DE2038473C3 - Metal-containing, sulfonic acid group-containing 2 to 1 azo complex dyes, process for their preparation and their use - Google Patents

Description

The present invention relates to metal-containing sulfonic acid group-containing 2: 1 azo complex dyes Formula I.

NQ ₂

¹ OH

(N = NR ₄ L

(R ₄ -N = N)

wherein R ₄ (A) is the radical of the formula II

^R i
NH

{n + m) moles of the amines of the formula III of the form

(H)

NH

R ₃

H ₂ N

(IV)

or (B) an optionally substituted by halogen, nitro, cyano, hydroxy, amino, alkyl or alkoxy groups with up to 4 carbon atoms, sulfo, carboxy, sulfonamido, carbonamido or alkylsulfonyl groups with up to 4 C atoms in the alkyl radical substituted phenyl, naphthyl, hydroxynaphthyl, sulfonaphthyl or hydroxysulfonaphthyl, and the substituents R, R ₁ , R ₂ and R _{3 are} hydrogen, halogen or nitro, cyano, hydroxyl, amino , an alkyl or alkoxy group with up to 4 carbon atoms, a sulfonic acid; Carboxyl, sulfonamide or carboxamides or an alkylsulfonyl group with up to 4 carbon atoms in the alkyl radical or an alkyl or alkoxy group with 1 to 4 carbon atoms optionally substituted by halogen atoms, the hydroxyl or cyano group, Me an iron, chromium or Cobalt atom and η and m together is 1, 2 or at most 3, with the proviso that the dye molecule has at least one radical of the formula II.

The new dyes can be obtained if (n + m) moles of the diazo compound are obtained from amines of the formula

(HI)

60

and, if the sum η + m is 2 or 3, the (it + τη) moles of the amines of the formula III used may be identical or different to one another, and the azo compound obtained in substance; metallized with a metal donor to the compound of formula I.

The dyes according to the invention can also be obtained by adding 1 mole of a compound of formula VI

NO ₂

O ₂ N

R ₄
with 2 moles of a compound of the formula

OH OH

HO

N = N

(VI)

OH

(V)

NO,

NO ₂

couples, where at least 1 mole of the used with (n + m) mole of the diazo compound from amines of the formula III couples, where at least 1 mole of the (n + m) moles of the amines of the formula III used corresponds to the formula IV and, if the sum

ir m 2 oftef .3 Äst- iJie in +, * ») Mol 4er emgeseteteia

* + w J <xier 2.

For <öe HerslidSittftg the ' gea kiäoBKOQ Eise »-, Ohxwö- or

Good A ^ .oiaj-b (StoSe eitt & piöiieii the

MH

MO ₅

HO-O
but especially the formula

OH

SOjH

J = * N -— <O> -

Me

HO

NO ₂

or the formula

NO ₂

10

SO, H

NH

O V-NO ₂

wherein Fe means an iron atom
Similar good azo dyes correspond to the formula

or the formula

; r of the formula

) betw. the formula

or the formula

12th

NO ₂

OH

-NO ₂

HO ₃ S

NO ₂

HO

NO ₂ R ₃ R2

NO,

OH

N = N- ( ^O ) - ^{N == N}

/ Y

HO ₃ S

O> -NH

<r

or the formula

NO,

HO ₃ S _r;

O> -NH - ^ (j ^>
R ₂ '

(XVI)

SO ₃ H

In the formulas VIII and IX as well as XIV to XVI the radicals R ₁ 'and R ₂ ' each denote a hydrogen or halogen atom, a nitro, carboxyl or sulfonic acid group or an alkyl or an alkyl or cyano group which is optionally substituted by halogen atoms Alkoxy group having 1 to 4 carbon atoms.

The coupling can be carried out by methods known per se; z. For example, the coupling of the diazo compound from picramic acid can resorcinol to the monoazo dye of the formula V in an aqueous, alkaline medium at temperatures of from - 10 ⁰ C to room temperature, optionally with the addition of sodium chloride are carried out.

The coupling of the monoazo dye of the formula V to Endfarbstoffmit a diazotized diazo component aminodiphenylamine or another may also be in an aqueous, alkaline medium at temperatures of from - 10 ⁰ C are performed to room temperature.

The metallization is advantageously carried out in an aqueous medium, optionally with the addition of an organic Solvent carried out alone. In the case of metallization, it is advantageous to work in an acidic environment Medium, but the metallization can optionally also be carried out in a neutral to alkaline medium be performed.

Suitable compounds of chromium are e.g. chromium trioxide, chromium fluoride, chromium sulfate, chromiformate, Chromium acetate, potassium chromisulfate, or ammonium chromium sulfate. The chromates, e.g. B. Sodium or potassium chromate or bichromate are ideally suited for metallization.

As iron or cobalt compounds z. B. iron or cobalt formate, acetate, sulfate or -chloride.

Halogen in any case represents bromine or fluorine, but preferably represents chlorine. Possibly advantageous substituted alkyl or alkoxy radicals are low molecular weight, for example 1, 2, 3 or 4 carbon atoms containing alkyl or alkoxy radicals. If these radicals are substituted, they contain halogen atoms, the hydroxyl or cyano group; these residues therefore particularly represent methyl, ethyl, Propyl, isopropyl, butyl, isobutyl, methoxy, ethoxy,

NO ₂

Cyanoethyl, hydroxyaryl, chloromethyl, chloroethyl. Residues of diazo components are diazo compounds of optionally substituted aminobenzenes, Aminonaphthalenes, aminohydroxynaphthalenes, aminonaphthalenes - sulfonic acids, aminohydroxynaphthalenes - sulfonic acids.

The compounds of formula 1 can carry 1 to 6 sulfonic acid or carboxylic acid groups, advantageously if they contain 1 to 4 identical or different such groups.

The metal-containing compounds of formula 1 are used for dyeing or printing leather. the The metal-containing dyes obtained are distinguished by good leveling power and constancy of shade on leather of different tanning, good dye build-up in neutral to slightly acidic Dyebath, good fastness to sanding on chrome plum leather; good fastness to water, washing, perspiration and formaldehyde, good fastness to ironing and good fastness to light. The dyes are based in particular on leather with a lower affinity, e.g. chrome-vegetable tanned or leather tanned by chrome synthesis, to deep, rich nuances; they also have a high Neutral drawability on this material.

Compared to the closest comparable known dyes from the French patent 14 31548 the dyes of the formula have a better solubility, especially in water, and better leveling ability on grain leather.

The new dyes have a better penetration capacity than the closest comparable dyes the DT-AS 1111318.

They also have better migration fastness in PVC than the closest comparable dyes of British patent 1099641 and better Color strength than the closest comparable dyes of US Pat. No. 21 36 650.

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

example 1

199 parts of 2-amino-4,6-dinitrophenol are diazotized in the usual way and at pH of 9 with 110 parts of 1,3-dihydroxybenzene according to be

known methods for the compound of the formula V coupled. The isolated compound of formula V is stirred in water and with the diazo compound obtained in the usual way from 309 (1 mol)

Parts of 4 - amino - 4 '- nitro coupled -T- sulfodiphenylamin at a value of. 9

To 1 mole of the disazo dyes of the formula thus obtained

N = N

OH

1 mol of the monoazo compound of the formula V is added and the mixture, dissolved in water, with 300 parts of iron sulfate are metallized at a pH of 4 and a temperature of 95 to 100 °. The iron-containing dye is isolated with sodium chloride and dried. He's a brown powder which dissolves in water with a dark brown color and leather, especially weakly affine, i.e. with vegetable or synthetic tanning agents retanned chrome leather in intense, real red-brown tones dyes of good lightfastness.

Example 2

2 moles of the compound of formula V obtained according to Example 1 are mixed with 1 mole of iron sulfate, dissolved in 500 parts of water, in water at a pH of 4 and the mixture is heated to 98 to 100 ° for one hour. After metallization, the dye is isolated and suspended in 500 parts of water. The suspension is at a pH of 9, the diazo compound of 309 parts of 4 - '- nitro -T- added dropwise sulfodiphenylamin.' - amino 4 After coupling, the dye is isolated by adding sodium chloride. When dry, it is a dark brown powder that dissolves easily in water and dyes leather in real red-brown tones.

Example 3

1 mol of the compound of the formula V prepared according to Example 1 is stirred into 500 parts of water and at a pH of 9 with the diazo compound from 132 parts (V2 mol) of 4-amino-2-sulfodiphenylamine coupled. After coupling, the diazo compound is made up of 86 parts at a pH of 9 l-Amino-4-sulfobenzene added and the mixture Stirred for 1 hour. After coupling, the solution is adjusted to a pH of 4 and with 150 parts of iron sulfate are added and the mixture is heated to 100 ° for 1 hour. The resulting metal complex dye is isolated by adding sodium chloride. He poses in dried State is a dark brown powder, which is easily soluble in water and leather in dark, reddish brown real tones.

Example 4

1 mol of the compounds of the formula IV prepared according to Example 1 is stirred into 500 parts of water and at a pH of 9 with the diazo compound from 264 parts of 2-amino-2-sulfodiphenylamine coupled.

Another mole of the compound of the formula V prepared according to Example 1 is dissolved in 500 parts of water stirred and at a pH of 9 with the diazo compound from 172 parts of 1-amino-3-sulfobenzene coupled.

The two disazo dye solutions thus obtained are combined, the pH is adjusted to 4 and the Solution by adding 300 parts of iron (3) chloride and heating for one hour 90 to 100 ° metallized.

The resulting dark red-brown metal complex dye is made by adding sodium chloride isolated.

When dry it is a water-soluble powder, the leather in dark red-brown real ones Tones colors.

The following table shows the structural design further dyes indicated. They can be prepared according to the information in Examples 1 to 4. They correspond to the formula I, with the metal-containing compound of the formula VI (1 mol) in column A, in column B the amines of the formula IV (1 mol), in column C the amines of the formula III [(n + m-1) Mol] and column D shows the shade of the color of the iron, cobalt and chromium complex compound Leather is indicated.

example
No.

AWAY

Ver amines of the formula IV

binding
of formula VI

Amines of formula III

D.
Fe

Co

Cr

CH ₃ SO ₃ H

5 the same. H ₂ N- ^ oV-NH-ZoV-NOj CH ₃
O) -SO ₃ H

dark-dark-dark red-violet-violet brown brown brown

Starting

At- A B

^ ¹ Ver Amine der Fonnd iV

Amines of the Funnel HI

TOdVl

COOH

dessl

O ^ NH-YoY-

desjl H _{J ^} ^

the same

Yo,

-NH- (O) -NQ ₂ SO ₃ H

SO ₃ H

SO ₃ H

H ₂ N-Vo) -NO ₂

SO ₃ H

desgL H ₂ N-YON-NH-Zo ^) - NO ₂

SO ₃ H

D. Fe

Cd Cr

dark-
Red-
Brown dark-
violet-
Brown dark
violet-
Brown duo
Red-
Brown dark-
violet-
Brown dark
violet
Brown dark-
Red-
Brown dark-
violet-
Brown dark-
violeti-
Brown dark-
Red-
Brown dark-
violet-
Brown dark-
violet
Brown

the same H ₂ N- i HO ₃ S SQjH dark-
raw
Brown dark-
violet
Brown dark
violet
Brown H ₂ N OH IO the same H ₂ N- H ₂ N- <
< Mk
SO ₃ H dark-
Red
Brown dark-
violet
Brown dark
violet-
Brown OH 11th the same H ₂ N- (^ 0Y-SO ₃ H dark-
Red
Brown dark-
violet
Brown dark-
violet
Brown NO ₇ . 12th <S> - ^NH - <°>
SO ₃ H <ö> ^NH - <°>
SO ₃ H CH ₃ NH ^ oV-SO.f -NO ₂ NO ₂

likewise. H ₂ N- ^ o ") SO ₃ H

NH-YoY-NO ₂ dark- dark · dark red- violet- violet brown brown brown

NO _{2 the} same. H ₂ N-YoY-NH-YoY-SO ₃ H dark- dark- dark red- violet violet brown brown brown

SO ₃ H SO ₃ H

likewise. H ₂ N-Yo

dark? dark- dark photo- violet- vioieu-

brown brown brown

continuation

example No.

connection of the formula Vl

Amines of the formula IV Amines of formula III

16 the same. H, N- <O

17 also Η, Ν

18 the same. H ₂ N-ZoV-NH

COOH

SO ₃ H

N / A

Cl
H ₂ N-ZoS-NO ₂

SO ₃ H

19 the same.

?, 0 the same.

21 the same.

H ₂ N - <^ C?> - NH -ZcTV-NO ₂
SO ₃ H

NO ₂

- \
O

SO ₃ H

Fe Co Cr

dark- dark- dark red- violet- violet-

brown brown brown

dark- dark- dark red- violet- violelthrauii brown brown

dark-

rol-

Brown

dark-

Red-

Brown

dark - dark vi.tlett - vinlellbraun brown

dark - dark purple - violet brown brown

O> SO ₃ H dark- dark- dark red- violet- violet brown brown brown

dark-dark-dark red-violet-violet brown brown brown

Dyeing example A

100 parts of freshly tanned and neutralized chrome grain leather are in a liquor of 250 parts Water of 65 ° and 1 part of that shown in Example 1 Dyestuff drummed for 30 minutes in the dyeing drum, in the same bath with 2 parts of an anionisehen Fettlickers treated on a sulfonated oil base for a further 30 minutes, and the leather in the usual kind dried and trimmed. A leather which is very evenly colored and has a reddish brown shade is obtained.

Dyeing example B

100 parts of calfskin suede are made with 1000 parts Water and 2 parts of ammonia were drummed up in the dyeing drum for 4 hours and then dyed in a fresh, Öade.

SOOTejle water of 65 °, 2 parts of ammonia, 10 Τςϊΐδ of the dissolved, described under Example 1, dye, are used together with the previously fumbled, calf leather for 1; Hour and 30 minutes; colored in the barrel. To exhaust the dyebath, 4 parts of formic acid (£ 5%) are slowly added and - until: the dye is completely fixed; further colored.

The suede, rinsed, dried and trimmed in the usual way, results after grinding the velor side is a reddish brown colored, very even suede.

Dyeing Example C

lOOTeöe lamb leather, chrome-vegetable tanned, 10 parts of the dye obtained in Example 1 are in the dyeing drum in a liquor of 1000 parts Water of 55 ° and 1.5 parts of an anionic Spennacetal emulsion drummed for 45 minutes and the Dye on the leather by slowly adding 5 parts of formic acid (85%) over 30 minutes fixed. After the usual drying and dressing, a good red-brown leather is obtained Equality.

Coloring example D

A solution of 20 parts of the according to Example 1 prepared dye in 847 parts of water, 150 parts Ethyl glycol and 3 parts formic acid (85%) is tanned by spraying, plushing and pouring onto the side of a sanded, combined tan Cowhide leather applied The leather is' under dried and trimmed in mild conditions. A leather with a reddish brown shade of good is obtained Fastnesses.

Claims (6)

Claims: 1. Metal-containing sulfonic acid group-containing 2: 1 azo complex dyes of the formula (N = NR ₄ ), (R ₄ -N = N), wherein R ₄ (A) is the radical of the formula II NH (Π) 35 or (B) an optionally substituted by halogen, nitro, cyano, hydroxy, amino, alkyl or alkoxy groups with up to 4 carbon atoms, sulfo, carboxy, sulfonamides »-, carbonamido or alkylsulfonyl groups with up to 4 C atoms in the alkyl radical of substituted phenyl, naphthyl, hydroxynaphthyl, sulfonaphthyl or hydroxysulfonaphthyl radical, and the substituents R, R ₁ , R ₂ and R _{3 are} a hydrogen, halogen atom or a nitro, cyano, hydroxyl, amino, an alkyl or alkoxy group with up to 4 carbon atoms, a sulfonic acid, carboxyl, sulfonic acid or carboxamide, or an alkylsulfonyl group with up to 4 carbon atoms in the alkyl radical, or an alkyl optionally substituted by halogen atoms, the hydroxyl or cyano group - Or alkoxy group with 1 to 4 carbon atoms, Me em iron, chromium or cobalt atom and η and m together is 1, 2 or at most 3, with the proviso that the dye molecule has at least one radical of the formula II. 2. Metal-containing polyazo dyes according to claim 1 of the formula O, N (VII) NO ₂ 3. Metal-containing polyazo dyes according to claim 1 of the formula NH R ₁ R ₃ R ₂ PCIIl) 4. Process for the preparation of metal-containing polyazo dyes of the formula I according to claim 1, characterized in that (n + m) moles of the diazo compound from amines of the formula R, --NH, with 2 moles of a compound of the formula Uli) 35 (V) 45 couples, where at least 1 mole of the (n + m) moles of the amines of the formula III of the formula used NH H ₉ N- R ₁ (IV) 60 and, if the sum η + m is 2 or 3, the (n + m) moles of the amines of the formula III used can be identical or different to one another, and the azo compound obtained is metallized in substance with a metal donor to give the compound of the formula I. . 5. Process for the preparation of metal-containing polvazo dyes of the formula I according to claim 1, characterized in that 1 mol of a compound of the formula NO, O ₂ N 4 °) -N = N HO (VI) NO, with (n + m) moles of the diazo compound from amines of the formula III, where at least 1 mole of the (n + m) moles of the amines of the formula III used corresponds to the formula IV and, if the sum η + m is 2 or 3, the (n + m) moles of the amines of the formula III used can be identical or different from one another. 6. A process for dyeing or printing leather, characterized in that metal-containing Polyazo dyes of the formula I according to claim 1 are used.