DE2345358A1 - AZO DYES CONTAINING CHROME, PROCESS FOR THEIR PRODUCTION AND THEIR USE FOR COLORING TEXTILE GOODS - Google Patents

Description

NIPPON KAYAKU KABUSHIKI KAISHA,
Tokyo, Japan

"Chromium-containing azo dyes, process for their preparation and their use for dyeing textiles "

Priority: September 8, 1972, Japan, No. 89571/72

The invention relates to yellow chromium-containing azo dyes, a process for their production and their use for dyeing textiles.

Yellow azo dyes containing chromium are commercially available, but these known commercial products have insufficient light and wet fastness. Also can be with

With the help of such dyes, no yellow colorations of good fastness achieve. Since yellow is one of the three basic colors, yellow dyes are often used in combination with other colors Dyes used. In this case, the yellow dyes are required to have fastness similar to that of the other dyes own. Otherwise, they cannot be used in color combinations.

The object of the invention is therefore to provide new yellow chromium-containing

409816/1049

To create azo dyes that have excellent fastness and produce brilliant yellow colorations.

The invention thus relates to chromium-containing azo dyes of the general formula I.

NR ²

(D

in the either

13 2

a) R and R phenyl groups and R and R phenyl or naphthyl

groups are or

b) one of the radicals R and R is a phenyl group and the other

O Λ

is a methyl group and R and R are naphthyl groups

2 or one of the radicals R and R is a naphthyl group and the other is a phenyl group,

TO ^ Vt

where the phenyl groups K, B, R, R, R and R are optionally substituted by halogen atoms, nitro groups or lower alkyl or alkoxy radicals and either A or R is substituted by a sulfonic acid group, and M represents an alkali metal or alkaline earth metal cation.

Specific examples of lower alkyl radicals are C _1-4 alkyl

409816/1049

P 23 45 358.9 Nippon Kayaku K.K. K 458 (FD-100)

* ii ^ |. ~ y Uv ^ w »I

TELEPHONE 47407 * ~ \

L- 3 - 2345358 - i2.BEl.197a

radicals such as the methyl, ethyl, propyl and n-butyl groups. the lower alkoxy radicals are derived, for example, from the special alkyl radicals mentioned. Among the halogen atoms are the chlorine and bromine atom are preferred. Specific examples of the M cation are the sodium and potassium cations.

The azo dyes of the invention can be prepared by adding a 1: 1 chromium complex of a monoazo dye

general formula II

COOH

(II)

or the general formula III

COOH OH

12 3 4

in which A, B, R, R, R and R have the above meaning, with the respective other, metal-free monoazo dye converts to the crimped 2: l chromium complex. Preferably if a 1: 1 chromium complex of the monoazo dye is used, which has the sulfonic acid group.

The monoazo dyes of the general formulas II and III leave in the usual way by coupling a diazo component with a coupling component in weakly acidic or alkaline Manufacture media. The diazo component used here is conducive to

differs from an amine, e.g. from 2-aminobenzoic acid, 2-amino

/, 0981 6/1 049

-4- 23A5358

4-sulfobenzoic acid, 2-amino-4-chlorobenzoic acid, 2-amino-4-bromobenzoic acid, 2-amino-5-sulfobenzoic acid, 2-amino-5-nitrobenzoic acid, 2-amino-3- or -S-nitro-4-sulfobenzoic acid, 2-amino-3-methoxybenzoic acid, 2-amino-3- or ^ -sulfo-S-chlorobenzoic acid, 2-amino-3- or -4-methylbenzoic acid or 2-amino-4-methoxy-5-brominobenzoic acid.

Specific examples of suitable coupling components are 1- (2'-ethylphenyl) -S-methyl-S-pyrazolone, 1- (4'-bromophenyl) -3-methyl-5-pyrazolone, 1- (2 * -chloro-6 ' -methy! phenyl) -3-methyl-5-pyrazolone, 1- (3 ^l -nitroplienyl) -3-methyl-5-pyrazolone _/ 1-phenyl-3-methyl-5-pyrazolone, 1- (2'- _# 3'- or 4'-chlorophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5' - or 3 *, 4 '-dichlorophenyl) -3-methyl-S-pyrazolone, 1- (2' , 5'-dibromophenyl) -S-methyl-S-pyrazolone, 1- (2 ', 4x, 6'-trichlorophenyl) -S-raethyl-S-pyrazolone, 1- (4-nitrophenyl) 3-methyl-5 -pyrazolone, 1- (2 * -nitro-5'-chlorophenyl) -3-methyl-S-pyrazolone, 1- (2'-methoxy-5'-methylphenyl) -3-methyl-S-pyrazolone, 1- ( 2.5'-dimethoxyphenyl) -S-methyl-S-pyrazolone, 1- (1'-naphthyl) 3-methyl-5-pyrazolone, 1,3-diphenyl-S-pyrazolone, 1- (2'-, 3- or 4'-nitrophenyl) -S-phenyl-S-pyrazolone, 1- (2 ', 3'- or 4'-chlorophenyl) -3-phenyl-5-pyrazolone, 1- (2' -, 3 '- or 4'-bromophenyl) -3-phenyl-5-pyrazolone, l-phenyl-3- (2' -, 3 · or 4'-chlorophenyl) -5-pyrazolone / l-phenyl- 3- (2 '-, S ¹ - or 4'-nitrophenyl) -5-pyrazolone, 1- (2' -, 3 ·! - or 4 '-chlorophenyl) -3- (2' -, 3 · - or 4 ethylphenyl) -5-pyrazolone, 1- (2 '-, 3 - or 4'-methoxyphenyl) -3- (2' -, 3 ¹ - or 4'chlorophenyl) -5-pyrazolone, 1- ( 2 '-, S ¹ - or 4'-nitrophenyl) -3- (2' -, 3'- or 4'-chlorophenyl) -5-pyrazolone, 1- (2 '-, 5'-dimethoxyphenyl) -3- (2 '-, 3 · or 4'-nitrophenyl) -5-pyrazolone,

409816 / 1G49

l- (2'-chloro-4'-nitrophenyl) -3- (2 '-, 3 ^l - or 4'-chlorophenyl) -5-pyrazolone, 1- (4'-methylphenyl) -3-phenyl-5- pyrazolone _/ 1- (2'-methyl-6'-chlorophenyl) -3-phenyl-5-pyrazolone, 1- (4'-methoxyphenyl) -3- (2 ', 4'-dichlorophenyl) -5-pyrazolone, l -Phenyl-3- (2 ', 4'-dichloro-5-methy! Phenyl) -5-pyrazolone, l-phenyl-3- (2' -nitro-3 "'- methoxyphenyl) -5-pyrazolone, l- Phenyl-3- (3'-methylphenyl) -5-pyrazolone, and 1- (l'-naphthyl) -3-phenyl-5-pyrazolone.

In the case of the general formula II, e.g. 1- (4 '-sulfophenyl) -S-methyl-S-pyrazolone, 1- (2' -chloro-4 '-sulfophenyl) -3-methyl-S-pyrazolone, 1- (2'-sulf o-4'-methyl-5'-chlorophenyl) -S-methyl-S-pyrazolone, 1- (2'-sulfo-4 * -nitrophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'-dichloro-4'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (4-sulfonaphthyl-1 ') -3-methyl-5-pyrazolone, 1- (5'-sulfonaphthy1-1') -3-methyl-5-pyrazolone, 1- (2 ·, 5'-dimethoxy-4'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (2, 3 or 4'-sulfophenyl) -3-phenyl-S-pyrazolone, 1- (2'-sulfo-4'-methyl-5'-chlorophenyl) -3- (2 '-, 3'- or 4'-methoxyphenyl) -5-pyrazolone, 1- (2'-chloro-4'-sulfophenyl) -3-phenyl-S-pyrazolone, 1- (4'-sulfophenyl) -3- (3'-methoxyphenyl) -5-pyrazolone, 1- (2 ', 5'-Dimethoxy-4'-sulfophenyl) -3-phenyl-5-pyrazolone and 1- (5'-sulfonaphthy1-1 ') - S-phenyl-o-pyrazolone.

The conversion of the monoazo dyes of the general formulas II and III into the 1 s 1-chromium complex takes place in the usual way, e.g. by reacting the dye in an acidic medium with excess chromium (III) salt, e.g. chromium (III) formate, Chromium (III) acetate, chromium (III) sulfate or chromium (III) fluoride,

409816/1049

the reaction temperature at the boiling point of the medium or me, if necessary, being above 100 ° C. Preferably complexation takes place in the usual way, e.g. in an aqueous medium or, if appropriate, in the presence of a organic solvents, e.g. an alcohol or formamides.

The starting compounds are preferred in the process of the invention used as solvent-based pastes, i.e. they are not dried after production and separation.

The conversion of the 1: 1 chromium complex with the metal-free one Dye is preferably carried out in a weakly acidic or weakly alkaline aqueous solvent in a closed or open reaction vessel at room temperature or at higher temperatures, e.g. at 50 to 120 ° C. By adding a organic solvent, e.g. an alcohol or a formamide or a surface-active compound implementation can be accelerated.

The 1 ϊ 1 chromic complex and the metal-free dye become preferably implemented in approximately stoichiometric amounts. The molar ratio of metal-free dye to 1: 1 chromium complex is usually at least 0.85: 1 and at most 1: 0.85 The use of excess 1: 1 chromium complex has an effect usually less disadvantageous than an excess of metallfroiem Dye. The best results are obtained with a molar ratio of about 1: 1.

40981 6/1 0A9

The new chromium-containing azo dyes of the invention are useful for dyeing and printing various materials, e.g. for dyeing materials of animal origin such as silk, Leather and especially wool, as well as for dyeing and printing synthetic materials such as polyamide, polyurethane and Polyacrylonxtrile fibers or fiber mixtures, e.g. from a wool / polyamide mixture. The dyes of the invention are useful mainly for neutral or weakly acidic dye baths, e.g. an acetic acid bath. The colorations achieved are uniform and have good light, rub and wet fastness. The dyeing of fibers with the azo dyes of the invention takes place according to the usual dyeing processes, e.g. by dip dyeing, printing or padding.

The dip dyeing of nitrogen-containing fibers is usually carried out at temperatures of 90 to 100 ° C in a dye liquor, the Glauber's salt, sodium chloride or an Amraonitiüisalz ,, like Ammonium acetate or ammonium sulphate and inorganic substances organic acid such as acetic acid or formic acid.

The pad steaming process is carried out by first preparing a padding liquor from the dye, urea, a migration preventing agent such as sodium alginate, a solubilizer for the dye and a dye permeation agent, the textile material in this liquor and then padding it at relatively high temperatures, for example 100 to 200 ⁰ C, heated dry or steamed. If appropriate, the dyeing can also be carried out in such a way that the textile material is kept at temperatures for 10 seconds to 5 minutes

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treated from 70 to 100 C in an acid shock bath, the an organic or inorganic acid such as phosphoric acid or formic acid. In this case, the textile material instead of dry heating or steaming after Padding can be boiled in an aqueous bath that contains small amounts of acidic components.

Printing is carried out by first adding the dye with a paste base mix and then with an acid-releasing Agents such as ammonium sulfate or ammonium tartrate.? or an organic acid such as acetic acid to a color paste mixes and prints the textile material with this paste and then heats it dry or steams it.

The examples illustrate the invention; Unless otherwise stated, the parts given relate to weight.

example 1

5.2 parts of a 1: 1 chromium complex of a monoazo dye, that of diazotized 2-amino-5-sulfobenzoic acid and 1,3-diphenyl-5-pyrazolone and 3.7 parts of a metal-free monoazo dye prepared from diazotized 2-aminobenzoic acid and 1,3-diphenyl-5-pyrazolone is, are stirred at 20 to 40 ° C in 300 parts of water. the

obtained suspension is obtained by adding dilute salt with stirring

satire or glacial acetic acid and optionally sodium carbonate / neutralized and then heated to 85 to 95 ° C. This forms

4098 16/10 ^ 9

a yellow clear solution. The reaction is continued in the neutral until the two different starting dyes are no longer perceptible. Sodium chloride is then added to the solution and the resulting mixed complex * is filtered off and dried. The dye obtained possesses the formula IV and represents a yellow-brown powder. It results when dyeing wool in an ammonium acetate Fleet a yellow shade of good fastness.

HO ₃ S

(IV)

Examples 2 to 17

According to Example 1, 1: 1 chromium complexes of the monoazo color

the first
substances in / row of the following table with the metal-free

The second
Monoazo dyes implemented in / series, with chromium-containing

the third
Azo dyes of the structure indicated in / series are obtained which, when dyeing wool, give a yellow shade of good fastness.

409816/1049

- OK -

2.

COOH HO

SO ₃ H

Cl

COOH HO

H ₃ CO

N = N- ^ l

OCH ₃

Cl

COOH HO.

N =

⁼ N

COOH

HO '

N = Vrf Y ^A = ^/

409816/1049 OFHGfNAL INSPECTED

- ii -

CH

COOH

HO

HO ₃ S

N =

"Cl HO ₂

C ₂ H

2Π5

Br

. N

COOH HO

SO ₃ H

IMSPECTED

409816/1049

COOH N =

HO

HO ₃ S

> ^N

= ν

COOH

HO

<- N

HO ₃ S

COOH

OCM,

HO

N = N

. CH ₃

SO ₃ H

CH ₃

COOH

HO.

N =

SO ₃ H

CH

■ ν - *

N =

COO /

.Cr> COO / 7 . ι

N CH3

OCH-

409816/1049

COOH -N

HO

= N

SO ₃ H

CH ₃

COOH

N =

SO ₃ H COOH

N-N

SO ₃ H

. CH ₃

COOH

ORIGJfNfAL JNSPECTED

409816 / 1O Λ 9

subsequently changed

- 14 -.

A09816 / 1049

^ 09816/1049 ^0RIGfw AL Inspected

4098 16/1049

ORIGINAL INSPECTED

16 17th

COOH

OH

SO ₃ H

^ COOH OH

■ N

Br

^0C 2 ^H S

SO ₃ H

COO /

«Ν-« 'i

^OC 2 ^H 5

-O

-ο COQH

OH

HO ₃ S

N = N

COOH OH

C ₂ H ₅

ro

N --- K I

COO ν /

-O

.'Cr _x

N =

^C 2 ^H 5

Well ⁰

409816/1049

.Q ^ U INSPECTED

Example 18

0.03 parts of the dye of the formula IV are in 150 parts Dissolved in water. The resulting solution is then 0.15 parts anhydrous Glauber's salt, 0.15 part of an ammonium salt, such as ammonium acetate, and finally mixed with 3 parts of wool, The temperature of the solution is increased from room temperature to 100 ° C. in the course of 20 to minutes and the dyeing is carried out for up to 60 minutes at this temperature. If necessary, the dye liquor can be mixed with acetic acid to the Accelerate color absorption. In this way, bright yellow dyeings of good lightfastness and washfastness are obtained.

Example 19

2 parts of the dye of the formula IV and 5 parts of urea are dissolved in 100 parts of water. One stock response nylon taffeta in the resulting liquor, then dried and finally heated in front of him 3 seconds 180 ⁰ C. The nylon taffeta is then 2O seconds treated at 100 ⁰ C with an aqueous solution containing O, containing 6 parts of formic acid, then with water washed and dried. This gives bright yellow dyeings of good fastness to light and washing.

409816/1049

Example 20

2 parts of the dye of the formula IV and 5 parts of urea are dissolved in 100 parts of water. One pounds in nylon taffeta of the resulting liquor, then pre-dries it, then steams it for 2 minutes at 120 ° C. and then washes it with it Water. The nylon taffeta is then treated for 20 seconds at 100 ° C. with an aqueous solution containing 0.6 parts of formic acid contains, then washed with water and dried. This produces yellow dyeings with good lightfastness and washfastness obtain.

Example 21

0.06 part of the dye from Example 2 is dissolved in 150 parts of water. The solution obtained is treated with O, 15 parts of anhydrous Glauber's salt, O _f 15 parts of an ammonium salt such as ammonium acetate, and thereto are added 3 parts of silk. The temperature of the solution is increased from room temperature to 100 ° C. in the course of 20 to 60 minutes and dyeing is carried out at this temperature for 40 to minutes. This gives bright yellow dyeings of good fastness to light and washing.

Example 22

0.06 parts of the dye from Example 2 are in 150 parts Dissolved in water. The solution obtained is treated with 0.6 parts of water

409816/1049

free Glauber's salt or sodium chloride and then mixed with 3 parts of vinylon. The temperature of the solution is increased from room temperature to 90 ° C. within 30 to 60 minutes and the dyeing takes place for 40 to 60 minutes at this temperature by. Here, bright yellow dyeings of good lightfastness and washfastness are achieved.

Example 23

3 parts of the dye from Example 2 and 5 parts of a dye solubilizer are dissolved in 31 parts of water. the The solution obtained is mixed with 60 parts of a pasting agent

/ -ige

(10% paste) and then mixed with 1 part ammonium sulfate, which forms a color paste. This color paste is printed on wool, steamed for 20 to 40 minutes at 100 to 105 ^° C. under normal pressure in order to fix the dye, and finally it is washed with water. Here, bright yellow dyeings of good lightfastness and washfastness are achieved.

40981R / KU9

Claims (3)

Claims: Chromium-containing azo dyes of the general formula I in the either 13 2 4 a) R land R phenyl groups and R and R phenyl or naphthyl groups are or b) one of the radicals R and R is a phenyl group and the other 2 4 is a methyl group and R and R are naphthyl groups 2 4 or one of the radicals R and R is a naphthyl group and the other is a phenyl group, 12 3 4 where the phenyl groups A, B, R, R, R and R are optionally by halogen atoms, nitro groups or lower alkyl or Alkoxy radicals are substituted and either A or R is substituted by a sulfonic acid group, and M is an alkali metal or Represents alkaline earth metal cation. 2. Process for the preparation of the azo dyes according to Claim 1, 409816/1049 characterized in that there is a 1 s 1-chromium compound of a monoazo dye of the general formula II COOH HO > = NR ¹ 1 2 in which A, R and R have the meaning given in claim 1, or the general formula III COOH _HQ YH - ^R% (in) R ³ 3 4 in which B, R and R have the meaning given in claim 1, with the respective other metal-free monoazo dye implements. 3. Use of the azo dyes according to Claim 1 for dyeing textiles. 409816/1049