DE2022364A1 - Metal-containing azo dyes, their production and use - Google Patents

Description

Dr. W. See !!; ,, OipUng. P- WhA

Dipl.-lny. C-. D ^ nnenberg

Or. V. f; V ^,? reil-Kowarzik

Dr. P. Wabhold, Dt. D. Gudel

6 Fronklurt / M., Gr. Eschenheimer Str. 39

S A N D O Z AG. Basel, Switzerland

Case 15-5066 / a

Metal-containing azo dyes, their manufacture and use

The purpose of the invention are metal-containing bisazo dyes, which especially suitable for dyeing paper.

The invention thus relates to metal-containing disazo dyes of the formula

0-Me-O Q-Me-0 SCLH

N = N- ^

(D /

SO H

where Me is a metal atom and the rings A and / or B can be further substituted.

The dyes of the formula (i) are mainly in the form of their alkali metal salts or their ammonium salts, but preferably as the sodium salt.
The metal atom preferably represents a copper atom; it can

but also stand for a nickel atom.

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The dyes of the formula (I) can be prepared by adding 1 mol of a tetrazotized 4,4'-diamino- ^ j ^ '- dimethoxy- or 3j3'-dihydroxydiphenyls with 1 mole of 2-hydroxynaphthalene-6,8-disulfonic acid and 1 mole of 2-hydroxynaphthalene-3 »6-disulfonic acid and the resulting azo dye with a metal donor Means treated.

The coupling can be carried out by methods known per se, for example in an aqueous alkaline medium, at temperatures from 0 to 20 ^° C. and, if appropriate, in the presence of a buffer.

The metallization can also be carried out according to methods known per se, e.g. in aqueous acidic or alkaline Medium and for example at elevated temperature / e.g. at boiling temperature.

The aromatic rings A and / or B can be formed by halogen, such as chlorine, bromine or fluorine, or by alkyl or alkoxy radicals further ^^ be substituted, for example by low molecular weight Alkyl or alkoxy radicals containing, for example, 1 to 3 carbon atoms. However, these rings are advantageously unsubstituted.

It is advantageous to metallize with a copper or nickel donor Means, 'for example with copper sulfate, chloride or -acetate.

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The new dyes are suitable for dyeing paper or also for dyeing or printing cellulose fibers such as cotton, linen, hemp, etc. by the usual methods, e.g. after the French patent 1,551,512. The dyes of the formula (I) are particularly suitable for Production of colored, sized or un-

glued paper ":
The dyes of the formula (I) can be used to produce concentrated solid, stable preparations which contain 30-90 # of dye and 70 to 10 # of an adjusting agent, for example ammonium sulfate, sodium chloride, etc. They can also be used to produce concentrated, stable, liquid preparations which contain 5 to 30 % dye, 5 to 1% , preferably 10-20%, of an amine, for example diethanolamine, and 40 to 90% water.

These preparations are excellent for making of dye tapes, padding liquors or printing pastes.

The preparations can contain further aids, e.g. FKrbehilfsrdLi tel, such as pH-stabilizing aids or detergents.

The preparations can be made by mixing and, if appropriate, briefly Heating the ingredients are produced. They can be used as real solutions or as a dispersion, if necessary after dilution with water, for dyeing paper.

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The preparations have the advantage of being easier to use . There is no annoying dust when weighing dye powder.

The preparations can be stored for several months at room temperature * constant They are not sensitive to frost and are insensitive against fungal attack.

With the dyes of the formula (I), genuine, level, reddish-tinged blue dyeings with good results are obtained on the substrates mentioned Fastness properties, se.B. good light fastness and good * wet fastness properties. From French patent 1 03.6 771 the dye is of the formula

HO., 30 - Cu - PO - Cu - O SO, H

or, T _3, i i:. ⁷ e "iatriiifüsaiK © to Färbeii of resenerf-örter C-ellüIose 'known in the trade is the dye of Förnisl (&) gum dyeing paper smpfohlen,

It ίΑΖ ffiieriv-i ^ 'i ^ rd that al'S dyes ύ & τ Formal (I) In Wa £ »s <·· - · - t> .i .'.-- j ·. ·; ···: .c -i3i-.it-JA SiM ;, άοΏ, es lasoesi is: te & a-11 them erte ^ a prepare aqueous solutions.

ιΐί-Α the dyes there? Fo ^ aiel (1) a «iaj. Nuance of

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white papers are more suitable and less sensitive to sizing than the dyestuff of the formula (a) and, in addition, there is a risk when dyeing paper with the dyestuffs of the formula (I) the mottling not at all, while the dye of the formula. Ca) mottled on paper. The whitening is mainly ■ Described by Berthold Cornely in "Das Färben von Papier", page 185.

In the following examples, the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius.

1. Example of the preparation of the dyes of the formula

O-Cu-O 0-Cu

1 «tetrazotization; .

■ 97 »6 parts of 4.4 ^l -diamino-5.3 ^l -dimethoxy-l, l'-diphenyl are used in

800 parts of water entered at 20 °. Then 276 parts of 50% hydrochloric acid are added and the mixture is stirred to form a homogeneous suspension. The mixture is then cooled to 2-3 ° by adding 350 parts of ice. Now letting a solution within J) O minutes, consisting of 58.4 parts · Natriumni- trit dissolved in J500 parts of water, zufHessen. The temperature is kept between 3 - 5 ° by the occasional addition of ice. The mixture is stirred for 1 hour at this temperature, then the excess sodium nitrite is destroyed with sulfamic acid

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2. clutch;

126 parts of 2-hydroxynaphthalene-6,8-diLsulfonic acid are used in 500 Parts of water entered and then dissolved by adding 66.5 parts of 3Q sodium hydroxide solution. After entering 220 parts of soda are cooled to 3-5 ° and then the tetrazotized ^, V-diamino-Jjy-dimethoxy-ljl'-diphenyl in ■ poured into a thin stream. The mixture is stirred well for 90 minutes and

then adds 135 parts of 2-hydroxynapthalene-3,6-disulfonic acid, dissolved W in 900 parts of water. After the reaction has ended, parts of crystallized copper sulfate and 364 parts of 25% ammonia are added and the mixture is stirred at 90 ° -95 ° for 15-20 hours. The metallized dye is precipitated by adding sodium chloride and isolated by filtration. After drying, 440 parts of the dye of the formula (b) are obtained

2. Example of a solid dye preparation

80 parts of a salt-containing dye powder with a content of 88 # of the dye of the formula (b) are in a mixer with 20 parts of a coupage agent, preferably Glauber's salt, mixed homogeneously. The dye preparation is very soluble in water.

3. Example of a liquid dye preparation

28 parts of a salt-containing Färbstoffpulvers with a content of 90 $ of pure dye (b) were dissolved 14 parts of water and 73 parts in Diaethanolarain "This liquid dyeing preparation exhibits a very good LageiggpgigfyLf | fy ₂ BAD ORIGINAL

Instructions for coloring paper

100 parts of chemically bleached sulphite are used in a dutchman cellulose ground in the presence of water. 3 parts of the preparation according to Example J5 are added to this mass. After 15 minutes the gluing and then its fixation takes place.

The paper produced in this way has a reddish cast medium intensity blue shade. The dyeing has good fastness properties such as alcohol fastness; it is particularly very wet strength. The wastewater is colorless. ™

If instead of the preparation according to Example 3, the Dyestuff as obtained according to Example 1, the result is an equally good coloration with the same good properties.

Dyeing instructions for cellulose fibers

A dye bath of 3000 parts of softened water, 2'Teilen anhydrous sodium carbonate and 1 part of the after. Example 2. Preparation dye is available at 30®'alt 100 parts, wetted cotton t charged. After adding 10 parts of sodium sulfate, the dye liquor is within 30. Heated to 100 ° for minutes, 10 parts of sodium sulfate being added to it at 50 ° and 70 °. The dyeing is continued for 15 minutes at 100 °, another 10 parts of sodium sulfate are added to the bath and it is now allowed to cool. »At 50 ° the dyed cotton is taken out of the bath and dried at 60 ° - it is ta eliaom red-

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dyed a pungent blue tone.

If, instead of the preparation according to Example 2, the dye as obtained according to Example 1 is used, the result is an equally good coloration with the same good properties.

The dyeings are light and wetfast. For example, you have a good fastness to water, washing and perspiration. The dyes migrate well and are boil-proof and resistant to high temperatures.

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ij i) 9 * j <!? / / <i PDO i

Claims (12)

wherein Me denotes a metal atom and the rings A and / or B can be further substituted. 2. Metal-containing disazo dyes according to claim 1 correspond to formula (I), in the form of their alkali metal salts or their ammonium salts, 3. Metal-containing disazo dyes according to claim 1 · the correspond to formula (i) in the form of their sodium salts. 4. Metal-containing disazo dyes according to claim 1 of formula (I) in which the metal atom is a copper atom means, 5. Metal-containing disazo dyes according to claim 1 * which correspond to the formula (I) in which the rings Ä and Jf are not further substituted « 6. Process for the preparation of disazo colors of the formula (I) characterized in that 1 mol of a tetrazotized '4,4'- 009847/1802
. BATH ORIGINAL ΑΌ Diamino-; 5> 3 '~ dimethoxy- or - ^, ^' - dihydroxydiphenyls with 1 mol 2-hydroxynaphthalene-6,8-disulfonic acid and 1 mole of 2-hydroxynaphthalene-3,6-disulfonic acid coupled and treated the resulting azo dye with a metal donor. 7. Use of the dyes of the formula (i) according to claim 1 for coloring paper. 8. Use of the dyes of the formula (i) according to claim 1 for dyeing, padding or printing cellulose fibers. 9. The according to claim 7 with the dyes of the formula (i) stained paper. 10. The according to claim 8 with the dyes of the formula (I) colored, padded or printed cellulose. 11. Use of the dyestuffs of the formula (I) according to patent claim 1 for the production of concentrated, solid "stable preparations" Contains 30 "$ 90 dye and $ 70-100 of a thickening agent" 12. Use of the dyes of the formula (I) according to claim 1 for the production of concentrated, stable liquid preparations containing 5 to 30 % of dye, 5 to 1% of an amine and. 40 to QO ^ water « The patent attorney BATH ORIGINAL 9847/1102