DEP0046231DA - Method of coloring with complex metal compounds - Google Patents

Description

Process for dyeing with complex metal compounds.

It has been found that with metal compounds of dyes that are sparingly soluble in water, valuable coloring

ά gene can be obtained when metal compounds used voh such dyes, which to a carboxyl group hydroxyl sites are free from in o-position and at least one but not more than twice an atomic grouping of the formula

X HO

a I Ib

contain * where X is a carboxyl or hydroxyl group, A is an aromatic and B is a ring-shaped radical, where the C-atoms indicated represent members of the mentioned ^ uge, and if these metal compounds are used in the form of such complexes, which, in addition to the metal, also contain ammonia or water-soluble organic bases.

The metal compounds to be used in the present process, which are sparingly soluble in water, can be the metals with the atomic numbers 2A to 30, for example those with the atomic numbers. 27 to 29 , but especially nickel and above

mainly contain copper in complex bonds. Particularly valuable results are obtained with such metal-containing, especially copper-containing azo dyes, which in the metal-free state are still soluble in water and are suitable for dyeing cellulose-containing materials, but which, as metal compounds, are sparingly soluble in water and, due to this property, are poorly suited for dyeing _? at least if one disregards dyeing from suspension, which method usually gives unsatisfactory results.

Metal compounds that are sparingly soluble in water are to be understood as meaning those which, as sodium salts in alkali-free Are sparingly soluble in water.

The dyes must contain an atom group of the formula mentioned at least once and at most twice. In this grouping, the azo group is, on the one hand, directly to an aromatic radical A, which can be, for example, a radical from the benzene or naphthalene series, and, on the other hand, directly to another ring-shaped radical B, e.g. likewise to an aromatic radical from the benzene or naphthalene series or an a heterocyclic radical _s bonded, for example, to a pyrazolone radical. As a rule, the present process gives particularly valuable colorations with those dyes which contain two such atom groupings.

The dyes to be used in the present process, which are sparingly or insoluble in water, can, for example, be metal complexes of dyes with the atomic grouping

COOH KO

be, for example, with the complex copper compound of the dye of the formula

OH HOCC COOH HO

CH ₃ H ₃ C ^

applies.

Metal compounds have proven to be particularly advantageous to fertilize ο, ο ¹ -dloxyazo dyes, that is to say of faz'bstoffen which are once or twice the atomic grouping

OH HO i t

-N = N -C A / \ B

contain. Among the metal compounds of o, o'-dioxyazo dyes, the copper compounds are particularly valuable. This contain once or twice the fltom grouping in the molecule, usually represented by the formula

0 - Cu - 0

I I

is shown. Those which contain this atom grouping in the following form, for example, are particularly suitable

0 -. Cu-0 0 - · Cu-0

1, j I

"% -N" N - / ™ \ "y ^ —N -N = N -C *

Copper compounds of this type which are sparingly to insoluble in water are known in greater numbers- They can be used in general, especially for the production water-soluble copper compounds known methods by treatment with copper-releasing agents from the corresponding metal-free azo dyes are produced, which the atomic grouping

OH OH

\ -N-H C

contain. Metal compounds of o, o ^s- dioxyazo dyes are also to be understood as meaning those which are composed of dyes with other atomic groupings, for example with the atomic grouping

0-alkyl OH

can be obtained by treatment with copper-releasing agents in such a way that the desired complex is formed during this treatment, e.g. in such a way that the copper complex formation takes place with splitting of the -0-alkyl group. In some cases, this can also be achieved with dyes that provide poorly soluble copper compounds by heating them with copper tetrammine compounds of ammonia in an alkaline medium for a long period of time »The method of the jkHn patent specification is particularly useful here», ^Η ΛΊ ^ζ 'ΑΎ 4 & Ö- & © -

. According to this method * which is characterized in that the treatment in the presence of hydroxyl

carries out group-containing aliphatic amines, not only the easily soluble but also difficult to produce soluble copper compounds of the specified type in a simple manner.

Examples of metal compounds that are sparingly soluble in water are, for example, metal compounds, especially copper » Mention should be made of compounds of the type of disazo dyes mentioned, which represent the atomic grouping

OHH O

¹ HO OH

! -N-N-R-X-R-N-N

^H 9 9 ^H.

contain, in which RXR is the remainder of a coupling component which is capable of coupling twice and specifically in the adjacent position z \ x to the specified hydroxyl groups and has substantive properties, which contains at least two aromatic nuclei and in which X is a direct bond or a bridge member.

In particular, metal compounds come into consideration here, which the atom grouping

contain, where X is a nitrogen-containing bridge member. A dye of this type is, for example, that of formula

The aforementioned general group also includes metal compounds which are sparingly soluble in water Disazo dyes with the atomic grouping

OH HO OH

^c ^ ΊΟ ^χ Ο? ^

H CH_

where X is a direct bond between the two benzene nuclei or a bridge member such as "CH = CH- and where the Benzene nuclei can also contain substituents, for example sulfonic acid groups. A dye of this type is one the formula

0 «- Cu-OC« «« »Ν - /""*%"" ¹ CIII ^ -Ν --- CO - Cu-0 Ι'Ν --- C _y NN _n 0 - NN-

₅ 3 3 CONiI ₂

Above all, however, for the present process compounds are those which have the aforementioned atom grouping

contain and which, for example, from the corresponding copper-free Parbstopfen with the atomic grouping

OH HO OH OH

-α

^V C -N = N - <_3 * /> NN C

OH H ₀ CO O-CH-HO

! 3,. 3 ι

Mc

can be produced, valuable, such as the copper-containing dyes of the formula

Ν-Ν—

HO-S-

——Ίί

_H0

-NH,

S0_H

0 — Cu

HO-CHp-OHp-HN-XsA .- N

HO-S

"NK-CH ₂ -CH ₂ -OH

HO ₃ S

O'I

Cu-.0 j

C -N-XsA.

- ^m "\ I UJ

J = C

CH

HU-CH ₂ -CH ₂ -HN-

3 0 — Cu

H ₃ C

Cu-O

HO S -

"NH-CH ₀ -CH ₀ -OH

HO-S-

0 — Cu «« - 0

* σ -N ^ n

-Cu -—- 0

Yy -N

CH, C = NH ₃ C

In the present process, the metal compounds of dyes, which are sparingly soluble in water, are used in the form of complexes which, in addition to the metal, also contain ammonia or suitable water-soluble organic bases. Water-soluble, primary aliphatic or alicyclic amines are particularly suitable for this purpose. Examples of suitable bases are the following: ethyl amines, n-propylamine, n-butylamine, η-amy larain, n-hexylamine, monoethanolamine, ethylenediamine, a-amino-p »diethylamino-ethane _# cyclohexylamine, also:

Diaethylamine, diaethanolamine, n-butyl-ethanol-amine, taurine. Particularly good results are achieved in some cases with monoethanolamine achieved.

According to the present method, two or more different bases can also be used at the same time »

The ammonia or the water-soluble organic bases enter the metal complexes, which are poorly or insoluble in water of the dyes, and the complex metal compounds obtainable in this way generally have the valuable property to give submicroscopically dispersed to true solutions in water. A number of them are also crystallized " bar; As a result, it can be assumed that these are precisely definable complexes in which the individual Components metal, dye and base are in a certain stoichiometric ratio to each other. These complexes are, however, “not very stable. It is common though

possible to deposit them in crystallized form in the presence of an excess of the base used; they disintegrate but apparently when dyeing by the present process * where the metal-containing dye apparently escapes the base is fixed as a practically insoluble pigment on the paser.

The metal compounds to be used according to the invention generally give colorations whose color strength reaches the color strength of those colorations which are obtained when a corresponding amount of the dyes free of metals and bases is colored by the post-metallization process. The dyeing obtained from a certain fraction of a mole (e.g. Tqqq mol) of a metal-containing dye according to the present process on a certain amount of textile material (e.g. 100 grams of cotton) is at least as strong as that obtained with the same fraction of a mole that is free from metal and bases corresponding dye to the same amount of the same textile material obtainable by a post-metallization process known per se. If the dyes to be used according to the present process contain the atomic grouping

0— «Cu—- 0

as the corresponding metal-free dyes are to be taken into account, which at the relevant point of the Molecule the grouping

OH OB

y \

ν --- ItS-.1 * 5 "w

• \

contain"

The complex metal compounds containing ammonia or organic bases and used for dyeing according to the present process can be used. can be produced in a simple manner by cran suspending the metal compounds, which are sparingly / insoluble in water, in water and adding the necessary amount of the Ease. In general it is advisable to use a certain excess of base and to warm up the tent. This reaction can be carried out in a relatively high concentration. In this way, valuable stock solutions are obtained which are suitable for the production of dye baths and which can then be diluted to the larger volume required for dyeing. However, if desired one can make the reaction in high dilution, that is, the '/ Tosliehen complex and the base directly in the dyebath voz ¹ to entering into the matching material to be colored in any order.

As a result of the instability of the complex, organic base-containing metal compounds in acidic medium In the present process, the materials to be dyed are primarily those that do not require an acid dye bath, but can be dyed from a neutral to alkaline medium, i.e. materials containing celixose such as linen, cotton and rayon or rayon made from regenerated cellulose. The dyeing can be done according to the known for direct dyeing cellulose

Dyes are customary methods, for example with the addition of sodium carbonate and sodium sulfate. The liquor ratio, ie the ratio of the amount of to be adapted to the coloring material to the amount of FärbeflÜHsigkelt 1st this widely varied and canoe largely to the demands of practice "This einfonüige and single-stage process results in accordance with the invention? U used dyes very

/ iii jäj5.r β strength, sb /

Uniform and strong colorations, which at least achieve those colorations in the authenticity properties which can be obtained with the appropriate, metal-free dyes according to the known post-metallization process »

In the French patent specification 808.258 § = pj a process is described according to which products to be addressed may be produced as complex compounds of metal-containing dyes and organic bases and used for dyeing. The dyes with which the colors described in this VorveröTfentliohung are, but always in dispersed form in the dye bath available and you consistently dyeings obtained with these products, which are weaker than those you get with AEEN corresponding metal-free dyes by the Nachraetallisierungsverfahren.

The following examples serve to illustrate the invention without restricting it in any way. Mean the parts by weight, the percentages by weight and the temperatures are given in degrees Celsius. Where the manufacture of dye baths and stock solutions is described, so-called condensation water (distilled water, that is obtained from Betrlobaöampf) can be used.

l part of _t Kypferverbindung of the dye of 1 mole of tetrazotised 3 * ^3! "'Dioxy = ^^ ¹ ·' -dlaminodiphersyl and 2 moles of i-oxynaphthalene-3-sulfonic acid are poured over with 200 parts of hot condensation · = water and the oil suspension is boiled after adding 2 parts of 24 # ammonia = the result is a clear blue color Solution from which the dye separates out as a crystalline complex when it cools,

The stock solution obtained in this way is prepared by diluting with water to 3,000 parts by volume and adding 2 parts len anhydrous sodium carbonate a dyebath, in which one enters at about 70 ° with 100 parts of pre-wetted cotton.

hdäj- _t

The temperature is withinH; Increased to the boil for 1/2 hour and kept boiling for 3/4 to 1 hour. Naoh 5 minutes of kosh duration 15 parts of crystallized sodium sulfate are added and, after boiling for 20 minutes, a further 15 parts of crystallized sodium sulfate are added. When the dyeing is complete, the cotton is rinsed thoroughly and dried. A reddish blue coloration of very good wash and lightfastness.

To prepare the stock solution of 2 parts of n-amyl amine, diethylamine or n can take ammonia harden - Butylaethanolarain _s may be added with similar results are obtained.

1 part of the copper compound of the dye from 1 mole of tetrazotized 3,3'-dioxy = 4,4'-d! Aminodiphenyl, 1 mole of 1- (2-SuIfO-phenyl) -azo-2-amino ~ 5-o; kynaptithalin- -7-sulfonic acid and 1 mole of 2-amino-5-oxynaphthalene-7-sulfonic acid are poured over with 200 parts of hot condensed water and, after the addition of 2 parts of n-butylamine, boiled. Then, a complex crystallizes in part of * he so in the mother liquor in part _1, fine suspension is present | in the dye bath, however, it completely dissolves.

The stock solution is prepared by diluting it with water to 3000 parts by volume and adding 2 parts of anhydrous Sodium carbonate a dyebath, in which one enters at about 70 ° with 100 parts of pre-wetted cotton. Within; l / 4 hour it is raised to the boil and kept at the boiling temperature for one hour, with 15 parts each after 5 minutes and after 20 minutes of boiling crystallized sodium sulfate are added. The dye pulls out well and gives a pure blue color of very good Wash and lightfastness.

To prepare the stock solution, instead of n-butylamine, 2 parts of monoaethanolamine, ethylamine, n-propylamine, Cyclohexylamine ethylenediamine or a-i-amino- / 3-diaethylamino-ethane are added, with a similar result is obtained.

The copper compound used to prepare the stock solution can be prepared as follows;

95 parts of the trisodium salt of the dye are dissolved in 2000 parts of warm water with the addition of 4 parts of sodium hydroxide. 100 parts of monoethanolamine are added to this solution and an am / non-alkaline copper sulfate solution consisting of 50 parts of crystallized copper sulfate, 80 parts of 25% ammonia and 150 parts of water is added dropwise at 60-70 °. Most of the copper compound separates out after a short time. The mixture is heated to 80 ° for a further 1 hour, 40 parts of sodium chloride are added, the dye is filtered off and dried.

Example 13.

™ ■■ ' um i ^ ~ pm ■ 1.1 Il ■ mm · " » m ι »

1 part of the copper compound of the dye from 1 mole of tetrazotized 3,3'-dioxide, ¹ I ¹ -diamlnodiphenyl and 2 moles of 2-0xyaethylamino-8-oxynaphthaXin-6-suXfonsäure is poured over with 200 parts of hot water and after addition of 2 parts n -Propylamine boiled. The result is a clear solution which is diluted to 3000 parts by volume with water. This dilute solution is heated to 60-70 ° and 2 parts of anhydrous sodium carbonate are added. 100 parts of pre-wetted viscose rayon are added, the temperature is raised to the boil and kept at the boil for one hour, 15 parts of crystallized sodium sulfate being added after 5 and 20 minutes from the start of boiling. This is followed by rinsing and drying. A gray-blue dyeing of good washfastness and lightfastness is obtained.

The Stamailösimg can also gat with 2 parts of n-butyl. arain or n-amylamine can be added.

1 part of the copper compound of the dye is made from 1 mol of cetrazotlertem 3,3 '-dloxy-4,4 ¹ -diamlnodlphenyl and 2 mol of 1- {8'-e-alfo-2 ¹ -naphthyl) -3-methyl-5-pyrazolone - Poured over 200 parts of hot water and, after adding 2 teaspoons of α-amino-0-diaethylamino-ethane, boiled. The clear stock solution obtained in this way is poured into 2800 parts of water at 60-70 °, the dye going into real solution as a complex. After adding 2 tellane trisodium phosphate, 100 parts of cotton are added and the temperature is increased to a boil within 1/2 hour while the goods are agitated. The mixture is boiled for one hour, adding 15 parts of crystallized sodium sulfate each after 5 and after 20 minutes of boiling. When the staining is complete, the bath is well drawn out. The goods are thoroughly rinsed and dried. The result is a clear, blue, bordeaux coloration with a remarkable wash finish and excellent lightfastness.

The stock solution can also be made up with 2 parts of monoethanolamine or ethylenediamine.

1 part of the copper compound of the dye from 1 mol tetrazo tier tem 3..3 ¹ -Dioxy- ^ V-diaminodlphenyl and 2 mol 2-Am.tno-5 ~ oxynaphthalene-7-sulfonic acid is poured over with 4-00 parts of hot condensed water and boiled with 2 parts of n-butylamine. The stock solution obtained in this way is dissolved in 2β00 parts of water

of 60 = 70 °, which contains two parts of anhydrous sodium carbonate in solution. 100 parts of pre-wetted cotton are now poured in, heated to a boil within 1/4 hour and dyed at the boil for one hour, 15 parts of crystallized sodium sulfate being added after 5 and 20 minutes. “After this time, the dyebath is completely exhausted. A pure, bright blue dyeing of very good washfastness and lightfastness is obtained.

The stock solution can also contain n-butylamine instead of

or 2 parts Monoaetfoanolaaiin, n-Araylamine, Ethylamine / Cyclohexyl-

amine.

The copper compound used to prepare the stock solution can be made as follows:

76 parts of the sodium salt of the dye are dissolved in 2000 parts of warm water with the addition of 10 parts of anhydrous Dissolved sodium carbonate and 50 parts of monoethanolamine. A solution consisting of is slowly added to this solution at 60-70 ° 50 parts of crystallized copper sulfate, 50 parts of monoethanolamine and 150 parts of water. The mixture is heated to 80 ° for one hour, then sets a little sodium chloride is added, the deposited dye is filtered off and dried.

Λ JL
1 part dsr obtained by demethylating copper u ^ g

KMpferverbindu (i3 the dye from 1 mole tetrazotlertem 3,3 ^! -Dlmethoxy -'- a ^ V »diamino-diphenyl and 2 moles S-QxyaethylaTilno-

is with 200 parts of condensation water and 2300 parts of water from

T) ⁰ , which contains 2 parts anhydrous sodium carbonate and 2 parts AethyJa * nin »dose / i. After a short turning over, 100 parts of cotton are added and the temperature is brought to a boil within 1/4 hour. After 5 minutes, 20 parts of crystallized sodium sulfate are added, and after 20 minutes another 20 parts are added. After einstü.idlgeTs cooking the product is thoroughly rinsed and dried gi. The result is a pure, strong green! Ih blue dyeing with very good wash and lightfastness.

Instead of ethanol, ethanolamine, dietethanolamine, isopropylamine or α-amino-β-dlaethylamino can also be added to the dyebath. ethane can be added.

The z \ xT preparation of the stock solution used copper »connection can be made after the uiiea Patent Str.) Beach rubbed method *

1 part of the copper compound of the dye from 1 mol of tetrazotlated 3 * 3 '~ Dloxy = 4, V-cUaminod! Phenyl and 2 mol 200 parts of hot condensed water are poured over l- {6 '-Sulfo-2' ~ naphthyX) ~ 3-mefehyl ~ 5-pyrazolone and after adding 2 parts Ethylenediamine boiled »The stock solution is passed through a fine sieve into the dye liquor from 2800 parts of 70 ° warm condensate · entered water and added 2 parts of anhydrous sodium carbonate. Then you go with 100 parts pre-wetted cotton and let the temperature rise within 1/2 hour to boilj naoh 5 and after 20 minutes of boiling add 15 parts each crystallized sodium sulfate and holds a total of one hour at the boiling temperature. The bathroom is well drawn. It results a full Bordeaux dyeing of remarkable washfastness and very good lightfastness.

Similar results are obtained with 2 parts of ethanolamine.

Example 8.

1 Tell the copper compound of the dyestuff from 2 moles of diazotised ^ 2-amino ~ l-oxy-4-benzoic acid anilide and ^s l mole of the triazines of 1 mole of cyanuric chloride, 2 mole of 2 ~ amino-5-oxynaphthalene-7-sulfonic acid and 1 Mol of aniline is boiled with 200 parts of hot condensed water containing 2 parts of ethanol arain and 0.5 parts of anhydrous sodium carbonate, a clear solution being formed. The dyebath of 300 parts of condensed water is charged with 2 parts of anhydrous sodium carbonate and set to 70 °, after which the stock solution is added.

W6,

100 parts of cotton are poured in, brought to a boil within 1/2 hour and boiled for an hour, after 5 and after 20 minutes, 15 parts of crystallized sodium sulfate are added each time. The bath throws well undressed, and the resulting The color is a pure ruby red with very good light and washfastness.

The copper compound used to prepare the stock solution is made as follows

115 parts of the dye are dissolved in 2000 parts of warm water with the addition of 8 parts of sodium hydroxide. One is prepared from 50 parts of crystallized copper sulfate, 80 parts of 25 ^ strength ammonia with 150 parts of water Add solution and heat to 80 ° for 1 hour. The copper compound is deposited by adding sodium chloride and filtered off and dried.

Claims (1)

Claims. lo) Process for dyeing with metal compounds of dyestuffs which are sparingly soluble in water. draws ^ that one uses metal compounds of such dyes which are in the o-position to a carboxyl group standing hydroxyl groups are free and at least once but at most twice ine atom grouping of the formula X HO containj where X is a carboxyl or hydroxyl group, A is an aromatic and B is a ring-shaped radical _? wherein the carbon atoms indicated represent members of said hinge, and that these metal compounds in the form of such complexes ver · _s = employs the metal besides the also contain ammonia or water soluble organic bases " 2o) Process according to claim ₈ characterized labeled in I = zeichnetj that metal compounds of dyes used _$ containing the atomic grouping of the formula given twice. 3e) Method according to claims 1 and 2 _? characterized by the fact that metal compounds of disazo dyes are used, which represent the atomic grouping CH HO C HO OH X CN = NRXRN = NC ^
₁ / \ HO OH
contain j, in which R- = X <=> R represents the remainder of a coupling component with noun properties which can be coupled twice and in each case adjacent to the specified hydroxyl groups, which contains at least two aromatic nuclei and in which X is a direct bond or a bridge member means ^ in which, furthermore, A ₁ and Ap are each an aromatic _? denoted radical containing the specified C "= atoms as ring members Ac) method according to claims 1 to. ^? characterized by the fact that metal compounds of disazo dyes are used which indicate the atomic grouping OH HO OH ^ = N ΛΑ a / ho-s-IJJ-x- contain ^ where X is a nitrogen-containing bridge member and A- and A ₂ each uniquely aromatic _$ denotes the specified C-atoms as a ring = members-containing radical. 5 «) Process according to claims 1 to 3 _S characterized in that metal compounds of disazo dyes are used which have the atomic grouping OH HO OH HO VHHC * I ^ * ^ - ^ I ^ C -N = NC ^ _A / ^N C = NH * C / \ _A ¹ CH, CH ^ ² contain ^ where X is a direct bond or a bridge member and A _n and a «j © an aromatic? denotes the specified radical containing C <= atoms as ring members. 60) Method according to claims 1 and 2 _? as a result denotes that metal compounds of disazo dyes are used, which indicate the atom grouping j ²¹ HO OH ^{H <} ? contain? where EL and Bp each denotes a ring-shaped radical containing the specified carbon atoms as ring members. 7 «) Method according to claims 1, 2 and 6 _? through this characterized ₉ that one metal compounds of a dye of the formula used, in which 1 is a «KH_ group or a β ^ Oxyaethylamino · = group. 8 ") Method according to one of claims 1 to 7 ₈ according to" characterized by the use of metal compounds ₈ which contain a complex-forming metal with one of the atomic numbers 27 to 29 »<> 9 ") Method according to claim 8", characterized by Pafenfanwcit the use of copper-containing dyes. DipL-lng.E.SplanGi-nsnn Hamburg 36 Neiy WaSI 10, 4th floor \ nrut 347900 - -