DE2345359A1 - CHROME-CONTAINING AZO DYES, PROCESS FOR THEIR PRODUCTION AND THEIR USE FOR COLORING TEXTILE GOODS - Google Patents

Description

NIPPON KAYAKU KABUSHIKI KAISHA,
Tokyo, Japan

"Chromium-containing azo dyes, procedures for their production and their use for coloring textile goods "

Priority: September 18, 1972, Japan No. 9286O / 72

The invention relates to red chromium-containing azo dyes, a process for their production and their use for dyeing of textile goods.

A number of chromium-containing azo dyes are commercially available, these known dyes, however, have insufficient light

and wet fastness.

The object of the invention is therefore to provide new red chromium-containing To create azo dyes which have excellent wet fastness.

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

409817/0991

R ¹

(I)

in the A and B the remainders <ς / ~ or

represent, which are optionally substituted by halogen atoms, nitro groups or lower alkyl or alkoxy radicals

2 4 1

are, R and R are phenyl or naphthyl groups, R

3
and R is either both phenyl groups or one of the radicals

1 3
R and R are a phenyl group and the other is a methyl group

12 3 4

where the phenyl groups R, R, R and R are replaced by halogen atoms, Nitro groups or lower alkyl or alkoxy groups sub-

2 and either A or R by a SuI-

Fonsäuregruppe is substituted, and M is an alkali metal or Represents alkaline earth metal cation.

Specific examples of lower alkyl radicals are C, ^ -alkyl radicals, such as the methyl, ethyl, propyl and n-butyl groups. The lower ones Alkoxy radicals are derived, for example, from the special alkyl radicals mentioned. In the case of halogen substances, the chlorine

409817/0991

and bromine atom are preferred. Specific examples for the cation M are the sodium and potassium cations.

The azo dyes of the invention can be prepared by that you have a 1: 1 chromium complex of a monoazo dye the general form! II

OH

—R ²

(II)

DH R ¹

1 2

in which A, R and R have the above meaning, or of the general formula III

OH

V ~ ^{N == N} \ 'you)

- \ / ^ N

OH R ³

in which B ₁ R and R have the above meaning with

desired other, metal-free monoazo dye to the / 2: l-dhrome complex implements. A 1: 1 chromium complex is preferably used of the monoazo dye containing the sulfonic acid group having.

The monoazo dyes of the general formulas II and III can be prepared in a customary manner by coupling a diazo component with a coupling component in weakly acidic or alkaline Manufacture media. The Diazokompo- ^ used here components are derived from amines, e.g. from 4-chloro-2-amino-

409817/0991

phenol, 5-chloro-2-aminophenol, 4-nitro-2-aminophenol, ^ 5-Ni ^- 2-aminophenol, 4-methyl-2-aminophenol, 4-chloro-5-nitro-2-aminp- _i phenol, 4-chloro-6-nitrρ-2-aminophenol, 4-nitro-6-chloro-2-aminophenol, 4,5-dichloro-2-aminophenol, 4,6-dinitro-2-aminophenol>. _r

or
4,6-dichloro-2-aminophenol / 1-amino-2-naphthol. In the case of the general formula II, the following are also to be mentioned as suitable amines: 4-sulfo-6-chloro-2-aminophenol, 4-chloro-6-sulfo-2-aminophenol, 4-chloro-5-sulfo-2-aminophenol, 4-sulfo-6-nitro-2-aminophenol,. 4-sulfo-2-aminophenol, 4-nitro-6-sulfo-2-aminophenol, 1-amino-2-naphthol-4-sulfonic acids, l-amino-2-naphthol-8-sulfonic acid, 6-nitro-1-amino -2-naphthol-4-sulfonic acid and 6-chloro-1-amino-2-naphthol-4-sulfonic acid. ,

Specific examples of suitable coupling components are 1- (2'-ethylphenyl) -3-methyl-S-pyrazolpn, 1- (4'-bromophenyl) -3-methy1-5-pyrazolone, 1- (2'-chloro-6'-methylphenyl) -3-methy1-5-pyrazolone, 1- (3'-nitrophenyl) -3-methy1-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolpn, 1- (2 '-, 3'- or 4' -chlorophenyl) -3-methy 1-5-pyrazolone, 1- (2 ', 5'- or 3', 4 '-dichlorophenyl) -3-methy 1-5-pyrazolone, 1- (2 ', 5'-dibromophenyl) -3-methyl-5-pyrazolone, 1-. (2 ', 4 ·, 6'-Trichlorophenyl) -3-methy1-5-pyrazolone, 1- (4'-Nitrophenyl) -3-methy 1-5-pyrazolone, 1- (2'-nitro-5'-chlorophenyl) -3-methyl-5-pyrazolone, 1- (2'-methoxy-5'-methylpheny1) -3-methy1-5-pyrazolone, l- (2 ', 5'-dimethoxyphenyl) -3-methy 1-5-pyrazolone, 1- (1'-naphthyl) -3-methy 1-5-pyrazolone, 1,3-diphenyl-5-pyrazolone, l- (2 '-, 3 - or 4'-nitrophenyl) -S-phenyl-S-jiyrazolon, l- (2'-, 3'- or 4'-chlorophenyl) -3-pheny1-5-pyrazolone, 1- (2 '-, 3'- or 4'-bromophenyl) -3-pheny1-5-pyrazolone, 1-phenyl-3- (2 ', 3'- or

409817/0991

4 · -chlorphenyi) -5-pyrazolone, 1-phenyl-3- (2 · -, 3'- or 4 · - nitxophenyl) -5-pyrazolone, 1- (2 '-, 3'- or 4'-chlorophenyi ) -3- (2 '-, S ¹ - or 4 · -Athylphenyl) -5-pyrazolone, 1- (2' -, 3 ^f - or 4'-methoxyphenyl) -3- (2 · -, 3'- or 4 -chlorphenyi) -5-pyrazolone, 1- (2 ^I -, 3 ^I - or 4 ^l -nitrophenyl) -3- (2 ', 3'- or 4'-chlorphenyi) -5-pyrazolone, 1- (2 '-, 5'-Dimethoxyphenyl) -3- (2' -, 3'- or 4'-nitrophenyl) -5-pyrazolone, 1- (2 ^f -chloro-4'-nitrophenyl) -3- (2 '-, 3' - or 4 '-chlorphenyi) -5-pyrazolone, 1- (4'-methylphenyl) -3- phenyl-5-pyrazolone, 1- (2'-methyl-6'-chlorophenyi) -3- phenyl-5-pyrazolone, 1- (4'-methoxyphenyl) -3- (2 '-, 4 ^l -dichlorophenyl) -5-pyrazolone, l-phenyl-3- (2', 4'-dichloro-5'- methylphenyl) -5-pyrazolone; 1-phenyl-3- (2'-nitro-3'-methoxyphenyl) -5-pyrazolone, 1-phenyl-3- (3 '-methylphenyl) -5-pyrazolone and 1- (1 ^f -naphthyl) 3-phenyl -S-pyrazolone. In the case of the general formula II, for example 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone, 1- (2'-chloro-4'-sulfophenyl) -S-methyl-S-pyrazolone, 1- (2 '-Sulf o-4' -methyl-5-chlorophenyi) -3-methyl-5-pyrazolone, 1- (2 ^f -Sulf o-4 '-nitrophenyl) -3-methyl-5-pyrazolone , 1- (2 ', 5-dichloro-4' -sulfophenyl) 3-methyl-S-pyrazolone, 1- (4'-sulfonaphthy 1-1 ') -3-methyl-S-pyrazolone, 1- (5'-sulfonaphthy1-1 ') - S-methyl-S-pyrazolone, 1- (2 *, 5'-dimethoxy-4'-sulfophenyl) -3-methyl-S-pyrazole Qn, 1- (2 * -Sulfo -4'-methyl-5'-chlorophenyl) -3- (2 '-, 3 * - or 4'methoxyphenyl) -5-pyrazolone, 1- (2'-chloro-4'-sulfophenyl) -S-phenyl- S-pyrazolone, 1- (4'-sulfophenyl) -3- (3'-methoxyphenyl) -5-pyrazolone, 1- (2 ^f , 5 * -dimethoxy-4'-sulfophenyl) -3-phenyl-5- pyrazolone and l- (5 ^f -Sulfonaphthyl-l ') -3-phenyl-5-pyrazolone. -

The implementation of the monoazo dyes of the general formula II

409817/0991

and III in the 1: 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, the reaction temperature being at the boiling point of the medium or also, if necessary, is above 100 ° C. The complex ' tion is preferably carried out in the usual way, for example in an aqueous medium and optionally in the presence of an organic medium Solvent such as an alcohol or formamide.

1: 1 chromium complexes of Ο, Ο'-dihydroxymonoazo dyes

s not

are known / only starting from the O, 0'-dihydroxymonoazo-

#: ■ ■ ■ '■

Make dye yourself, but also using the

_M corresponding O-alkoxy-O'-hydroxymonoazo dye. In the

Production of a chromium complex of monoazo dyes II or '. III can therefore be used as the starting compound O — Hydroxy— diazo compound by a corresponding 0-alkoxide iazo compound, especially a methoxy derivative.

In the process described, the starting compounds are preferably used in the form of solvent-containing pastes, i.e. they are not dried after manufacture and separation.

The 1: 1 chromium complex is tinted with the metal-free monoazo dye preferably in a weakly acidic or weakly alkaline aqueous solvent in an open or closed reaction vessel at room temperature or at higher temperatures, for example at 50 to 120 ^° C. By addition

L _

409817/0991

Fine organic solvent, for example an alcohol or Förfilimids ι or ^ a surface-active compound, the reaction can be accelerated.

The 1; l-cairomkoirtplex and the metal-free monoazo dye are preferably implemented in approximately stoichiometric amounts. The molar ratio of metal-free monoazo dye to 1: 1 ^ -Chroinkcanplex is usually at least 0.85: 1 and at most 1: 0.85. Excess 1: 1 chromium complex has an effect here generally less detrimental than an excess of metal-free monoazo dye. The best results are achieved with a molar ratio of about 1: 1.

The chromium-containing azo dyes of the invention are useful for Dyeing and printing of a wide variety of materials, especially for dyeing animal materials, such as silk, leather and in particular Wool, but also for dyeing and printing polyamide, polyurethane and polyacrylonxtrile fibers as well as fiber mixtures, e.g. made of wool / polyamide.

The azo dyes are mainly suitable for neutral or weakly acidic dye liquors, e.g. an acetic acid liquor. With The dyeings obtained with it are uniform and have good light, rub and wet fastness. The dyeing of fibers with the azo dyes of the invention is carried out by conventional dyeing processes, e.g., by dip dyeing, printing or padding.

Dip dyeing of nitrogenous fibers is usually done,

409817/0991

carried out at temperatures of 90 to 100 C in a Parb liquor, the Glauber's salt, sodium chloride or an ammonium salt, such as ammonium acetate or ammonium sulfate, as well as an organic one or inorganic acid such as acetic acid or formic acid , contains.

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 and a permeation-promoting agent for the dye, then padding the textile in the liquor and then at relatively high temperatures, e.g. 100 up to 200 ° C, dry heated or steamed. However, the dyeing may optionally also be such that the textile material is treated for 10 seconds to 5 minutes at 70 to 100 ⁰ C in an acidic Schockbad containing an organic or inorganic acid such as phosphoric acid or formic acid. In this case, instead of dry heating or steaming after padding, the textile material can be boiled in an aqueous bath which contains small amounts of acidic constituents.

For printing, the dye is first mixed with a basic paste mixture and then with an acid-releasing agent such as ammonium sulfate or ammonium tartrate .. or an organic acid, like acetic acid, to a color paste, prints the textile goods with this paste and finally subjects it to a dry heat ' treatment or attenuates it.

409817/0991

The examples illustrate the invention; Unless otherwise stated, all parts are based on weight.

example 1

3.5 parts of a 1: 1 chromium complex of a monoazo dye prepared from diazotized 4-chloro-2-aminophenol and 1- (4'-sulfophenyl) -3-methyl-5-pyrazolone, and 4.0 parts of a metal-free monoazo dye which has been prepared from diazotized 5-nitro-2-aminophenol and 1,3-diphenyl-5-pyrazolone are ^{stirred at 20 to 40 °} C. in 300 parts of water. The suspension obtained is neutralized by adding dilute hydrochloric acid or glacial acetic acid and optionally sodium carbonate with stirring and then heated to 85 to 95.degree. The reaction is carried out in the neutral until the two starting dyes used are no longer perceptible. Sodium chloride is then added to the solution and the resulting mixed complex is filtered off and dried. The resulting dye of the formula IV is a reddish

Powder
Lich black / md gives a red shade of good fastness when dyeing wool in a liquor containing ammonium acetate.

409817/0991

SO ₃ H

Na ^v

(IV)

Examples 2 to 29

1 chromium complexes of monoazo dyes listed in the first row of the following table with those listed in the second row of metal-free Monoazofarb- materials to chromium-containing azo dyes of the structure shown in the third row reacted, the red wool dyeing shades of: according to Example 1 1 good authenticity.

409817/0991

OCH.

OHH O

N = N

NO ₂ .

N OCH ₃

HO

OCH ₃

HO ₃ S

= ν ■ - <r ι

> = N CH ₃

CH ₃

Cl

HO

Cl

= N

n '- ^ V HO,

OHH O.

N =

CH.

O ₂ N

Cl

. Cl

CH ₃

M = H

/

OCH ₃

N = N

f = N

Cl

ORIGINAL INSPECTED

409817/0991

4 0 9 8 17/0991 O ^{RlG1NAL! NSPECTED}

409817ΛΟ991 _oR1G iNAL INSPEOiBD

23 ^ 5359

409817/0991

4098 17/09 9 1

Original

OH

HO

N = N- / I

-O

• CH ₃ ,

OH

- N = N -X

Well ³

A09817 / 0991

ORiGSNAt

INSPECTED

409817/0991

ORIGINAL

16 17th

OH

■ OH

Br

OHH O

N = N

O ₂ N

Br

N = N

ο _{χ v} o

Cr

ο - '/ "ο

N = N

3 ^H.

SO ₃ H

r-O

= Ν OHH O

HO ₃ S

Br

CH ₃

OH

HO

Cl

HO,

Cl

409817/099 1 ORIGINAL INSPECTED

- C ₂ H

OH

₂ H ₅

HO

SO ₃ H

N =

CH

₃

C2H5

SO3H

C ₂ H ₅

HO,

OH

HO

N Cl

CH

Br

OH ■

OC ₂ H ₅

■. j

Well I

j ί

HO ₃ S

Α0981 7/0991

ORIGINAL INSPECTED

20th

CH ₂

OH

N = N

Cl

Cl

SO ₃ H

Br

SO ₃ K

Br

21

OH

OH

SO ₃ H

OH

O ₂ N

NO ₂

C ₂ H

2Π5

Well "SOaH

O ₂ N

C2H5

NO

4 0 9 8 17/0991 ORIGINAL INSPECTED

22nd

OH

N-

Cl

OH

HO

O ₂ N

Cl

N-

N- = N-C I

O

23

OC, H

SO ₃ H

OC ₂ H

2Π5

OH

HO

Cl

OH HQ

N = N

CH ₃

/ ο

Cr

θ "' ^Χ Ο

Cl

O ₂ N

Well * ³

409817/0991

/ NSPECTED

24 25

OH

HO

N Cl

CH ₃

OHH O

O ₂ N

O ₂ N

OH

HO ₃ S-ZSp-N =

HO

Cl

CH ₃

OH

Cl

CH ₃

/

Na ^v

Cr ν

Ν - Ν

Cl

N / A

OWGlNAL

INSPECTED

409817/0 9-9

27

HD

N =

NO ₂

CH

• Ö

Cr

, 0

t *

N = N

Cl

N == N

O ₂ N

N - / V-SO ₃ H

OHH O

N =

O ₂ N '

-O

409817/09 91 ORIGINAL INSPECTED

28 29

OH

HO ₃ S

NO ₂

Cl OH

i-N —Ν - \ _ I

y ~ u ci

CH ₃

OH HO ₁

Cl

NO,

HO ₃ S

= N C

/ 7 ~ N

'

Cl

Cl

OH OH

N = N

NO ₂

-O

HO ₃ S

CH

N = N

O / O

Cr /

NO,

ORIGINAL! HSPECTED

409817/0991

Example 30

0.03 parts of the dye of the formula IV are in 150 parts

with

Dissolved in water. The resulting solution becomes / 0.15 part anhydrous Glauber's salt, 0.15 part of an ammonium salt such as Ammoniuiaacetat, and then mixed with 3 parts of wool. Man increases the temperature of the solution within 20 to 60 minutes from room temperature to 100 ° C and leads to the coloration 30 to 60 Minutes at this temperature. If necessary, acetic acid can be added to the dye liquor in order to increase the absorption of the dye accelerate. Red dyeings of good fastness to light and washing are obtained.

Example 31

2 parts of the dye of the formula IV and 5 parts of urea are dissolved in 100 parts of water. Then we padded nylon taffeta in the resulting solution, then pre-dried and finally heated dry for 3 seconds at 180 ° C. The nylon taffeta was then treated for 20 seconds at 100 ⁰ C with an aqueous solution containing 0.6 parts of formic acid, then washed with water and finally dried. Here, red dyeings of good lightfastness and washfastness are achieved.

Example 32

2 parts of the dye of the formula IV and 5 parts of urea

409817/0991

are dissolved in 100 parts of water. Then nylon taffeta is used padded in the resulting solution, then predried and steamed for 2 minutes at 120 ° C. and finally with water washed. The nylon taffeta is then treated with an aqueous solution containing 0.6 parts of formic acid at 100 ° C. for 20 seconds contains, then washed with water and then dried. Here are red colorations of good light and Washfastness achieved.

Example 33

0.06 parts of the dye from Example 2 are in .150 parts Dissolved in water. The solution obtained is with 0.15 parts anhydrous Glauber's salt, 0.15 part of an ammonium salt, such as ammonium acetate, and finally 3 parts of silk are added. The temperature of the solution is increased from room temperature to 100 ° C. within up to 60 minutes and the dyeing is carried out 40 to 60 minutes at this temperature. Here, red dyeings of good lightfastness and washfastness are achieved.

Example 34

0.06 part of the dye from Example 2 is dissolved in 150 parts of water. The solution obtained is mixed with 0.6 part of anhydrous Glauber's salt or sodium chloride and then with 3 parts of vinylon. ^ Man rhöht the temperature of the solution within 30 to 60 minutes from room temperature to 90 ⁰ C and the dyeing leads 40 to 60 minutes at this temperature through.

J 409817/0991

Here, red dyeings of good lightfastness and washfastness are achieved.

Example 35

3 parts of the dye from Example 2 and 5 parts of a solubilizer for the dye are dissolved in 31 parts of water. The solution obtained is mixed with 60 parts of a pasting agent (10% paste) and then with 1 part of ammonium sulfate to form a color paste. With the resulting color paste is printed wool which subsequently fixing dye 20 to 4O minutes with steam at 100 to 105 ⁰ C under atmospheric pressure and finally washed with water to. Here, red colorations of good lightfastness and washfastness are achieved.

409817/0991

Claims (3)

Claims 1. Chromium-containing azo dyes of the general formula I in the A and B the remains (I) represent, VA C ^ which may be replaced by halogen atoms, nitro groups or 2 4 whose alkyl or alkoxy radicals are substituted, R and R Denote phenyl or naphthyl groups, R and R either 1 3 de are phenyl groups or one of the radicals R and R is a phenyl group and the other is a methyl group, v / obei the Phe- 12 3 4
nyl groups R, R, R and R can be 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. 2. Process for the preparation of the azo dyes according to claim 1, characterized in that one has a 1: 1 chromium complex Monoazo dye of the general formula II 17/0991 KjtS ^^ r-dOS) ^ ^ 12.12.1973 HO NR ² A> -N ^ N- OM _Rl 1 2 in which A, R and R have the meaning given in Anspx'uch 1 ben or the general formula III HO sr- • OH 3 4 in which B, R and R have the meaning given in claim 1, with the respective other, metal-free monoazo dye implements. f 3. Use of the azo dyes according to Claim 1 for dyeing textiles. 409817/0991