DEP0034089DA - Dyeing processes and preparations for the implementation thereof - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Patent attorney Dipl.-Ing. E. Splanemann

Hamburg 36
Neuer Wall 10.4th floor

p 2 * 089 ^ cL - / $ 4n / D.

Dyeing processes and preparations for the implementation thereof.

Chromium-containing acidic monoazo dyes which each have a hydroxyl group and a hydroxyl group in the ortho position to the azo group Have aminogroup, have in part the disadvantageous property when dyeing from a sulfuric acid bath, in particular but, if the dyeing time is prolonged, cloudy and unsightly dyeings can be obtained, suggesting a decomposition, probably a partial one Entmetalllslerung of the dye is due. Even if this disadvantage depends on the chemical constitution The dye, the dyeing process and the fiber to be dyed occurs to a very unequal extent, but it is as Disadvantage to be considered, which adheres to the group of dyes mentioned.

According to known methods
2. ^ 22,586). This disadvantage can now be largely eliminated by coloring formaldehyde or formaldehyde-releasing agents in particular with the addition of lower aliphatic aldehydes. Such lower aliphatic aldehydes are highly volatile. The dyeing must, however, be carried out at a high temperature, boiling in the cone, and the aldehyde must always be present in the dye bath in sufficient quantities to be effective.

ⁿ araus a result, this method, although it ka lead to good results ■; vi, in its operation, with positive disadvantages Istr "afflicted These consist essentially in a • S-II, saw g.cossen consumption of aldehyde by Verdarnpfungsvarluste is still increased considerably. If the dyeing takes longer, the volatile aldehydes have to be added repeatedly. This makes the predatory results offc unsafe.

The present invention relates to a process in which the advantages of the addition of aldehyde have been utilized and at the same time the disadvantages occurring in the above-mentioned known process are eliminated. Compared to the known method, the new method of sending out 'has the advantage that the colorings can be nuanced with the same, a similar or a different color, if desired, in a fresh p.:'.de - without a new aldehyde .susafcs is required. This new process for the production of dyeings of acid-dyeable complex chromium compounds of ο-oxy "O ¹ -aminomono-azo dyes is characterized in that the dyeing process is carried out in the presence of a water-soluble aldehyde which has an affinity for the fiber.

Under o-Osy-o * -amino-monoazo dyestuffs are those monoazo dyestuffs which contain the atomic grouping

OH

contain. ,, wherein. A denotes hydrogen or an optionally substituted alkyl radical (but preferably hydrogen), monoazo dyes of this type and their complex metal, in particular chromium compounds, are known in large numbers = they can, for example, be derived from azo components that couple to an amino group, in particular 2-amines naphthalene and its Sulfonic acids on the one hand and derived from c-oxydiazo compounds on the other hand, the presence of at least one sulfonic acid group in at least one of the components ensures that the dyes obtained are suitable for dyeing from acidic baths. Aminonaphthalene-5-% -6- and -7-sulfonic acid and 2-'-minonaphthalene-3> 6- -4,7- or -5,7-disulfonic acid are suitable. Examples of diazo components are 2-amino-1-oxybenzene-4-sulfonic acid, 2-amino-1-oxy-4-nitrobenzene-6-sulfonic acids, 2-amino-l-oxy-6-nitrobenzene-4-sulfonic acids, 2-amino- 4-ohIor ~ l "oxybenzene-6-sulfonic acid, 2-amino-4-methyl-1-oxybenzene-5- or -6-su If on acid, 2-amino-4- or -5-nltro-l- oxybenzolj, 2-> amino-4-chloro => 5-nitro- or -6 ~ nitro-l-ox3 ^r benzpl called.

The metal-containing and in particular the chromium-containing dyes obtainable from these components show different behavior when dyeing. A limited number of them can also be used without the addition of aldehyde in a satisfactory manner, i.e. can be colored without suffering demetallization. This applies e.g. to certain chromhaj.

term dyes derived from o-aralnophenols with two nitro groups or from o-aminophenols with one sulfonic acid group and one nitro group. The present process is of particular advantage when using chromium-containing dyes which are derived from nitroaminophenols without further substituents and from 2-nmlnonaphfch, alln-sulphonic acid; for example when using dyes from 2-amino-5-nitro-2-loxybenzoX and Aminonaphthaline- * -6- or -7-sulfonic acid or 2-aminonaphthalene ~ 5,7-, -4,7- or -3,6 -disulfonic acid; also with dyes that differ from 2-amino-1-oxybenzene- '4 -sulfonic acid or 2-amino-4-chloro-1-oxybenzene-6-sulfonic acid or 2-amino- ² i -'> methyl-1-oxybenzene- Derive 5- or -6-sulfonic acid and 2-aminonaphthalene.

According to the present process, the complex chromium compounds produced in substance are used for coloring used. Among these products, in particular those which contain an atom of chromium bonded to a dye molecule prove to be advantageous for dyeing according to the present invention Proceedings.

The aldehydes to be used in the present process must be water soluble. Above all, there can be such Aldehydes come into consideration which, in addition to the aldehyde group, have a soluble acidic group such as, for example, a carboxyl group or, expediently, a have a sulfonic acid group.

The aldehydes must also have an affinity for the fiber. Among aldehydes, which have an affinity for fibers,

these are to be understood as those that are at least 60 percent absorbed by the fibers, with the following test procedure It is decisive for the decision whether this condition is fulfilled or not.

In a solution which, in 1900 parts of distilled water, contains 4 parts of HgSO ^ and 0.6 parts of the 100% to be tested Aldehyde or the 0.6 parts of pure aldehyde contained, one goes with 100 parts of dry wool at 60-70 ° and slowly heats the solution to the boil. After 1/2-second boiling, 40 parts of 10% sulfuric acid are added and acts at the boil for another hour. The wool is then squeezed out so that the squeezed out liquid is absorbed into the solution flows back. The latter is supplemented after cooling with distilled water to a volume of 2000 parts and used for analysis (solution l).

The pressed-out Full is inserted into I9OO parts of distilled water of 50 ⁰ J ^ T dorfc and left without changing clothes, until the temperature at 20 ⁰ JK''gesunken is what takes about 2 hours. Then it is pressed out as indicated above. The solution obtained in this way is made up to 2000 parts by volume with distilled water and also used for the analysis (solution II).

The amount of aldehyde present in solutions I and XI must be determined using methods which

ij. make it possible to determine the aldehyde in a dilution of 1 ι 10 to 1:10 with sufficient accuracy. The determination

can therefore ζ »3» be carried out according to those methods known per se in which these conditions are met »

By subtracting the two values found for solutions I and XI from the total amount of aldehyde used the amount of aldehyde fixed on the Paser can easily be calculated »The value found in this way then results in the total amount Aldehyde related, the above-mentioned measure of the fiber affinity.

The aldehydes can be colorless or colored. Here, colorless aldehydes are to be understood as meaning "which are not." contain chromophoric groups.

Colorless aldehydes which can be used with advantage in the present process are, for example, those which one of the atom groupings

-HN-C-NH- I Γ M ^or -HN-C X-NH-

but do not contain chromophoric groups. These atom groupings can be attached to an aromatic radical, preferably one be bound to those of the benzene series. The aldehyde group and the solubilizing group can be in the same or in various such residues bound to one of the specified atomic groups may be found ». It can also be more than one Aldehyde group and / or soluble group in the molecule of such fiber-affine groups. Connections be present »

The aldehydes with the abovementioned Afcom groups can be prepared using methods known per se. So you can aldehydes, which unfold the group -NH-OO-HN-, by linking two molecules of an aromatic one Prepare aminaldehyde sulfonic acid using phosgene.

Aldehydes, which contain the cyanuric residue, prove to be particularly valuable. This can also include those Products are used in which only two carbon atoms of the gyanur residue are bonded to an -NH group and in which the remaining carbon atom of the cyanuric group is bonded to a halogen atom or a hydroxyl group.

Such aldehydes containing the quinazollnrest or cyanuric radical can also be according to known methods Build up methods by, for example, adding the chlorine atoms of 2,4-dichloroquinazolln or cyanuric chloride ^ in a suitable order replaced by substituents of the type indicated, the easiest in cyanuric chloride being expediently the easiest reacting amino compounds (e.g. aniline or ammonia) with the last remaining ^ O-Cl residue.

To build up the aldehydes containing the above-mentioned atomic groups, for example, the following compounds can be used in the specified catfish are used:

/ U ^ compounds which contain the acidic residue of the groups mentioned.
Phosgene.

Cyanuric chloride,

2,4 -D. 1 c h, 1 ο right. h i na ^ cIl n ..

B ^ _- compounds which contain -NH radicals of the groups mentioned.

Ammonia, alkylamines such as butylamine, mono- or di-ethanolamine, aniline, benzidine.

Sulphonic acids of primary or secondary aliphatic amines such as taurine or N-methyl-taurine.

Amlnobenzene mono- or disulfonic acids such as l-aminobenzene-2-, -3- or -4-sulfonic acid, l-aminobenzene ^^ - disulfonic acid, aminonaphthalene mono-, di- or trisulfonic acids such as 1-aminonaphthalene-4- , -5-, -6-, -7- or -8-sulfonic acid, 1-aminonaphthalene-3, 6-, -k, 8- or -3,8-disulfonic acid, 2-aminonaphthalene-5-, -6- ,, -7- or -8 ~ su If on acid, 2-aminonaphthalene-3,6- or -6,8-disulfonic acid.

Diarainobenzenesulfonic acids such as 1,3-diaminobenzene-4-sulfonic acids, 1,4-diaminobenzene-2-sulfonic acid.

4,4'-DIaminodiphenyl-mono- or -disulphonic acids such as 4,4'-Dlaminodiphenyl-3-sulphonic acid or 4,4'-diamino-diphenyl-2,2 ¹ -disulphonic acid.

4,4 · -diaminostilbene-2,2 · -disulfonic acid and ^ rw ·. . Amlnodiaryl ether sulfonic acids such as 2-amino-4 ^! -methy1-1,1'-diphenylether-4-sulfonic acid.

Amino aldehydes such as 2-, 3- or 4-aminobenzaldehyde, 2-chloro-5-ainino -1-benzaldehyde.

Aminoaldehyde sulfonic acids such as 4-amino -! - benzaldehyde-2-sulfonic acids, 3-amino-1-benzaldehyde-6-sulfonic acid, 3-amino-1-benzaldehyde -4-sulfonic acid.

PA.2461O (HA50

It can easily be seen that a very large number of such water-soluble aldehydes have an affinity to have fiber, can be produced. Some typical representatives of such compounds are shown in the exemplary embodiments and processes for their production are described.

The present process is in no way restricted to the use of aldehydes with the atom groupings mentioned j aldehydes of other compositions can also be used, provided that they are water-soluble and have affinity for the paser.

Are colored, water-soluble aldehydes, which have an affinity for the Paser, and which are therefore themselves dyes are used, it is advantageous to choose those which by themselves are the yellow pasers, preferably color greenish yellow tones. It is easy that the use of yellow-coloring aldehydes is particularly favorable Understandable, as the blue-green hue that the complex chromium compound provides, only a little and that of the dyer mostly desired direction, namely to yellow is shifted.

Apart from the fact that the colored water-soluble aldehydes must have an affinity for the fiber, they can be used as desired be built. Azo dyes, especially yellow, are particularly suitable for use in the present process Coloring monoazo dyes ,, For example, the monoazo dyes of the general formula are suitable

OH.

' ^H 3

In what f? ₃ denotes a radical from the benzene series and Rp denotes a radical from the benzene or naphthalene series, with at least one sulfonic acid group and one aldehyde group in the dye molecule - preferably one of these two groups each, very good. The dyes of this composition not only have the favorable property of producing pure, mostly greenish yellow hues, but they also produce uniform colorations with very good fastness properties. Examples of dyes of the above general formula, some of which are described in German Patent 409,563 and Swiss Patent 106,929 *, those of the following constitution can be given;

C-Zs J [J

J [JN ^ N SC ₃ H

OH

fl

OH Cl i

ν- *

CH.

OH

0— -N- <f ~ \ .- S0 ,,

PA.246100-3.451

OH Cl

j! -NC "N. -SO ₀ H

HCVS-N = NC ^ I f *

11 N ^ c ^ N dl

° CH

CH ₃

OH
.C — N - <"" - \ - S0 _o H

I)

CH

OH Cl
.CW-

0 KJ ^ ^{N SO} 3 ^H COOH

The present process is not limited to the use of a single water-soluble aldehyde, which has an affinity for the fiber, in combination with a single complex chromium compound of an o-oxy-o ¹ -aminoazo dye. For example, particularly valuable dyeings are obtained if the dyeing operation is carried out with a complex chromium compound of an o-Qxy-o ¹ -aminomonoazo dye in the presence of two water-soluble aldehydes, both of which have an affinity for the fiber, but one of which is colorless (e.g. one Cyanuric derivative of the composition given above) and the other colored (e.g. a monoazo color, which corresponds to one of the formulas given above).

Fibers to be dyed are those which are usually produced with acidic chromium-containing dyes are dyed, in particular animal fibers such as silk and, above all, full wool, possibly also casel fibers and other similarly behaving pasers; also synthetic fibers made from super polyamides or super polyurethanes. The term Affinity to the Paser is to be related to the Paser used in each case.

The amount of the present method to be added to the dyebath aldehyde BEZW. the aldehyde can vary within wide limits. However, it is an advantage of this method that, as already indicated, very favorable results can be achieved even with very small amounts. Even a very small addition of around 0.10 % (based on the amount of material to be colored) can produce a good effect. In many cases it is advisable to add about 0.2 to 1 % of an aldehyde.

The staining with the addition of water-soluble aldehydes, plural marriage possess affinity to the fiber, may, after the complex for dyeing chromium compounds acidic azo dyes customary methods to be made, ie, (calculated on the fibers to be dyed) advantageously in the presence of h to 8% sulfuric acid and at boiling temperature, if desired with the addition of salts such as sodium sulfate.

The subject matter of the present s ^ ind also dye preparations for carrying out the above process, which in addition to an acidic dyeable complex chromium compound of an o-oxy-o'-aminomonoazo dye nooh at least one contain such water-soluble aldehyde, which has an affinity for the fiber.

In such preparations, both the chromium-containing dyes and the aldehydes in the form of their water-soluble metal salts, in particular as alkali metal salts such as sodium salts. For example, you can by mixing the individually prepared salts of the dye and the aldehyde or by mixing them together Neutralization of a mixture of the corresponding chromium-containing dye and aldehyde in an aqueous medium and subsequently Drying can be obtained. If desired, these preparations can contain further additives such as salts, e.g. sodium chloride or sodium sulfate and iKS of dispersants.

The following. Examples serve to illustrate the invention without restricting its scope in any way. The parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees of Celsius.

In a dye bath containing 1.5 parts of the complex chromium compound of the dye from dlazotlertem 5-nitro-2-amino-l oxybenzene and 2-aminonaphtha.lin-6-sulfonic acid, 3000 parts of water, 10 parts of crystalline. Sodium sulfate, kO parts of 10 ^ iger sulfuric acid and 0.2 parts of the compound of the formula

CS \ -NH-C ^ ^ C

O V N ^ N

HC -.

i!

contains 100 parts of well-wetted wool at 60 to 70 and slowly heats the bath to the boil. After 1/2 hour When boiling, another 40 parts of 10 # strength sulfuric acid are added and the color is boiled for 1 1/2 hours. Then the wool becomes like Usually rinsed with cold water and dried. It is colored in even, pure, green tones. Without the addition the compound of the formula above gives a more cloudy and bluer coloration with otherwise identical execution.

The compound corresponding to the formula above can be prepared as follows:

A solution of 19 »5 parts of 1-aminobenzene-4-sulfonic acids, which reacts neutrally in a lacquer nut! Sodium in 200 parts of Wasier allowed within 30 minutes to add dropwise to a suspension of 18 parts of cyanuric chloride in 800 parts of water. The cyanuric chloride should be in the finest possible form, and the reaction tem-

temperature is set to 0-5 ° by indirect cooling. Dilute sodium carbonate solution is added continuously, so that the reaction mixture on Congo paper always shows a purple reaction. After about 3 hours it is condensation theoretically required amount of 5.3 parts of sodium carbonate consumed.

IA /

A solution is then allowed to run into the reaction mixture thus obtained within 30 minutes, which solution is then dissolved in the heat of 12.1 parts of 3-amino -! - benzaldehyde in βΟΟ parts of water with the addition of 11.5 parts of 30% hydrochloric acid and has received subsequent cooling to 60 °. The reaction temperature is allowed to rise to about 30 °. With constant stirring at 30.degree. To 40.degree. C., dilute sodium carbonate solution is then added continuously, always so much that the reaction mixture reacts neutrally. It takes about 10 hours until the theoretically required amount of 10.6 parts of sodium carbonate for the condensation has been consumed, the first half, which essentially only releases the base from the chlorohydrate of aminobenzaldehyde,

XA

is used up within a short time.

Which had become gelatinous reaction mixture, 6.5 parts 27 ^> aqueous ammonia added and the whole within one hour at 9 to 98 & ⁰ heated. A permanent, weakly alkaline reaction occurs. After cooking for two hours.

At the reflux condenser, traces of impurities are filtered off while hot. One still gives it to the piltrat hot state hydrochloric acid to weakly Congo acidic reaction, whereby the condensation product separates out as a slimy mass. After cooling, this is separated off, stirred in 200 parts of water and added by adding sodium carbonate solution Brought into solution until the litmus-neutral reaction. The condensation product is obtained by evaporating this solution as the sodium salt in the form of a slightly brownish colored substance »

If desired, the product can also be used after it has reacted with the ammonia and the solution has been separated off remove minor impurities by adding sodium chloride, filter off and dry.

According to the information above, the aldehydes of the formulas can also be used

N Ji

Uf S \ * Mtl ι * > A VM .Λ. PA U XJf S \. KTU _ / ^ · Vf * -JUW _ V ** "" ^ie \. -.QPi U

WO ~ ^> * - £ in * \ j L -itJM - <r \ -οϋ-, π WL - / ^> -WH -ν ν -fin - <^ -dU-, λ

be prepared if instead of 19 »5 parts of 1-amlnobenzene-4-SU If ons from sodium 19.5 parts of l-amlnobenzene-3-sulfonated sodium or. 24.5 parts of l ~ aminonaphthalln-4 ~ sulphonic acid catalyst are used. Xni the latter).

Chloride Tinnäfclg., Since the product fails for the most part by itself.

If you use the complex chromium compound from diazotized! 5-nitro-2-ami.no-1-oxybenzene and. 2 ~ Ami.nonaphfchalin-4, "7 - disulfonic acid or the complex chromium compound of the dye from diazotized 5 ~ N: l.tro-2 ~ amino ~ 3 .-- oxybenzene and 2-ß-oxyaethylaminonaphthalene-7-sulfonic acid for dyeing in the manner indicated with addition one of the * in this example specified aldehydes, you also get pure green colors, while without the addition Clay aldehyde gets cloudy and bluer colorations with otherwise the same execution.

If the dye bath instead of the triazine derivative described in Example 1 is 0.1 part of the compound formula

% -HN - / - \ - S "> -NH <P ^ C -NH -

v ⁿ

HO - / S -WH -C% -HN - / - \ - S "> -NH <P ^ C -NH - / \ -CH

\ / ΓΙ S ^ ^

«ΓΙ S ^ hv ⁿ

₂ NH ₂

and if you proceed exactly as described in game 1, you get the same result as in the first paragraph of example 1.

The dialdehyde of the above formula can be prepared as follows:

A litmus-neutral solution of 34.4 parts 4.4 ^! -Diamino-diphenyl-2., 2 * -disulfonic acid in 300 parts of water is added dropwise to a suspension of 36 parts of cyanuric chloride in 160 parts of water over the course of one hour, the temperature being kept at 0-5 ° by indirect cooling. The reaction mixture is always kept weakly minerally acidic by adding a solution of sodium carbonate. After about 3 hours, the amount of 10.6 parts of sodium carbonate required for condensation has been consumed. A solution is now allowed to run into the reaction mixture obtained in this way within a period of 0 minutes, which is obtained by dissolving 24.2 parts of 3-amino -! - benzaldehyde in 1200 parts of water with the addition of 23 parts of 30% hydrochloric acid in the heat and received subsequent cooling to 60 °. After about 12 hours, the amount of 21.2 parts of sodium carbonate required for condensation has been consumed. 13 parts of ammonia are added to the reaction mixture over the course of an hour

heated to 96-93 ° C. A permanent, weakly alkaline reaction occurs and the initially gelatinous mass becomes crystalline. You hold at Qo-98 ^{0 for} half an hour, then set 400 parts

Sodium chloride is allowed to cool and the precipitated sodium salt is filtered off at room temperature away. The body thus obtained can, if necessary, be purified by recrystallization from water.

The same effect as with the product, the production of which has just been described, is achieved by using the

Coloring indicated in this example undertakes with the addition of the product that is obtained when 4,4'-di-amino stilbene-2,2'-disulfonic acid is reacted in the manner indicated with cyanuric chloride., 3 ^ ^A raino-HDenzaldehyde and ammonia .

Instead of the triazine derivative described in Example 1, 0.1 part of the triazine derivative of the formula _{Q is added to the dyebath}

It

HC- / s -HN <T ^ Z -HN - / S-CH

A,

IG-Ss. -HN <r ^ C -HN -

NH ₂

to. otherwise proceed exactly as described in Example 1 and achieve practically the same result.

The triazine derivative of the above formula can be prepared as follows ϊ

A laokmus-neutral solution of 20.1 parts of 3-amino-benzaldehyde-6-sulfonic acid in 500 parts of water is left inside / one hour to a suspension of 18 parts of cyanuric chloride, to be added dropwise in 800 parts of v / water. Then you work continue as in example 1 (3 »paragraph). After carrying out the reaction with the ammonia in the manner indicated and the solution has filtered off trace amounts of impurities, the hot piltrate is added 200 parts of sodium chloride. The decay falls as it cools down

binding of the above formula as a pale brownish colored sodium salt. It is filtered off and dried.

Instead of the triazine derivative described in Example 1, 0.1 part of the urea derivative is added to the dyebath the formula

-NK-C-HN-.

y- ^CH

NaO ₃ S SO ₃ Na

and proceed exactly according to the information in Example 1. The result is a coloration that is still somewhat yellower than that of example 1.

, The urea derivative of the above formula can be prepared as follows:

In a solution of 24.5 parts of 4-aminobenzaldehyde-2 "sulfonic acids! Sodium in 350 parts of water are mixed under good Stirring initiated within 6 to 8 hours at 20-25 ° 5.5 parts of phosgene. By adding dropwise dilute sodium carbonate solution the released hydrochloric acid is continuously neutralized. After the reaction has ended, the precipitated urea is a derivative filtered off and, if desired, purified by dissolving. When dry it is a pale brownish color Substance.

Instead of the triazine derivative described in Example 1, 0.2 part of the dye is added to the dyebath

the formula

OH Cl

-SO-Na

HC-ZS-N = NC ^ I ¹¹ JJ ^N r- «N

ov y ~ * ^N

CH-

/ _ obtainable by domes of diazotized! 3-Amino-1-benzaldehyde with 1- {2 ', 5 ^! Dichloro-4 ¹ -sulfo) phenyl-3-methyl-5-pyrazolon_ / to and the procedure is otherwise exactly according to the instructions of Example 1 obtained in this manner, a likewise pure and gleiohmässige, but still more yellow green coloration than the under Example 1 available.

With a very similar result can be used instead of the above

indicated dye one of the dyes of the formulas

HO \

C ~ S \ 0 V

HC- / S-N-N-C * I

^ CN. SO ₃ K

COOH

HO I

^and HC-ZS-NNv, -

"L J ^

CH
be used in the manner indicated.

PA.246! 00 * -3A5i

In a dyebath containing 1.5 parts of the complex chromium compound of the dye from diazotized 5-nitro-2-amino-1-oxybenzene and 2-aminonaphthalene-6-sulfonic acid, 3000 parts of water, 10 parts. Sodium sulfate, KO parts of 10 ^ iger sulfuric acid, 0.15 part of the compound of the formula

HC- / S ₁ -NH-C ^ C-HN-

NH ₂

and 0.1 part of the dye of the formula

OH Cl

IO

contains 100 parts of well-wetted wool at 60 to 70 ° and slowly heated the bath to the boil. After 1/2 an hour, gladly. When boiling, further kQ parts of 10% sulfuric acid are added and the color is boiled for 1 1/2 hours. The wool is then rinsed with cold water as usual and dried * It is dyed in evenly yellowish green tones.

Instead of the dye of the above formula you can also use the dye of the formula

HO CH ₃

Jj --N - Λ """" Y -SC ₃ H HC - / SNN <Ζ I ^ "~

ti I I Ν.Λ-. M.

and come to practically the same result.

75 parts of the complex chromium compound of the dye from diazotized! 5-Nitro ~ 2-amino-1-oxybenzene and 2-aminonapbthalene-6-sulfonic acid are combined with 25 parts of the compound of the formula

Yt HG - / Ν -NH ^ \ -HNf- / S-

^ -SO ^ Na

3 I.

mixed. In a dyebath containing 2 parts of the dye preparation thus produced , 3000 parts of water, 10 parts of crystallized sodium sulfate and 40 parts of 10 ^ ige sulfuric acid , 100 parts of well- wetted wool are placed at 60 to 70 ° and the dyeing process is carried out as in the example 1 at the end. A wool dyed in uniform, pure yellowish green tones is obtained.

The following preparations result, after the above

or a similar process, also very valuable, even green to yellowish green colors:

PA.2461OO-3A5II

70 parts of the complex chromium compound of the dye from oil-azotized 5-nitro-2-amino-1-oxybenzene and -Aminonaphthai in -6 -sulfonsäure,

50 parts of the dye of the formula

HO Cl

.C-N-.

HC-Xs-N-N-C ^ I ~ -y

OV _t 3

CH-

b) 70 parts of the complex chromium compound of the dye from diazotized 5-nitro-2-amino-X-oxybenzene and 2-aminonaphthalene-β-sulfonic acids

22 parts of the compound of formula

iC -Xx -NH -cf \ - -HN - / \

lQ Π Q-

- ^S0 3 ^Well

SJ

NH ₂

8 parts of the dye of the formula

HO Cl

ό ν ^ r * ^s0 3 ^Na

c) The individually prepared aqueous solutions of 70 parts of the complex chromium compound of the dye from diazotized 5-nitro-2-amino-1-oxybenzene and 2-aminonaphthalene-6-sulfonic acids

22 parts of the compound of formula

JL HC - / \ -NH -C ^ C -HN -

s Q

NH ₂

8 parts of the dye of the formula

HO Cl

HC - A. -NeN-C ^ I

SV? ~ ^{N S0} 3 ^Na

PtJ

are mixed with one another, and evaporated to dryness the whole.

Example 8.

- * ■ - ·· * m, «dft» r «« ll HU im mn «. ■ * .-« ■

In a dye bath that diazotized 1.5 parts of the complex chromium compound of the dye! 4-chloro-2-amino-1-phenol and 2 ~ aminonaphthalene ~ 6-sulfonic acid, 3000 parts of water, 10 parts of Glauber's salt, 40 parts of 10% sulfuric acid and

0.3 parts of the compound of formula

HC ~ / \ -NH -C \ -HN -jAw

0 V NN V

NH ₂

contains 100 parts of well-wetted wool at 60 to 70 ° and slowly heats the bath to the boil. After boiling for an hour and a half, add a further 40 parts of 10% sulfur.

acidic and stains 1 1/2 hours at the boil. The wool is then rinsed with cold water as usual and dried. It is colored in uniform green-blue tones. Without the addition of the condensation product, a cloudy gray color is obtained Coloring.

In a dyebath containing 1.5 parts of the complex chromium compound of the dye from diazotized 4-chloro- 2 -amino-1-phenol-6-sulfonic acid and 2-aminonaphthalene, 3OOO parts V / water, 10 parts Glauber's salt, 40 parts 10 #lge sulfuric acid and 0.3 part of the compound of the formula

HC - / S -NH -C ^ C -HN -,

iS U - ^S0 3 ^Na

1C- / N -NH-C OVN

contains 100 parts of well-wetted wool at 60 to 70 ° and slowly heats the bath to the boil. Nttch 1/2 hour boiling is given more. 40 parts of 10% sulfuric acid are added and the color is boiled for 1½ hours. Then the Wool rinsed with cold water as usual and dried. It is in uniform, pure, bluish green tones colored. Without the addition of the condensation product, a cloudy, grayish coloration is obtained.

Claims (1)

PA.246100-l4.5i Fa tentajisgrüche._ 1.) Process for the production of dyeings from saue? dyeable complex chromium compounds of o-0;: y-o '-aminomonoazo dyes, characterized in that the color process is carried out in the presence of a water-soluble aldehyde, which has affinity for the fiber ν 2.). Process according to claim 1, characterized in that a colorless aldehyde is chosen. 3 ·) Process according to claim 2, characterized in that an aldehyde is selected which has one of the atomic groups -HN-C-NH »or -HN-C ^ X-NH- ·· Ii I O N N contains. 4.) Process according to claim 2, characterized in that an aldehyde is chosen which has the atomic grouping contains. Procedure according to Pa i; entered-spoke 1, thereby exemerated, that ?; v & m.i as Aldehvü a; i.ldeh; vagc ^: upp (inhal> lgcn: Dye, preferably a yellow-coloring monoazo dye containing aldehyde groups. 6.) Process according to one of claims 1 to 5, characterized in that complex chromium compounds of such o-oxy-o ¹ -aminoazo dyes are chosen which are derived from nitro-aminoxybenzenes without further substituents and from 2-aminonaphthalenesulfonic acids. 7.) Dyeing preparations, characterized by a content of acid-dyeable complex chromium compounds of o-oxy-o ¹ -amlnomonoazo dyes and a content of water-soluble aldehydes which have an affinity for fibers. 8.) Coloring preparations according to claim 1, characterized by the content of a colorless aldehyde. 9 ·) dyeing preparations according to claim 8, characterized by the content of an aldehyde which is one of the Atom groupings -HN-C-NH- oöer -HN-c '\ -NH-0 N contains. 10.) Furbepräparate, according to claim 8, characterized by the content of an aldehyde, which the atomic grouping contains, 11.) F6, rbepräparate according to Ba Cent claim 7 , characterized by the content of an aldehyde-group half-cigenic dye, preferably a yellow monoazo dye containing aldehyde groups. 12.) Ptrbepräparate according to one of the claims to 11, characterized by the content of a complex chromium compound of such an ο-oxy-ο'-aminoazo dye, the derived from a nitro-amino-oxybenzene without further substituents and from a 2-aminonaphthalenesulfonic acid. Pcrtenfanwoft D? PL »! N§. T ;. . ff General VollmaditNr.33 / * 8