DE1125881B - Level when dyeing with sulfur or Kuepen dyes - Google Patents

Description

INTERNAT. KL. D 06 P

GERMAN

PATENT OFFICE

B 59915 IVc / 8m

REGISTRATION DATE: OCTOBER 29 E R 1960

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL: MARCH 22, 1962

Dyeings with sulfur or vat dyes are often uneven. They are different Substances have been proposed to remedy this deficiency and as leveling agents in dyeings of the aforementioned Dye classes should work. So it is known to use low molecular weight betaines, ζ. Β. such off Pyridine and chloroacetic acid or from C-alkyl pyridines and ß-hydroxy-y-chloro-propanesulfonic acid, for this purpose use. Also pyrrolidone and its simple N-alkyl, N-acyl and N-hydroxyalkyl derivatives as well High molecular weight polymers of vinylpyrrolidone are already recommended as auxiliaries for vat dyeing been. However, these known means have not been able to fully satisfy, partly because they are only high Concentrations have a noticeable effect, partly because they are too retarding.

It has now been found that level sulfur and vat dyeings are excellent on fibers natural or regenerated cellulose and obtained on wool if you use water-soluble leveling agents Polyamides from a) aliphatic, cycloaliphatic or aromatic polyamines or heterocycles, the contain at least two acylatable nitrogen atoms, and b) «, / ^ - unsaturated carboxylic acids, aliphatic, polycarboxylic acids optionally containing heteroatoms or their functional parts capable of amide formation Derivatives used.

Of the aliphatic polyamines mentioned under a), in particular those are used as starting materials which correspond to the following general formula:

N- (CH ₂ ), -

-N- (CH ₂ ), -

- N

in which each of the radicals denoted by R can be a hydrogen atom, an alkyl or a hydroxyalkyl radical with up to 4 carbon atoms, χ and y each one of the integers from 1 to 6 and η one of the integers from 0 to 20 and the The sum of χ and η is greater than or equal to 2.

Examples of such aliphatic polyamines are: ethylenediamine, hydroxyethylethylenediamine, Hexamethylenediamine, di- (aminopropyl) -ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, Tripropylenetetramine, N-methyl-dipropylenetriamine.

Aromatic and cycloaliphatic polyamines that can be used as starting materials are Leveling when dyeing with sulfur or vat dyes

Applicant:

Aniline & Soda Factory in Baden

Corporation,

Ludwigshafen / Rhine

Dipl.-Ing. Bjarne Hartmark,

Hambach (a. D. Weinstrasse),

Dr. Hans-Gerhard Reppe, Dr. Rudolf Rokohl

and Dr. Matthias Seefelder, Ludwigshafen / Rhein, have been named as the inventor

z. B. phenylenediamines, xylylenediamines, tolylenediamines, 4,4'-diaminodiphenylmethane, N, N'-di- (secbutyl) -p-phenylenediamine, 1,5-naphthylenediamine and their hydrogenation products, such as 1,2-diaminocyclohexane and 4,4'-diaminodicyclohexyl methane.

Examples of heterocycles containing at least two acylatable nitrogen atoms are piperazine and piperazines substituted with low molecular weight alkyl groups.

The starting materials mentioned under b) can either be «, ^ - unsaturated carboxylic acids, preferably those of the general formula

R ₁ -CH = C -COOH

R ₂

in which R _{1 is} a hydrogen atom or an alkyl radical having up to 3 carbon atoms and R _{2 is} a hydrogen atom or a methyl radical. Acrylic and methacrylic acid may be mentioned as examples. But they can also be saturated or unsaturated aliphatic polycarboxylic acids, preferably dicarboxylic acids with a chain of 1 to 6 carbon atoms between the two carboxyl groups, for example succinic acid, adipic acid, suberic acid, maleic acid and fumaric acid. Furthermore, aliphatic polycarboxylic acids can be used as starting materials of group b) which contain heteroatoms, in particular oxygen, sulfur or nitrogen atoms, in the aliphatic molecular structure. As examples of such

209 520/384

Acids are dipropyl ether-y, y'-dicarboxylic acid, Thiodibutyric acid, ethylenediaminotetraacetic acid and nitrilotriacetic acid.

Instead of the free acids, the functional derivatives of the above-described polycarboxylic acids capable of amide formation, ie their halides, anhydrides, amides or esters, can also be used as substances of group b). The substances to be used as leveling agents according to the invention, some of which are known from French patent specification 1,173,573, can be prepared from the abovementioned starting materials by known processes by e.g. B. the substances of group a) with those of group b) in the absence or in the presence of inert 30 minutes ^{heated to 200 0} C, at the same time the water formed in the reaction is distilled off. 70 parts of the desired oligomeric polyamide are obtained as a viscous, brownish-colored resin of good solubility in water.

III. 54 parts of acrylic acid, 98 parts of dipropylenetriamine and 0.1 part of hydroquinone are added with stirring The water of reaction is distilled off and heated to 200 ° C. for 30 minutes. 132 parts of a brown,

ίο viscous oil that easily dissolves in water.

IV 51.5 parts of y / -. Thiodibuttersäure and 26 parts of diethylene triamine are heated for 30 minutes 180 ⁰ C with stirring. The water formed in the reaction is distilled off at the same time. It left behind

Solvents such as glycerin, polyglycols, 67 parts of a brown, highly viscous liquid which point about 160 ⁰ C and tetrahydronaphthalene, with each disengages from boiling 15 with good basic reaction in water, other condensed. The quantitative ratio of the reactants should preferably be chosen so that
that when using saturated polycarboxylic acids and
their functional derivatives for each carboxyl group ao
1 to 3, preferably 1 to 1.5, primary and / or secondary amino groups and when using unsaturated carboxylic acids and their functional derivatives for
every carboxy group and every reactive double

V. 47.7 parts of nitrilo-triacetic acid and 32 parts of piperazine are stirred for 30 minutes at 18O ⁰ C. At the same time, the water of reaction is distilled off. 65 parts of a tough, brown resin which dissolves well in water are obtained.

In an analogous manner, z. B. condense the following raw materials into leveling agents:

bond a total of 0.7 to 3, preferably 1 to 1.5, primary and / or secondary amino groups are available stand.

When using ", / ^ - unsaturated carboxylic acids as starting materials, it can be advantageous to add small amounts of compounds which prevent self-polymerization of these unsaturated bodies, for example hydroquinone and methylene blue. The condensation temperature to be used depends on the type of starting materials, in particular on the type of component b). Substituting the polyamines with free acids, acid anhydrides, acid amides or Säureestern a way, it has proven useful to carry out the condensation in the absence of solvents at temperatures of 170-225 ⁰ C, preferably at 200 ° C. The condensation of the amines with acid halides, on the other hand, can be carried out particularly advantageously in the presence of one of the abovementioned solvents and with the assistance of a proton acceptor such as pyridine or a tertiary VI. Succinic acid and piperazine in a molar ratio of 1: 1.5 according to regulation V.

VII. Maleic acid and diethylenetriamine in a molar ratio of 1: 1 according to regulation II. VIII. Suberic acid and piperazine in a molar ratio of 1: 1.5 according to regulation V.

IX. Dipropyl ether-y, y'-dicarboxylic acid and piperazine in a molar ratio of 1: 2 according to regulation I.

X. Thiodibutyric acid and N-methyl-dipropylenetriamine in a molar ratio of 1: 1 according to regulation IV.

IX. Nitrilo-triacetic acid and diethylenetriamine im

Molar ratio 1: 3 according to regulation V. XII. Ethylenediamino tetraacetic acid and piperazine im Molar ratio 1: 4 according to regulation V.

The agents obtainable by the above-mentioned processes are dye-affine and have with dyeing Vat and sulfur dyes are excellent even in very low application concentrations equalizing effect. As a rule, they are used in aliphatic amines, at a normal temperature of 45 concentrations of 0.2 to 1 g / l treatment bath. carry out. The duration of the condensation is in the rest of the established dyeing processes As a rule - depending on the grains used - the dyes mentioned when using the level components - between about 10 and about 60 minutes. siermittel according to the present invention unchanged. In any case, the reaction must be interrupted before the invention brings particularly advantageous results formed products become insoluble in water; this 50 according to the invention leveling agent for vat dyes is taken by testing during the implementation with very little migration capacity, their type

Easy to control of samples.

The water-soluble condensates formed in this way generally have an average molecular weight between 600 and 1500.

The preparation of the substances to be used according to the invention is explained in more detail below. For the However, no protection is sought for production within the framework of this property right. The parts mentioned are Parts by weight.

I. 47.5 parts of dipropyl ether-y, j ″ -dicarboxylic acid and 33 parts of dipropylenetriamine are ^{heated to 200 °} C. for 1 hour while stirring and at the same time distilling off the volatile components. 68 parts of a light brown, viscous oil which dissolves well in water are obtained.

II. 54 parts of acrylic acid are mixed with 31 parts of dipropylenetriamine and 0.1 part of hydroquinone with stirring application has caused great difficulties so far. They have no surface-active properties and develop no foam in the dye bath; likewise, they do not show any dye-dispersing or protective colloids Properties. One can use the ones that are suitable for dyeing with the dyes mentioned Kinds of fibers in each processing stage, e.g. B. as flake, card sliver, strand or piece goods, in the presence of the remedies explained above with success regardless of color. The leveling agent can also be used for aftertreatment use, which has the purpose of leveling out unevenly unusual colorings afterwards. Another advantage is that in the presence of the in 65 new means at any temperature - also at the maximum temperatures sometimes required and possible for vat dyes - be nuanced can; that means any amount of dye

can be added without, as is otherwise customary, first having to lower the dyeing temperature.

The funds are always with those in vat dyeing customary protective colloids and dispersants, such as formaldehyde-naphthalenesulfonic acid condensation products or lignosulfonic acids, can be used together. The addition of dispersants is z. B. required if process water that contains not negligible amounts of Ca and Mg ions contains, must be used for the preparation of the dye baths.

It is known that condensation products of polyethylene polyamines and dicarboxylic acid or disul on acid halides with the majority of the waterless Dyes form water-insoluble precipitates, so-called lacquers, and are therefore used to make them water-resistant of dyeings with such water-soluble ones Dyes are usable.

It is also known that higher molecular weight condensation products from compounds with at least two reactive groups which can react with one another to form esters or amides, are useful as animalizers for cellulosic fibers; are for the same purpose too already high molecular weight compounds from aliphatic amines with at least two amino groups and halogen-free aliphatic Λ, / 3-unsaturated monocarboxylic acids has been proposed. Animalizing agents are fiber-affine according to their intended use. It was therefore not to be assumed that the substances to be used according to the present invention were excellent Dye-affine leveling agents for vat and sulfur dyes would be that with the water-soluble the reduced forms of these dyes do not form any insoluble precipitates.

The percentages given in the following examples are weight units. You are referring to that Dry weight of the textile to be treated.

. .
example 1

Hanks of cotton was dyed with 2 ° / ₀ of a vat dye violet (CI 60 005/1956) according to the procedure in addition without aids. It was then that per liter of 5 g of sodium dithionite and 12 mL of sodium hydroxide solution (38 ° Be) contained in "blind vat", together with the same amount unstained Baumwollstranggarns without further additives in a liquor ratio 1: 45 minutes treated at 6O ⁰ C twentieth The initially uncolored material was hardly colored after this treatment. If, on the other hand, 0.5 g / l of the oligomeric acid amide I from dipropyl ether-y, y'-dicarboxylic acid and dipropylenetriamine was added to the blind vat, the dye began to migrate after a very short time, and the originally white textile material was after 45 minutes intensely colored after long treatment. Only very small amounts of dye remained in the liquor. In view of the good leveling effect achieved, the low loss of dye is surprising and of great economic advantage.

Example ₂

The superior effect of the agents used according to this invention is evident from the following comparative tests emerge:

Dyeing seven samples Baumwollstranggarn in seven different baths a) to g) with a Färbstoff combination of 0.35 ° / ₀ Indanthrengoldorange

3 G PIv. fine f. col. (C. I. 69 025/1956) and 0.30% Indanthr dark blue BOA PIv. fine. f. col. (C.I. 59 800/1956) according to the method IW in the following way:

In the 45 ° C warm dyebaths (liquor 1:20) charged with the dyestuff, the lye and the reducing agent, only half of the material to be dyed is initially added and the second half is added 4 minutes later. Both strands are then dyed to the end together with movement of the material for 45 minutes at 45 ^° C. and finished as usual. The baths contain the following additives:

N-methylpyrrolidön,
> _0.5 g / l polyvinylpyrrolidone,

d) 5 g / l of betam from pyndine and chloroacetic acid,

e) O ^ g / l of the polyglycol ether made from 1 mol oleyl alcohol

_A ™ ^a f,. ^Mo ' ^Amy . ? ^xy 7 _T '..... _n .

f) 0.2 g / l of acid amide II from acrylic acid and di-

, Ρ ^Γ ° Ρ ^γ , _{de <5} means _{like n}
%> ^{u / fg / 1 aes iVllueis like 1} ^

Both dyes have very different migration capacities and are absorbed at different speeds. In the staining samples a) one can clearly see that the first strand is predominantly colored dark blue, ie that the component with low migration capacity has remained in the places where it was absorbed within the first few minutes of the process, while only the golden orange component has migrated . In addition to a small amount of the blue component, the second strand mainly contains the orange component. Both strands show an extraordinarily large difference in color tone. The effect of the leveling agent can be recognized by the color shades of the two strands dyed in the same bath. The more similar these are to one another, the better the leveling agent has worked. In the case of the test dyeing f) the strands are almost completely the same in color, in the case of dyeing g) they are practically completely the same. The known agents used in ^ _6n p _{ar un} b g _s b) _unc jd) are only little effect, although they have been used in much larger amounts. Polyvinylpyrrolidone [coloration c)] cannot be used as a leveling agent; As a result of the high affinity for the dye, the result is a weak dyeing which also has considerable dye differences between the two strands. The so-called non-ionic leveling agents that have been in use for a long time, as used in dyeing e), have a clearly recognizable leveling effect, but the nuance is shifted as a result of the strongly pronounced retarding effect; the result is a shade in which the orange component predominates, without the differences in the shade of the two strands being able to be sufficiently compensated for.

Example 3

Warp beams made of cotton are made on a closed dyeing machine using the IN im Liquor ratio 1:10 with 2% indanthrene blue green FFB PIv. fine f. col. (C.I. 70305/1956) colored. This dye is known to be extremely poor in leveling and is used in warp beam dyeing usually not used for this reason.

In the usual way of working, the only leveling agent used is 0.75 g / l of Saureamides IV y, y'-thiodibutyric acid and diethylenetriamine added to the dyebath. The winding bodies show up

Claims (1)

7 8 after finishing in the usual way an excellent example 7 Levelness and coloration. In the rest of the liquor, previously boiled cotton poplin is placed on the remarkably small amounts of dye remain. Jigger in the liquor ratio 1: 5 in the usual way In the same way as the condensation product IV according to process IN with a combination of 1.2% are used as leveling agents such. B. the oligomeric acid 5 indanthrene olive green B PIv. fine f. col. (C.I. 69500 / amide V from succinic acid and piperazine in Mol- 1956) and 1% indanthrene yellow 3 R PIv. fine f. col. ratio 1: 1.5, I from Dipropyläther- ^ y'-dicarbon- (CI 70 805/1956) at 60 ⁰ C colored. The product shows acid and piperazine in a molar ratio of 1: 2 and XI from a restless picture, but above all there are strong nitrilo-triacetic acid and diethylenetriamine in the mole color difference between the inner and outer ratio 1: 3 suitable. io layers of the fabric: the olive green portion was . -IA mostly fixed on the outside. The goods cannot continue Example 4 are processed, since the yellow compo- Previously, absences are very much predominant on an automatic reel skid. If you use otherwise Boiled tricot fabric in tubular form made of cotton under the same conditions as a leveling agent 2 g / l des in a liquor ratio of 1:30 with 2% indanthrene blue BC 15 oligomeric acid amides III from acrylic acid and dipro- "Colloisol" (C.I. 69 825/1956) under the following bedinpylenetriamine, one obtains a well colored one dyed: goods with a uniform shade that suits all The liquor is charged at about 20 ^° C. with the additions of sodium hydroxide solution and sodium dithionite required for the process IN, 1 g / l of the oligomeric acid amide X from y, / - thiodibutyric acid and N-Me is added the mechanical yarn dyeing machine according to thyldipropylenetriamine in a molar ratio of 1: 1 and the tanners are made of rayon yarns according to the IN calculated amount of dye in the form of an up with 2% indanthrene brilliant green GG PIv. finely slurry in water. The material is added to conc. f. col. (CI 59 830/1956) in an operating Next 20 minutes in the dye liquor at 20 ⁰ C behan- water colored by about 8 ° dH 25, wherein the one Färbedelt, then increases within 30 minutes, the bath bad 0.5 g / l of the oligomeric amic acid VIII of temperature uniformly to 6O ⁰ C is 1 g / l Triätha- suberic acid and piperazine in the molar ratio 1: 1.5 and ethanolamine, and 0.5 g / l sodium nitrite, and brings the protective colloid for the dyeing in hard water bath over 10 minutes at 8O ⁰ C. after a further lg / l of the following German Patent 752 830 er-10 minutes at 8O ⁰ C is completed, the coloring, the 30 keeps handy reaction product of sulfite waste liquor and liquor contains only small proportions of dye . Dichlorodiethyl ether added. The dye pulls long-after finishing in the usual way shows the sam and evenly on the fiber. No disruptive foam is formed during the tubular fabric a perfect levelness and through-dyeing process; the coloration, which can be recognized by the fact that inner threads and threads do not float. The final liquor does not contain any outside of the material, no color differences 35 significant amounts of dye. The yarns are show. The nuance is clear and pure. after the usual finishing, it does not matter and is well colored. . . _T. The hue is not changed undesirably. If ti e 1 s ρ 1 e 1 _{If there is no} auxiliary additive, then the dye is absorbed very quickly on an automatic jigger, and the dyeing becomes uneven. Uses dyed raincoat poplin. Before that on a 40 one a surface-active leveling agent, z. B. the foulard with 0.5% indanthrene olive T PIv. fine f. col. Polyglycol ether of a fatty alcohol or fatty amine or (CI 69525/1956) padded tissue is developed in the liquor a quaternary ammonium compound with an oxyethyl ratio of 1: 5 on the jigger according to the IN process, so one also obtains level. In the developing bath there are not only colorings, but they differ considerably from the usual additions of lye, sodium dithionite and the desired hue. Apart from the fact that the padding liquor has no other auxiliaries other than 1.25 g / l dyeing due to the strong retarding effect of the acid amides I from dipropyl ether-y ^ '- dicarboxylic called surface-active leveling agents, essentially acid and dipropylenetriamine. The result is a level product that is lighter and has a very strong shade of yellow, well-dyed goods which displace a noticeably calm image. In addition, the dyebath foams, results. A low retarding effect of the leveling 50 so that the yarns float on the liquor. This means that it does not matter. mechanical moving becomes more difficult, sometimes. even made impossible, because otherwise 6 ^ g of _a ^ _mentioned polyglycol ether as an auxiliary On the tub, rayon yarns with 20% medium no level coloring would be achieved, a purple sulfur dye (CI 53440/1956) 55
in a liquor ratio of 1:30 at 95 ° C with 8% soda, % Sodium Sulfur and 50% Glauber's _{Salt 1 V 2} StUn- Patent ON SPRUCH; the colored. The color tends to bronze, is friction-resistant and irrelevant. A completely flawless use of water-soluble polyamides from a) Coloring is obtained, however, if the dyebath has 60 aliphatic, cycloaliphatic or aromatic 0.5 g / l of the oligomeric acid amide XI from nitrilo- see polyamines or heterocycles, the min- triacetic acid and piperazine as leveling agents contain at least two acylatable nitrogen atoms, are set. and b) «, ^ - unsaturated carboxylic acids, alipha- Equalizing tables, optionally containing heteroatoms, can be used with equally good success means the oligomeric acid amide XII from ethylene- 65 polycarboxylic acids or their amide formation diaminotetraacetic acid and piperazine in the molar ratio functional derivatives as leveling agents nis 1: 4 after use. when dyeing with sulfur or vat dyes. © 209 520/384 3.62