DE1220826B - Process for dyeing or printing textile material made of vegetable fibers using the methods of the ice dye technique - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

D06p

German class: 8 m -12

1220 826
F34891IVc / 8m
September 9, 1961
July 14, 1966

In the production of water-insoluble azo dyes A large number of textile auxiliaries are found on the fiber using the methods of the ice color technique Use, so for the preparation of solutions or thickened solutions of the coupling components or the diazonium compounds. They are usually used for the production of coupling components containing primer baths protective colloids, such as. B. sulfonates of unsaturated fatty acids, Condensation products from higher molecular weight carboxylic acids and protein degradation products or condensation products from aminoalkylsulfonic acids and higher molecular weight carboxylic acids, while the developing baths dispersants, such as. B. Products for action from ethylene oxide to fatty alcohols or alkylphenols. These well-known tools all tend more or less to foam, which has long been felt to be a disadvantage in practice will. In addition, the use of these compounds increases the flow rate of the dye liquors greatly reduced; this phenomenon can be detrimental to the dyeing process in several ways and affect the failure of the stains.

In the case of dyeing, the material resting according to the system - moving liquor is carried out relatively long dyeing times are necessary to achieve level dyeing. Often remains in the material to be colored, e.g. B. in cotton bobbins, trapped air back that causes unstained areas or uneven staining, provided the material to be dyed is not in pre-wetted in a separate operation or unless a wetting agent has been added to the primer solution will. Furthermore, when dyeing tightly beaten material on the padder through the short time available for deaeration during the passage through the one containing the dye liquor Chassis often only insufficiently colored.

It has now been found that the disadvantages outlined above in dyeing or printing can be achieved can avoid textile material made of vegetable fibers using the methods of the ice color technique, if in the presence of water-soluble condensation products which contain several, preferably 2 to 6, via methylene bridges directly or with the interposition of residues of aromatic compounds linked residues of oxyalkylated aromatic hydroxyl or carboxylic acid groups containing compounds contained in the molecule, colors or prints.

The water-soluble condensation products mentioned can, for. B. by the method of the method for dyeing or printing
Textile material made from vegetable fibers according to the
Methods of ice color technique

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning, Frankfurt / M.

Named as inventor:

Dr. Hans Thaler,

Dr. Alfred Scharf,

Dr. Richard Groß, Frankfurt / M.

Belgian patent 615 449 can be prepared by

A. aromatic compounds that can react with formaldehyde with

B. water-soluble addition products of alkylene oxides to compounds containing aromatic, hydroxyl or carboxylic acid groups and

C. Formaldehyde condenses in the presence of an acidic catalyst and the condensation products optionally with an alkylating agent in on

alkylated in a known manner.

The water-soluble condensation products mentioned can also be prepared by first precondensing the aromatic compounds (A.) with formaldehyde and condensing these precondensates with the alkylene oxide addition compounds (B.) in the presence of an acidic catalyst.
For the preparation of the water-soluble condensation products used according to the invention, aromatic compounds which can react with formaldehyde (A.) are above all compounds which contain hydroxyl groups bonded to the aromatic nucleus, which can also be etherified. Also suitable are: addition products of 2 to about 50 moles of ethylene oxide with 1 mole of an aromatic amine and aromatic hydrocarbons suitable for reaction with formaldehyde. The following compounds may be mentioned as examples: phenol, resorcinol, butylphenol, chlorophenol, naphtol, methylnaphtol, 4,4'-dioxydiphenyl, anisole, and also adducts of

609 589/283

3 4

2 to 50 moles of ethylene oxide in 1 mole of a phenol, as from yarns or fabrics made of natural or

as well as the hydrocarbons xylene, mesitylene and regenerated cellulose, according to the methods of

Naphthalene. Ice color technique largely avoided. It occurs z. B.

As water-soluble addition products of alky- no foaming, so that in rope dyeing Lene oxides on aromatic hydroxyl or carbon 5 undesirable swimming of the yarns and in foulardic acid groups Compounds containing (B.) come colorations foaming over the chassis contents as well first and foremost, reaction products of about 8 to the staining on the goods due to adhering 50 moles of alkylene oxide, preferably ethylene oxide foam bubbles, is avoided. When printing with and / or propylene oxide, with 1 mole of the aromatic printing pastes, which coupling components or Io diazonium compounds containing hydroxyl or carboxylic acid groups or mixtures of Connections into consideration. As aromatic hydroxyl coupling components and diazoamino compounds or compounds containing carboxylic acid groups, antidiazotates or diazosulfonic acids, come mainly mono- or dihydric phenols, how are Unz. B. phenol, cresol, butylphenol, oc-naphtol, ß-naphthole and blurred contours avoided, toi, resorcinol, 2,2'-dioxydiphenylpropane or methyl. The water-soluble ones that can be used according to the invention len-di - ^ - naphtol in question. Furthermore, condensation products can also have the advantage Alkylene oxide addition products based on aro- on that they are in contrast to some known matic compounds are used in which auxiliaries are not polynuclear Diazoverbindundie functional group by one or more, gene or metal salts, such as. B. aluminum sulfate, the preferably up to about three methylene groups of 20 as stabilizers for solid diazonium salt aromatics Core is separated, such as B. Benzyl preparations and, as alkali binders, extensive veralcohol, p-Xylylene glycol, phenylacetic acid, phenoxy are used to form water-insoluble compounds acetic acid or naphthylacetic acid. react.

It is particularly advantageous to use such as opposed to those used in the production of water-soluble ones Condensation products that are usually acidic due to the insoluble azo dyes on the fiber Condensation of about 1 mole of phenol, about wise used auxiliaries set the invention-2 Mole of formaldehyde and about 1 mole of the compounds used according to the plant, the flow compound from about 10 to 30 mol of ethylene oxide speed of the liquors in both acidic and of 1 mole of phenol or naphthol and then only insignificantly decreases in alkaline solution. at Reaction with dimethyl sulfate can be obtained. 30 a comparison of the flow times of dyeing

According to the invention, one can proceed in such a way that liquor which has been prepared with the various auxiliaries of the water-soluble condensation products of the type mentioned standing in a dyeing apparatus of the system, the priming baths or stationary material — moving liquor shows that it is added to the printing pastes, which the coupling flow times of primer baths or component parts and other common additives, such as winding baths by adding the known auxiliary sodium hydroxide solution, formaldehyde and, if necessary, agents, such as. B. castor oil-sulfonic acid sodium, condensing agent, contain. The water-soluble condensation products of higher fatty acids with protein denaturation products can, however, also be used in the area of degradation products, condensation products of amino acids in the developing baths or printing pastes containing alkylsulfonic acids, such as methyltaurine with higher diazonium compounds and the other usual fatty acids or ethylene oxide condensation products such as additives. B. acetic acid, alkali phosphates, alkali of fatty alcohols or alkylphenols, to the 4 to bicarbonate and optionally thickener, 15 times the value of the baths without additives or still contain, or such printing pastes that a coupling is increased. In contrast, the permeability component and a stabilized diazonium flow time when the compound according to the invention is used in the form of a diazoamino compound increases to a maximum of I ¹ I _{2 to 2} times that of an antidiazotate or a diazosulfonic acid and the values as they are with solutions without the addition of auxiliaries customary additives such as alkali and _r Ver convey be observed
thickeners included. By this faster flow of the after

The amounts in which the water-soluble condensation processes of the present invention are obtained

sation products are used, it is possible in 50 liquors, which are usually long

wide limits fluctuate. The quantities used are priming and development times for dyeing

Above all to shorten significantly by the liquor ratio of the wound packages used. Farther

addicted. In the case of a high liquor ratio, it is sufficient by using the inventive

generally low concentrations of the auxiliaries auxiliaries as protective colloids possible, wound bodies

from, while at a low liquor ratio 55 from cotton without prior decoction or

it is necessary to prime larger amounts of the pre-wetting of the invention without difficulties

to use appropriate aids. Generally caused by the air inclusions mentioned,

come the auxiliaries used according to the invention. It should be noted here that the according to the invention

in amounts ranging from about 0.2 ° / ₀ to about 1%, products used no surfactant properties

preferably 0.4. , per kilogram of goods have. to 0.8 ° / ₀ 60

weight, for application. The upper limit can optionally be exceeded in the following examples explain the invention-specific cases, the method according to the invention. The condensation products used here will, however, for economic reasons, have been sought to use the smallest possible amounts of the auxiliaries:
to use funds. 65. Connect T

According to the method according to the invention

The previous. Disadvantages of dyeing or printing 293 the adduct of 30 moles of ethylene

of textile material made of vegetable fibers, for example oxide on 1 mol of ß-naphthol, were mixed with 19 g of phenol

5 6

and wraps 80 g of 30% formaldehyde solution in the presence. It was then soaped in a usual manner, washed by 40 cc of 64 ° / ₀ sulfuric acid for 30 minutes under and dried.
Stirring heated to 100 to 105 ^{° C.} The received primer bath
The solution was then neutralized with sodium hydroxide solution. 5 27 g of 1- (2 ', 3'-oxynaphthoylamino) -2-methyl-4-chloro compound II benzene were dissolved in 40 ecm of ethyl alcohol, 13.5 ecm

32.5 ° / _o aqueous sodium hydroxide solution, 54 cc water and 27 cc

194.8 g of the adduct of 20 mol of 33 ° / _o dissolved formaldehyde solution and with water

Ethylene oxide and 1 mole of phenol with 18.8 g of 35 ⁰ C, 27 g of Compound II and 90 cc of 32.5 ° / _o sodium

Phenol, 40 cc of 30 ° / ₀ solution of formaldehyde and sodium hydroxide to 9 io 1 is set.
35.2 cc of 64 ° / ₀ sulfuric acid for 1 hour at 95 to

Stirred at 105 ° C. The resulting condensation product developing bath

was in the form at pH 8 to 10 and 50 to 55 ^° C. with 50.6 g of 6.8 g of 1-amino-2-methyl-4-chlorobenzene

Methylated dimethyl sulfate. the diazonium produced in the usual way

wa TTT ^1S compound were dissolved in 91 water, the 9 g

Compound III ^ Compound II, 18 g of mononatrium phosphate and 7 g

Contains 239 g of the adduct of 25 moles of ethyl disodium phosphate. It turned out to be a total

lenoxide to 1 mole of phenol was mixed with 18.8 g of phenol level, well-dyed cheese with full color

and 40 ecm 30% formaldehyde solution in the opposite depth.

waiting of 42.5 cc of 64 ° / _o sulfuric acid condensed ao Using known protective colloids

sated. The condensation product obtained was treated with and dispersants such as are, for. B. in example 1 am

50.6 g of dimethyl sulfate methylated. In conclusion, it was not possible in these

. -I ₁ times even and completely developed colorations

Example 1 obtained. To achieve the same effects as with

A rayon roll of 800 g was put into a compound II, it was rather necessary to boil or pre-wet the cross-closed apparatus in the liquor ratio 1:12 or to add wetting agent to the green-45 ° C for 20 to 30 minutes in the subsequent dierungsbad. In addition, the primer bath was treated, rinsed with 3 g of calcined for the primer then times of about 30 to soda and 30 g of table salt per liter of water between 45 minutes and for the development about 15 minutes and 15 minutes in the following process,
developing bath. Example 3

Grundierungsbad _{600 g} g _e k _ämmtes BaumwoUkardenband were 15.4 g of 1 - (2 ', 3' - oxynaphthoylamino) - naphthalene closed apparatus at a liquor ratio of 1:15 at 23.2 cc of ethyl alcohol were in, 7.8 cc of caustic soda 35 40 ⁰ C for 15 to 20 minutes in the subsequent Grunlauge, 32.5 ° / _o ig> 23.2 cc of water and 7.8 cc of 33 ° / _o sodium dierungsbad treated with 1 cc of 32.5 ° / _o sulfuric soda Dissolved formaldehyde solution and rinsed between -27 g of compound I and 28 g of calcined soda with water of 45 ° C alkali and 20 g of sodium chloride in liter of water and adjusted to 9.6 1 in the developing bath for 10 minutes. wraps. It was then soaped and rinsed in the usual way

Development bath * ° ^and dried.

"""..",. . , ■ ~ primer bath
7.8 g of l-amino-2-methoxy-4-nitrobenzene in the form

of the diazonium 10.8 g of 2 - (2 ', 3' - oxynaphthoylamino) - naphthalene prepared in the usual way

compound was dissolved in 9.61 water, which was 9.6 g in 13 cc of ethyl alcohol, 4.3 cc of 32.5 ° / _o sodium

Compound I and 6 g of sodium bicarbonate. 45 caustic soda, 10.8 ecm water and 5.4 ecm 33%

After about 10 to 15 minutes of development, the formaldehyde solution was dissolved and washed with water at 4O ⁰ C,

Artificial silk wrap completely dyed through. 27 g compound III and 90 ecm 32.5% sodium

When using known protective colloids, lye adjusted to 91 water,
such as B. oil sulfonates, condensation products

higher molecular weight fatty acids and protein degradation pro- 50 developing bath
products or condensation products from a

Aminoalkylsulfonic acid and a higher molecular weight 6.1 g of 4-amino-2,5-dimethoxy-2 ', 6'-dichloro-4'-nitro fatty acid and dispersants, such as. B. Einwir- Ι, Ι'-azobenzene in the form of in the usual way kungsprodukte of ethylene oxide on an alkyl produced diazonium compound were dissolved in 9 1 phenol, action products of ethylene oxide on 55 water, the 9 g of compound III and 90 ecm a fatty alcohol or condensation products from 50% acetic acid. When dyeing an aminoalkylsulphonic acid and a higher molecular weight with low pump pressure, such as for cottonseed fatty acid, it was not possible to obtain level card sliver to maintain the spinning properties and solid-colored laps during this time. it is necessary to have a full “. . - - 60 developed and level blue coloration. When using .Bebeispiel I _yon burned protective colloids, such as those z. B. in a cotton package of 600 g was mentioned in an example 1 at the end, it was necessary to prime the closed apparatus in the liquor ratio 1:15 for a long time, up to about 60 minutes; 35 ° C 15 to 20 minutes in a primer bath using known dispersants, treated with the following composition, with 65 such. B. exposure products of ethylene oxide to 1 cc of 32.5 ° / _o aqueous sodium hydroxide solution and 30 g of sodium chloride in an alkyl phenol, exposure products of ethylene-liter water between rinsed and 5 minutes in the oxide to a fatty alcohol, condensation products developing bath-adjusting described corresponds from an aminoalkylsulfonic and a higher

molecular fatty acid, level development was only achieved after about 25 to 30 minutes.

Example 4

Napped cotton flannel was applied to a high-speed padder with a 80 to 90 ⁰ C warm solution containing 1001 g of water in 500 g of l- (2 ', 3'-oxynaphthoylamino) -2-methyl-4-methoxybenzene, compound III 500 and 750 cc 32.5 ° / oig ^he sodium hydroxide solution, padded and dried in the hot flue. A solution was then developed on a three-roll foulard, which contained 5.3 g of 4-amino-2,5-dimethoxy-4-nitro-l, l'-azobenzene in the form of the diazonium chloride-chlorozinc double salt, 40 ecm 50 ^o / oiger acetic acid and 5 g of compound II contained. After 30 seconds of air passage, the product was ^{treated with water at 80 °} C. in a trough, rinsed with cold water, soaped off at the boiling point, rinsed and dried. A navy blue color was obtained.

When using known protective colloids, such as those used, for. B. are mentioned in example 1 at the end, After a short time there was strong foaming caused by the air entrained by the goods so that the contents of the chassis foamed over and foam lumps formed on the goods. Likewise the height of the liquor level was no longer controllable due to the strong foam formation, what of The disadvantage is that with fluctuating liquor level, fluctuations due to the different immersion times appear in the depth of the staining.

Example 5

Cotton fabric was padded on the padder with a solution of 12 g of 2,3-oxynaphthoylaminobenzene, 12 g of compound II and 18 cm of 32.5% sodium hydroxide solution in one liter of water at 80 to 90 ° C. and dried. The dried fabric was printed with a printing paste containing kg in 1 10 g of l-amino - ^ - methyl ^ chlorobenzene in the form of the diazonium compound prepared in the usual way, 5 g of compound II, 10 cc of 50 ° / _o acetic acid and when Containing thickener tragacanth. After drying, the substance was left by a 8O ⁰ C hot bath happen that ECM in 10 liters of water containing 38 ° / _o sodium bisulfite solution. It was then treated several times in a soda-alkaline bath, soaped in the usual way, rinsed and dried. A red, level print was obtained. When using known dispersants, as they are, for. B. are mentioned in Example 1, the printing pastes tended to foam particularly at higher printing speeds, which resulted in a blotchy, uneven and blurred print.

Example 6

A mixture of 18 g of l- (2 ', 3'-oxynaphthoylamino) -2-ethoxybenzene, 13.7 g of sodium salts of the nitrosamine of l-amino-2,5-dichlorobenzene and 21 g of sodium acetate, anhydrous, was added to 30 g of 32 , 5 ° / _o aqueous sodium hydroxide solution, 20 g of compound I and 30 g ethyl alcohol made into a paste after brief standing with 370 g of water at 30 ⁰ C and washed neutral in 500 g of starch tragacanth thickener are stirred in. This printing paste was used for printing and drying in the usual way. This was followed by treatment with moist steam in the high-speed steamer for 3 to 5 minutes.

Then the product in a wide state was passed through a 70 to 80 ° C hot bath containing 30 cc of 50 ° / ₀ acetic acid and 25 g of Glauber's salt out in liters, well rinsed and soaped at the boil.
Was a commonly used protective colloid, z. B. an oil sulfonate added to the printing pastes, these tended to foam, especially in high-speed printing machines, which resulted in a blotchy, restless and fuzzy print.

Claims (1)

Claim: Process for dyeing or printing textile material made from vegetable fibers according to the Methods of ice color technology, characterized in that in the presence of water-soluble condensation products, which are several, preferably 2 to 6, via methylene bridges connected directly or with the interposition of residues of aromatic compounds Compounds containing residues of alkoxylated aromatic hydroxyl or carboxylic acid groups contain, color or print. Considered publications: Schaeffer, Handbuch der Färberei, 1949, Vol. 1, p. 405, and Vol. 5, pp. 460 and 461. A test report was displayed when the registration was announced.