DE2102899C3 - Low-foaming, water-soluble dyeing auxiliaries - Google Patents

Description

The invention relates to low-foam, water-soluble dyeing auxiliaries which are clear in the dye liquor dissolve with little or no foam.

The dyeing auxiliaries can, depending on their special composition, be used for dyeing Natural and synthetic fibers of all kinds are used, provided one is dyeing in one pH range of 2.5 to 8 remains.

The dyeing auxiliaries used to date in the textile industry are in most cases surface-active Surfactants (detergents) in aqueous solution at the usual use concentrations have a strong foaming power. This can result in a strong foam in many dyeing processes form, which leads to sensitive disorders. Because of this, there was great interest in education to reduce the foam or to prevent it at all.

The simplest way would be to use non-foaming products as dyeing auxiliaries. Until now Such products could only be found in a few cases and were the ones already known Foam-forming products are often clearly inferior in various important properties. It was

ίο tries to foam by adding defoamers to prevent or to eliminate a foam that has once formed. Defoamers are particularly effective which contain silicone oils (Walter Noil, Chemie und Technologie der Silicones, Verlag Chemie, Weinheim / Bergstrasse, 1960, p. 401). The formation of a surface film of silicone oil that is insoluble in the liquor is the prerequisite for a defoaming effect. After D. G. Dervichian, journal für Elektrochemie 59, 240 (1955), calls for the theory

ao the defoaming that the defoamer should be insoluble in the medium to be defoamed. It is however, it is not easy to emulsify the insoluble silicone oils so that they form uniform surface films form. These emulsions often break, causing the silicone oils to precipitate and deposit on the textile material. There they form spots that can practically no longer be removed.

Likewise, according to the last-mentioned references loc. cit. others insoluble in water Products as defoamers, e.g. B. mineral oils or tributyl phosphate. The defoaming effect of this Products is significantly worse than the silicone oils; they also form emulsions that are insufficient are stable and can cause stains if broken. The same applies to fatty acids and their Aluminum or alkaline earth salts and for mixtures of aliphatic alcohols, ketones and esters. These connections are characterized in part by a more or less strong, unpleasant one Smell, which can be quite annoying for the operating staff.

Fatty acids and their water-insoluble salts as well as silicones often have an undesirable hydrophobing property Effect. From French Patent 15 43 714 it is known that one mole of an ester Addition product of ethylene oxide and optionally then propylene oxide with a polypropylene glycol ether, that has an average molecular weight of 1000 to 5000 and a content of 15 to

thus contains 60% of etherified ethylene glycol groups, based on the total weight of the addition product, and 2 moles of a saturated fatty acid with 12 to 18 carbon atoms can also be used as foam suppressors. These connections but are very sparingly soluble in water and form cloudy emulsions or dispersions from which they often fail, which causes them to deposit on the material to be dyed and lead to stains. When flowing through the dye liquor these compounds are filtered off through the material to be dyed, becoming ineffective and disruptive Forming deposits. If these products are used to defoam padding liquors, they form Specks and spots on the goods due to the failed insoluble defoamers.

The object on which the present invention is based was therefore to give the technology a water-soluble one and to propose a foam-free dyeing aid which does not have the above disadvantages and

that when dyeing from a long liquor improves the levelness of the dyeings when making up dyebaths and padding liquors, poorly soluble dyes on the addition of the individual components.
Prevents failure and improves tear resistance. Surfactants, which should also be used as component a) in the sense of such an agent, the wetting effect invention are, for example: improve and ensure an even distribution of the 5 nonionic compounds, such as dyestuff padded on the fiber. products of ethylene oxide, propylene oxide, butylene oxide This object was surprisingly achieved with or mixtures of these epoxides on saturated low-fat foaming water-soluble dyeing auxiliaries based on acids, fatty alcohols, fatty amines, fatty amides, alkyls based on nonionic surfactants, the phenols, glycols and other compounds whose active ingredient is a mixture from io active hydrogen atoms an addition of lower

a) 10 to 70 percent by weight, based on the molecular epoxides.
Dyeing auxiliaries, of a nonionic Tensäds 8 ^{The date set out} compounds are well known detergents,

b) 10 to 70 percent by weight, based on the ^network " ^and leveling aids, which alone ver-dyeing aids, an esterification product uses cause a very strong foam, which consists of 2 molar equivalents of a fatty acid mixture, ^{15 during the} dyeing process the above disadvantages of at least 30% contains oleic acid, and one causes ■

Molecular equivalent of a two terminal OH group component b) of the dye works according to the invention

The defoaming component is the block copolymer containing the pen and made from an ethylene auxiliary.

oxide and 1,2-propylene oxide, which is a molecular?. ^{s are} esterification products of

has a weight of about 1500 to 7000, the ^{fatty acid mixtures containing ao oleic} acid with two

Sum a) + b) g is 95 percent by weight and block copoly-

c) <20 to 5 percent by weight based on the mensaten, in which the proportion of polymerized Dyeing auxiliaries, of water and / or organic ethylene oxide between 10 and 80 percent by weight, Niche solvents, preferably 20 to 60 percent by weight, the proportion

25 of polymerized propylene oxide between 20 and

contain. 90 percent by weight, preferably 40 and 80 percent

The fact that the dyeing weight percent according to the invention lies.

Auxiliaries do not have a foaming effect, is surprising, These block copolymers, which then with

because according to D. G. Dervichian (loc. cit) the theory of the fatty acid mixture can be esterified

the defoaming demands that the defoamer be set to 30 by adding ethylene oxide to poly-

is insoluble in the medium to be defoamed. propylene glycol or propylene oxide on poly

But it was also particularly surprising that it accumulates due to the ethylene glycol. These procedural measures

partial or complete replacement of the saturated can also be alternated in several steps

Fatty acids can be carried out through oleic acid and clear dye baths. You can z. B. alternating

Padding liquors are obtained, while the esters of ethylene oxide and propylene oxide on polypropylene glycol

saturated fatty acids alone also in the presence of or propylene oxide and ethylene oxide on polyethylene

Surfactants are absolutely insoluble in water. add glycol.

The saturated fatty acid esters are in water. The dyeing auxiliaries according to the invention are

insoluble if no other additives are used. obtained by combining these surfactants with the initially

The dissolution of these compounds in dyebaths is 40 mentioned ester mixtures, water and / or organic

but in the presence of surfactants awkward and niche solvents that are miscible with water

time consuming, larger particles can be undissolved mixed. The dyeing auxiliaries work depending on the

remain and stain the goods. equalizing, wetting or the detergent used

The dyeing auxiliaries according to the invention know washing, the liquors hardly or at all now not foaming simply by stirring the said mixtures. The effect of the detergents is retained by mixing oil and fatty acid esters with surfactants; in some cases even a verWasser as clear, homogeneous mixtures could be observed improvement of the effect,
The dyeing auxiliaries according to the invention have a very good storage stability at room temperature. individual following composition:

If these dyeing auxiliaries are additionally used 50 10 to 70 percent by weight, based on the dyeing water-soluble organic solvents such as butyl auxiliaries, preferably 15 to 65 percent by weight diglycol, butyl triglycol, isopropanol, dipropylene, one of the surfactants mentioned above,
glycol, butyrolactone, N-methylpyrrolidone or di- 10 to 70 percent by weight, based on the dyeing methylformamide, the storage stability of the esterification product from 2 mol of these dyeing auxiliaries can be further improved. 55 equivalents of a fatty acid mixture containing at least

Depending on the additives used, it contains 30% water, preferably 40 to 80%, oleic acid Soluble organic solvents are the new one molar equivalent of a two terminal OH dyeing aid Also weakly to strongly viscous and block copolymers of ethylene bearing groups Surprisingly with water in each oxide and 1,2-propylene oxide that have a molecular weight Ratio miscible, immediately having clear, homogeneous 60 from 1500 to 7000, the weight of this Solutions. They make it easier to mix 20 to 95% of the total weight of the dye stable, foam-free dye baths and padding liquors in auxiliaries, and <20 to 5, preferably downright ideal, because working with finished 10 to 5 percent by weight, based on the dyeing auxiliary mixtures Anyway, it is easier than using aids, water and / or an organic one each of the components weighed individually for coloring solvent.

or block liquor must be given. In addition, the dyeing auxiliaries according to the invention can

The mixing of the individual components can be used in all dyeing and padding liquors to make them stable

Mixtures with a pH between 2 and 8 are better monitored and controlled. In ätzalka-

They cannot be used in a commercial fleet, B e i s d i e 1 1

because the defoamer component saponifies and thereby

is inactivated 50 parts of esterification product are mixed

For the individual types of fiber there are now 2 moles of tallow fatty acid with the addition product of

the following settings of the inventive dyeing 5 20 mol of ethylene oxide to a polypropylene oxide from

processing aids particularly proven: Molecular weight 2600 with 40 parts of an additive

When dyeing wool with a metal complex dye product of 35 moles of ethylene oxide on castor oil and

Fen and acid dyes give these mixtures level 10 parts of water. A viscous liquid is obtained,

Dyeings and largely foam-free dye liquors. which are stable in storage and with water in every proportion

In addition, known anion-active io can be mixed.

Add dyeing auxiliaries, for example terminal ones. 100 parts of a knitted fabric made from textured sulfated adducts of ethylene oxide with fatty alcohols, polyester fibers in 2000 parts of a liquor containing alkylphenols, fatty amides or fatty amines; 1 part of the above mixture, 1 part of the bath stability of the dye liquor is improved in a known manner from the sodium salt of a condensation product and the often quite strong foaming, 15 naphthalene sulfonic acid and formaldehyde and 2 parts soft these products cause in dye liquors, the finely dispersed dye of the formula
It is also significantly reduced by the added
Aid that eliminates foam caused by thickening agents in the dyes. The claimed aids can have the effect of such 20
It is best to suppress foaming agents when
they contain less surfactant component a) and more defoamer component b).

When dyeing anionically modified polyacrylic

nitrile fibers can be the claimed aids 25
together with known cation-active fiber affins
Funds are used.

When dyeing with disperse dyes on synthetic polyamide fibers and polyester fibers, especially

Polyester fibers based on glycol terephthalate, 30

if the mixtures mentioned give foam-free, stable IV contains ₂ hours at 125 ° C., a

Dye liquors and level dyeings. You can use the level, rub-resistant, greenish-yellow colored material.

Dye liquors still add additional dispersants. The dye liquor does not show any foam formation, see above

set, for example conversion products of form- that the goods do not float and during the

aldehyde with naphthalenesulfonic acid as well as carrier of all 35 total staining runs flawlessly.

Kind, whose active substance halobenzenes, esters This mixture stabilizes in amounts from 2 to

of salicylic or homosalicylic acid with methanol, 5 parts to 1000 parts of aqueous plastic dispersions

Ethanol or propanol, monoglycol ether of chlorine from copolymers of acrylic esters. Acrylonitrile,

phenols and diphenyl or o-hydroxydiphenyl be acrylic acid or acrylamides, which with a padder

be able. 40 can be applied to textile fabrics or fleeces.

Furthermore, these auxiliaries give foam-free padding. Further auxiliaries have been made from the following

briskly mixed with disperse dyes of all kinds for the components:
Thermosol dyeing of polyester and polyamide fiber material can be used. These log fleets

can also be used in a known manner.

thickeners, wetting agents and contraceptives component A:

the pigment migration included. Addition product of 20 mol of ethylene oxide

In addition, these auxiliaries improve the stability of polypropylene glycol with a molecular weight of 2600.

of plastic dispersions, which in aqueous liquor component B:

can be applied to the textile material with a padder. 50 addition product of 18 moles of ethylene oxide with the presence of the nonionic Tens.d- polypropylene glycol with a molecular weight of 1700.
Component, the stability of the dispersion is improved, so that there are no deposits on the padding rollers. Component C:

can train. The foam-suppressing component ester of 2 moles of tallow fatty acid and 1 mole of com

prevents the annoying foam formation, which is caused by the 55 component A.

sole use of the surfactant would cause comoonent D

and thereby lead to great difficulties. _. . ... ...,. . .-,. ,, ·; ^ ,, ..

The use of the combination of surfactant and castor oil, oxathyl.ert with 47 moles of Athylenox.d.

foam-absorbing component has a syner- component E:

Gistic effect regarding the stabilization of the artificial oleic acid, oxethylated with 5 moles of ethylene oxide.

Material dispersion, the prevention of a roller coating _

on the padding rollers and the foam damping. component r:

As surfactants, oxethylation products of stearic acid, oxethylated with 9 moles of ethylene oxide, can be used.

Castor oil, the fatty alcohols, oxo alcohols, the alkyl component G:

phenols, fatty acids and fatty amides added 65 _Nony iphenol, oxethylated with 14 mol of ethylene oxide.

The parts of component H mentioned in the following examples:

are parts by weight. Nonylphenol, oxethylated with 20 mol of ethylene oxide.

To demonstrate the low foaming, solutions with 0.5 and 1 g / l of these auxiliaries were used according to DIN 53902 in a graduated cylinder with a punch and the time stopped in which the foam had disintegrated. With the regulation according to DIN 53902, 6.2 the Foam height read off after 1 minute at the earliest; but because with the present aids the foam in most cases had already disintegrated after less than 30 seconds, was changed to read the time in which the foam had completely disintegrated.

In dyeing tests it could be determined again and again that the according to DIN 53902 with standing cylinder and punches obtained values very well with the behavior of the corresponding dye liquors in the Practice matched.

Example 2

20 parts A, 50 parts C, 20 parts D, 10 parts water. Viscous liquid, clearly soluble in water. Foam disintegration in the standing cylinder according to DIN 53902.

Room temperature 0.5 g / l 29 sec. 1 g / l 8 sec. 60 ° C 0.5 g / l 9 sec. Lg / 1 13 sec.

Example 3

30 parts A, 50 parts C, 10 parts G, 10 parts water. Viscous liquid that is clearly soluble in water. Foam disintegration in the standing cylinder according to DIN 53902.

Room temperature 0.5 g / l 16 sec. Lg / 1 10 sec. 60 ⁰ C 0.5 g / l 14 sec. Lg / 1 30 sec.

Example 4

20 parts A, 50 parts C, 20 parts H, 10 parts water. Viscous liquid that is clearly soluble in water. Foam breakdown in the standing cylinder according to DIN 53902.

Room temperature 0.5 g / l 25 sec. Lg / 1 20 sec. 60 ⁰ C 0.5g / l 10 sec. lg / 1 18 sec.

Example 5

20 parts B, 50 parts C, 20 parts D, 10 parts water. Viscous liquid that is clearly soluble in water. Foam breakdown in the standing cylinder according to DIN 53902.

Example 6

30 parts B, 50 parts C, 10 parts H, 10 parts water. Viscous liquid, clearly soluble in water. Foam breakdown in the standing cylinder according to DIN 53902.

Room temperature 0.5 g / l 27 sec. 1 g / l 19 sec. 6O ⁰ C 0.5 g / l 22 sec. Lg / 1 30 sec.

At spie 1 7

50 parts C, 30 parts D, 10 parts E, 10 parts water. Viscous liquid, clearly soluble in water. Foam breakdown in the standing cylinder according to DIN 53902.

Room temperature 0.5 g / l 6 sec. 1 g / l 10 sec. 60 ° C 0.5 g / l 10 sec. Lg / 1 16 sec.

Example 8

50 parts C, 20 parts D, 20 parts E, 10 parts water. Viscous liquid, clearly soluble in water. Foam breakdown in the standing cylinder according to DIN 53902.

Room temperature 0.5 g / l
6O ⁰ C 0.5 g / l

7 sec. Lg / 1 11 sec. Lg / 1

11 sec. 15 sec.

Example 9

50 parts C, 20 parts E, 20 parts H ₁ 10 parts water. Viscous liquid, clearly soluble in water. Foam disintegration in the standing cylinder according to DIN 53902. Room temperature 0.5g / l 10sec. lg / 1 11 sec. 60 ⁰ C 0.5 g / l 18 sec. lg / 1 28 sec.

Example 10

60 parts C, 10 parts E, 20 parts G, 10 parts water. Viscous liquid, clearly soluble in water. Foam breakdown in the standing cylinder according to DIN 53902.

Room temperature 0.5 g / l 15 sec. 1 g / l 30 sec. 60 ⁰ C 0.5 g / l 18 sec. Lg / 1 30 sec.

Example 11

40 parts C, 20 parts E, 30 parts H, 10 parts water. Viscous liquid, clearly soluble in water. Foam breakdown in the standing cylinder according to DIN 53902.

Room temperature 0.5 g / l 14 sec. 1 g / l 29 sec. 60 ⁰ C 0.5 g / l 9 sec. Lg / 1 30 sec.

Room temperature 0.5 g / l 16 sec. 60 ° C 0.5 g / l 14 sec.

lg / 1 30 sec. 180 ml, foam after 30 sec. 40 ml, foam after 60 seconds no foam after 120 seconds. The auxiliary mixtures mentioned from Example 2 to 11 can be used as low-foam or foam-absorbing leveling agents when dyeing polyester fibers be used with disperse dyes. Very good, level dyeings are obtained, and at the same time a reduction in the formation of wrinkles occurs. The dye liquors are absolutely stable and occur no deposits, as when using water-insoluble Defoamer based on silicone, mineral oil or phosphoric acid ester.

409 682/149

Claims (4)

Patent claims: 1. Low-foaming, water-soluble dyeing auxiliaries based on nonionic Surfactants, characterized in that they are a mixture of active ingredients a) 10 to 70 percent by weight, based on the dyeing aid, of a nonionic surfactant, b) 10 to 70 percent by weight, based on the dyeing auxiliary, of a Veresierungsprüduktes from 2 molar equivalents of a mixture of higher fatty acids containing at least 30% oleic acid, and one molar equivalent of a two terminal OH-bearing block copolymer of ethylene oxide and 1,2-propylene oxide, the has a molecular weight of about 1500 to 7000, the sum of a) + b) ■ £ 95 percent by weight, and c) <20 to 5 percent by weight, based on the dyeing aid, of water and / or organic Solvents, contain. 2. dyeing aid according to claim 1, characterized in that it is used as component b) an esterification product of a block copolymer bearing two terminal OH groups, which - Based on the weight of the block copolymer - from 10 to 80% of ethylene oxide units and is composed of 90 to 20% of propylene oxide units. 3. dyeing auxiliaries according to claim 1 or 2, characterized in that they are used as a component b) an esterification product of an addition product of two terminal OH groups Contain ethylene oxide with a polypropylene glycol or propylene oxide with a polyethylene glycol. 4. dyeing aid according to claim 1 or 2, characterized in that it is used as a component b) an esterification product of a block copolymer bearing two terminal OH groups, through repeated alternating addition of ethylene oxide and propylene oxide to polypropylene glycol or was obtained from propylene oxide and ethylene oxide on polyethylene glycol.