferably at 200 to 210 ° C and optionally after subsequent soapy in a dye bath or a padding liquor with one of the components a), b), c) or d) or mixtures thereof.

As a dispersing or emulsifying agent that adds to the starting components or in the course of the above Dyeing process advantageous are added, the commercially available products are suitable, such as sulphite cellulose liquor products, Condensation products from higher alcohols and ethylene oxide, soaps, polyglycol ethers aromatic fatty acid amides, condensation products from aromatic sulfonic acids or mixtures of these compounds.

Substances with a reducing effect, optionally the azomethine component are added, are among others sodium sulfide, sodium sulfite, sodium dithionite, Sodium thiosulfate, hydroxylamine, hydrazine hydrate, hydrazine sulfate, sodium boranate or mixtures of these compounds.

The dyeings obtained by the new process are distinguished very good fastness properties, in particular also excellent sublimation and very good lightfastness. Particularly noteworthy are the real black tones, which is based on materials made from aromatic polyesters, especially from fibers and Polyethylene terephthalate fabrics are obtained.

It is already known from German patent 1079 587 that true black colorations can be obtained on polyester materials by allowing aromatic, mononuclear or polynuclear black bases suitable for oxidation coloring to be attached to the materials and then with chlorite in the presence of acid or with hypohalous acid or certain hypohalous acid-releasing agents, z. B. with N - chloro- or N - bromocarbamic acid ethyl ester, N-halogen compounds, preferably of cyclic imides such as N-bromosuccinimide, but especially N-halogen compounds of sulfonamides, preferably those of the aromatic series, such as benzenesulfodichloramide, p- chlorobenzene - dichloramide and p -Toluene-sulfochloramide-sodium. This process has the disadvantage that it is necessary to work with chlorine-releasing agents which, moreover, tend to hydrolyze even at room temperature when exposed to moisture and thus question the uniformity of the dyeings. Furthermore, according to this procedure, the amines are used in the form of aqueous dispersions, which are known to be sensitive to oxidation and tend to separate out.

The new process avoids these disadvantages and, due to the better shelf life of the starting components and the water solubility of the azomethine components, offers more favorable application possibilities. The quinones and the derivatives of quinones and N, N'-dihaloquinonimines which can be used in the present new process are stable compounds which, for. B. half-hour boiling in an aqueous medium - according to the usual dyeing conditions - withstand without being changed.

The dyeings obtained according to the invention differ from the dyeings which are obtained on polyester fibers by the process of Belgian patent specification 586 911 in that they are significantly better rubbing fastness.

Example 1 1.6 g of the azomethine from 4-aminodiphenylamine and benzaldehyde-o-, -m- or -p-sulfonic acid sodium are dissolved in 30 ml of water which contains 2 g of a weakly cationic alkylphenylammonium sulfonate and placed in a dyebath of 200 ml Water containing 1.5 g of hydrazine hydrate and 5 g of trichlorobenzene per liter is added. After adding 10 g of polyethylene glycol terephthalate fiber in the form of hanks or piece goods, the dyebath is brought to boiling temperature in the course of about 15 to 20 minutes. After one hour of dyeing at this temperature, the yellow-colored goods are rinsed well and placed in a fresh bath containing 1 g of 2,5-dichloroquinone-1,4, 0.4 g of a nonionic alkyl polyglycol ether and 5 g / l of trichlorobenzene in 200 ml of water , Post-treated for 30 minutes at boiling temperature.

To improve the rubbing fastness, 2 g of sodium bisulfite and 1 g of a polyglycol ether of a fatty acid amide can be aftertreated for 10 to 30 minutes after rinsing in a slightly boiling bath with 4 ml of sodium hydroxide solution (38 ' B8) per liter.

A black dyeing with very good fastness properties is obtained. Example 2 0.5 g of Azornethins from 2-amino-4'-methoxydiphenylamine and benzaldehyde-o-, -m- or -p-sulfonic acid sodium are dissolved in 20 ml of water and placed in a dyebath of 200 ml of water, which is in Liter contains 2 g sodium dithionite and 3 g cresotinic acid methyl ester. In this bath, 5 g of polyethylene glycol terephthalate fibers in the form of hanks or piece goods are dyed for 1 to 11/2 hours at the boiling temperature. The pre-dyed goods are then rinsed and in a bath containing 0.5 g of trichlorobenzoquinone or any mixture of the products benzoquinone, mono-, di-, tri- or tetrachlorobenzoquinone-1,4, 0.2 g of a nonionic alkyl polyglycol ether and 3 g / 1 of any dye accelerator such as chlorobenzene, developed for about 30 minutes at boiling temperature. As described in Example 1 , aftertreatment can be carried out to improve the rub fastness. A black dyeing with good fastness properties is obtained.

Example 3 5 g of polyethylene glycol terephthalate fiber fabric are made with the aid of a laboratory high-temperature dyeing apparatus in a bath of 200 ml of water containing 0.8 g of azomethine from 4-amino-2'-methoxydiphenylamine and sodium benzaldehyde-o-sulfonic acid and 2 g of sodium sulfide per liter contains, pre-colored for one hour at 120 to 125'C. After this time, the yellowish-colored goods are rinsed and placed in a bath of 200 ml of water containing 0.5 g of 2,6-dichloroquinone-1,4 and 0.2 g of a nonionic alkyl polyglycol ether for about 30 minutes at 120 to 125 'C aftertreated. The goods are then rinsed and, if the rub fastness is insufficient, as described in Example 1 , subjected to reductive aftertreatment. A black dyeing with very good fastness properties is obtained.

Example 4 1g of the azomethine from 4-amino-4'-methoxydiphenylamine and benzaldehyde-2,4-disulphonic acid sodium is dissolved in 30 ml of water and placed in a dyebath of 200 ml of water which contains 1 g of sodium sulphide per liter. 10 g of polyester fabric are treated for 11/2 hours at 120.degree. C. in this dye liquor. After an intermediate cleaning, the color is developed in a dyebath of 200 ml of water, which contains 0.4 g of 2,5-dichloroquinone-1,4-0.10 g of potassium dichromate and 0.10 g of sulfuric acid, for 30 minutes at 120.degree . After a reductive aftertreatment, a black dyeing with good fastness properties is obtained. Example 5 10 g of polyethylene glycol terephthalate fiber fabric are padded with a liquor containing 80 g of azomethine from 4-aminodiphenylamine and sodium benzaldehyde-sulfonic acid, 10 g / l of a neutral or weakly cationic emulsifier, e.g. B. contains an alkylphenylammonium sulfonate, and 10 g / 1 250 / () hydrazine hydrate, the liquor pick-up being 100%. After intermediate drying, the padded fabric is heated to 180 ° C. for 90 seconds. After a short intermediate rinse, the dyeing is carried out in a bath containing 0.8 g of 2,5-dichloroquinone-1,4 in 400 ml of water, as is obtained in the technical description, and about 0.5 g of a commercially available dyeing accelerator, during a half an hour at boiling temperature. After a reductive aftertreatment, as described in Example 1 , a black dyeing with excellent fastness properties is obtained. Example 6 50g of the azomethine from 4-amino-4'-methoxydiphenylamine and benzaldehyde-o-sulphonate sodium are dissolved together with 10 g of technical sodium sulfide in 500 ml of water and placed in a dyebath g in 121 water 500 polyester fibers in the form of a combed contains. The dyeing is carried out for one hour at 120.degree. It is then rinsed and coloring in a fresh bath of 121 water, 30 g of 2,5-dichloroquinone-1,4 and 30 g of a naphthalenesulfonic acid - containing condensation product, for 30 minutes completed at a temperature of 120'C - formaldehyde. After the aftertreatment described in Example 1 , a black dyeing with excellent fastness properties is obtained. EXAMPLE 7 1.5 g of the azomethine from N, N'-di- (p-aminophenyl) -4,4'-diamino-diphenylamine and sodium benzaldehyde, -m- or -p-sulfonic acid, together with 0.4 g of sodium sulfide dissolved in 50 ml of water and placed in a dyebath of 200 ml of water which still contains 5 g of trichlorobenzene per liter. In this dyebath 10 g of polyethylene glycol terephthalate fiber fabric are treated for 1 hour at boiling temperature. Then wIrd rinsed and in a fresh bath containing 0.8 g of 1,4-tetrachloroquinone or the same amount of 1,4-dichloronaphthoquinone and 0.4 g of a nonionic alkyl polyglycol ether in 200 ml of water for 30 minutes Post-treated at boiling temperature. After a final reductive aftertreatment, as described in Example 1 , a black dyeing with good fastness properties is obtained.

If, instead of the aforementioned azomethine, those made from N, N'-bis [4-aminophenyl] -4,4'-diaminodiphenyl ether are used. N, N'-bis- [4-aminophenyl) -4,4-diaminostilbene or N, N'-bis- [4-aminophenyl] -4,4-diamino -3,3 ' -dimethoxy - diphenyl , gray to black dyeings with good fastness properties are also obtained.

Example 8 10 g of fiber fabric made of 'polyethylene glycol terephthalate are placed in a bath of 300 ml of water, the 1.2 g of dissolved azomethine from 4-amino-2'-methoxy - diphenylamine and benzaldehyde - o-, - m- or -p-sulfonic acid sodium contains 0.3 g of sodium sulfide and 2 9 trichlorobenzene, for 1 to 11/2 hours at boiling temperature. After intermediate cleaning, the color is developed in a bath of 300 ml of water containing 0.6 g of 1,4-phenylbenzoquinone and 2 g of trichlorobenzene for half an hour at boiling temperature. A black-gray dyeing with good fastness properties is obtained.

If 1 g of heptachloro-cyclohexenone or 1 g of pentachloro-tetralone is used instead of 2-phenylbenzoquinone-1,4, black dyeings with good fastness properties are likewise obtained. Example 9 500 g of polyethylene glycol terephthalate fiber sliver are treated for 1 hour at NO'C in a bath of 12 1 of water containing 50 g of the azomethine from 4-amino-diphenylamine and contains benzaldehyde sodium sulphonate and 6 g of sodium sulphide. After subsequent rinsing, the dyeing is done in a bath containing 25 g of N, N'-dichloroquinone diimine in 121 water and contains 25 g of a naphthalenesulfonic acid-formaldehyde condensation product, completed for 30 minutes at 120.degree . After a final reductive aftertreatment, as described in Example 1 , a black dyeing with excellent fastness properties is obtained.

If the same amount is used instead of the N, N'-dichloroquinone diimine N, N # -dichloro-naphthoquinonediimine-1,4 or N-chloro-2,6-dichloroquinoneimine, is obtained there are also black dyeings with very good fastness properties.

EXAMPLE 10 50g of polyethylene glycol terephthalate fiber in the form of strand material applied to a cross-wound bobbin are mixed with 1 g of sodium sulfide or the same amount of sodium hydrogen sulfite or potassium boronate and 5 g of azomethine from 4-amino-4 # -methoxy-diphenylamine and benzaldehyde in a bath which is in 5ffl ml of water -4-Sodium sulfonic acid, treated for 1 hour at HO'C. After this time has elapsed, the yellow-colored goods are rinsed and placed in a bath containing 3 g of quinone-anil-N-chlorimide in 500 ml of water Contains 4 g of a customary dispersant (for example a naphthalenesulfonic acid-formaldehyde condensation product) and 2 g of trichlorobenzene, treated for 15 minutes at boiling temperature. After a reductive aftertreatment, as described in Example 1 , a black dyeing with good fastness properties is obtained.

Example Ü lOg triacetate fiber in the form of hank are in a bath of 400 ml of water, the 1.0 g of the azomethine from 4-amino-4-methoxy-diphenylamine and sodium o-, -m- or -p-benzaldehyde sulfonic acid and 2 g Contains trichlorobenzene, treated for 1 hour at boiling temperature. After an intermediate rinse of the goods, the dye is treated for 1/2 hour in a bath of 400 ml of water containing 0.5 g of 2,5-dichloroquinone-1,4 and 0.5 g of a naphthalenesulfonic acid-formaldehyde condensation product Cooking temperature developed. After a reductive aftertreatment, a black dyeing with very good fastness properties is obtained. Example 12 25 g of polyacrylonitrile fibers are dyed at the boil for 1 hour in a bath of 1000 ml of water with 2 g of the azomethine from 4-aminodiphenylamine and sodium benzaldehyde-p-sulfonic acid and, after an intermediate rinse, with 1.2 g of N, N # -dichloroquinone diimine for 30 minutes Developed minutes at boiling temperature. A black dyeing with very good fastness properties is obtained. A black coloration is also obtained if, instead of the polyacrylonitrile fiber, polyvinyl chloride fiber is colored using this method. Example 13 5 g of acetate fiber are dyed in a bath of 200 ml of water with 0.5 g of the azomethine from 4-amino-4 # -cyclohexyl-diphenylamine and sodium benzaldehyde-o-sulfonic acid for 1 hour at 85.degree. At the end of this time, the goods are rinsed and developed for the development of the dye with 0.3 g of trichloroquinone with the addition of 0.3 g of a nonionic alkyl polyglycol ether for 1/2 hour at 85.degree. A black dyeing with good fastness properties is obtained. Example 14 0.5 g of the azomethine from 7-amino-fl-naphthol and benzaldehyde-o, -m- or -p-sulfonic acid sodium are dissolved in 20 ml of water and placed in a dyebath of 200 ml of water, which is 2 g per liter Contains sodium sulfide and 3 g of methyl cresotinate. In this bath, 5 g of polyethylene glycol terephthalate fibers in the form of strand or piece goods are dyed for 1 to 11/2 hours at boiling temperature. The pre-dyed goods are then rinsed and placed in a bath containing 0.5 g of N, N-dichloro-2,5-dichloroquinonediimine-1,4, 0.2 g of a nonionic alkyl polyglycol ether and 3 gll of any dye accelerator such as chlorobenzene - Developed for about 30 minutes at boiling temperature. As described in Example 1 , aftertreatment can be carried out to improve the rub fastness. A brown color is obtained. Instead of the azomethine used here, the bis-azomethine from 1,5-diamine naphthalene and benzaldehyde-o-, -m- or -p-sulfonic acid sodium can also be used.

EXAMPLE 15 lg of azomethine from 2,4-dinitro-4'-aminodiphenylamine and benzaldehyde-2,4-disulfonic acid sodium are dissolved in 30 ml of water and placed in a dyebath of 200 ml of water which contains 1 g of sodium sulfide per liter. 10 g of polyester fabric are treated for 11/2 hours at 120.degree. C. in this dye liquor. After intermediate cleaning, the color is developed in a dyebath of 200 ml of water, which contains 0.4 g of 2,5-dichloroquinone-1,4, P, 10 g of potassium dichromate and 0.1 g of sulfuric acid, for 30 minutes at 120.degree . A brown coloration is obtained after a reductive aftertreatment.

Claims (2)

Claims: 1.- Process for dyeing and padding structures made of hydrophobic materials, such as threads, fibers, foils, tapes and the like, made of aromatic polyesters, in particular polyethylene terephthalates, of polyamides, polyurethanes, polyvinyl chlorides, polyacrylonitrile and their copolymers, Cellulose esters and polyolefins, characterized in that the structures to be colored are successively treated in any order with azomethines of aromatic amines which have at least one solubilizing group in the remainder of the aldehyde component, and with a) quinones or b) N-haloquinone imines or N, N'- Dihaloquinonimines of preferably substituted quinones or c) with compounds which form the group in a carbocyclic ring contain, in which X and Y are carbon-carbon bonds, hydrogen or halogen, or d) treated with quinonanil-N-haloimides, it being possible, if appropriate, to use components a) to d) as a mixture with one another. 2. The method according to claim 1, characterized in that the material is treated at temperatures of 60 to 140'C after application of the starting components. 3. Process according to Claims 1 and 2, characterized in that the azomethine component is first applied, briefly heat-set at elevated temperature, preferably at 200 to 20'C, and then components a) and / or b) and / or c) and / or d) applies. Considered publications: German Auslegeschriften Nos. 1088 461, 1079 587; Belgian Patent No. 586 911; D iseren s , The latest advances in the application of dyes, Vol. 2 (1949), pp. 264 to 274. When the application was announced, a sample card with a test report was laid out.