DE2000298A1 - New disazo pigments and processes for their production - Google Patents

Description

'DR. BERQ DIFL.-iV'S. STAPF

PAr; -:. IrA \ wÄLTii

8 MUNICH a, HILEiLEDYRASSIi SO ^ _{Ä Ä}

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6641 / R

Germany

Attorney's file 19 154 Munich, Jan. 5, 197o

New disazo pigments and processes for their production.

N ^R 5 ⁵ N

Il 'II

j OH ^ HO _n ,

^R 2 \ ·. '/ ^R 2.

CONH R, HNOO

009830/1625

It has been found that new valuable disazo pigments of the formula f

^R r ^S0 2- \ w * - ^S0 2- ^R l

arrives, in which R is an aryl radical in which the sulfonamide group is in the m- or p-position to the azo group, R is a 'naphthalene radical in which the azo, hydroxy and -CO groups in the 1,2,3-position stand, R is an arylene radical, R is an aralkyl or aryl radical and R is a hydrogen, an alkyl or aralkyl radical, if one
a) a carboxylic acid halide of the formula

/ 4

Il

OH

COHaI

condensed with an arylenediamine in a molar ratio of 2: 1, or b) a diazo or diazoamino compound of an arylamine of the formula HpN-R ₁ -SOpNRrRp. with a 2,3-hydroxynaphthoic acid arylide of the formula

/ ^0H HO _n

^R 2 V

CONH R - NHOC

couples in a molar ratio of 2: 1.

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Since the dyes according to the invention Pigments are water-solubilizing groups, in particular acidic water-solubilizing groups, such as sulfonic acid or carboxylic acid groups are of course excluded.

Disazo pigments of the formula are of particular interest

where X is a. Hydrogen or halocenatorr. or an alkoxy group, X is a hydrogen or halogen atom, an alkyl, alkoxy, Phenoxy or sulfonic acid amide group means R, R]. and R which have ance.'j level meaning.

Pie Azofarbstoffcarbonsäuren that the present invention "u vorwon-ior.den Säurehaloeeniden γλι underlie receives rr.nn <iurch Kuri-Pedal of entcrrechenrien Arr.ino'irylsulfon- • irr.ides, incl Osora ^ ve a Airinoben ^ olsulfonand- .les with a P,) -HyJ.i'i. xyr.arlithoeG acid, in particular such a formula

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BATH ORIGINAL

OH

Z ^ COOH

χα.

wherein Z is a hydrogen or halogen atom or an alkoxy group means.

Amines of the formula are of particular interest as diazo components

wherein X is a hydrogen or halogen atom, an alkyl, Alkoxy, phenoxy or sulfonic acid amide group and R ^ and Rp. Have the meaning given. As examples the following diazo components are called:

l-aminobenzene-5-sulfonic acid benzylamide, l-aminobenzene-5-sulfonic acid phenylamide, l-aminobenzene -> - sulfonic acid-N-methyl ~ N-phenylamide, l-aminobenzene-5-sulfonic acid-N-ethyl-N-phenylamine, l- Aminobenzene-5-sulfonic acid-N-butyl-N-phenylamide, l-aminobenzene-4-sulfonic acid benzylamide, l-aminobenzene-4-sulfonic acid dibenzylamide, l-aminobenzene- ^J i-sulfonic acid phenylamide,

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_ 5 -

1-aminobenzenesulfonic acid-a-naphthylamide, 1-aminobenzene- ^ l-sulfonic acid-β-naphthylamide, l-aminobenzene-4-sulfonic acid-N-methyl-N-phenylamide, l-aminobenzene-4-sulfonic acid-N -ethyl-N-phenylamide, l-amino-2-chlorobenzene-4-sulfonic acid-ephenyl amide _J l-amino-2-chlorobenzene-4-sulfonic acid-a-naphthylamide _J l-amino-2-chlorobenzene-5-sulfonic acid-N -methyl-N-phenylamide _J.

l-Amino-2-chlorobenzene-5-sulfonic acid-phenylamide _J. Ä

l-Amino-2-chlorobenzene-5-sulfonic acid-α-naphthylamide, l-amino-2,4-dichlorobenzene-5-sul "f onic acid benzylamide, l-amino-2 _ί 5-dichlorobenzene- ^ί ^ -sulfonic acid- phenylamide, l-amino-2-methylbenzene-5-sulfonic acid-phenylamide _J l-amino-2-methylbenzene-5-sulfonic acid-N-methyl-N-phenylamide _J l-amino-2-methylbenzene-5-sulfonic acid _{benzylamide ί} l- Aίnino-2-methylbenzene-5-sulfonic acid-N-methyl-benzylamide, l-amino-2-methylbenzene-5-sulfonic acid-dibenzylamide 1-amino-2-methylbenzene-5-sulfonic acid-2'-chlorophenylamide, l-amino 2-methylbenzene-5-sulfonic acid- ¹ l -'-chlorophenylamide _J l-amino-2-methylbenzene-5-sulfonic acid-2 ', 4'-dichlorophenylamide, l-amino-2-methylbenzene-5-sulfonic acid-2 ¹ , 4- '^' - trichlorophenylamide, 1-amino-2-methylbenzene-5-sulfonic acid-2'-methyl-phenyl-amidj l-amino-2-methylbenzene-5-su ^ f.onic acid-4 ^! -Methylphenylamide _ί

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1-Amino-2-methylbenzene-5-sulfonic acid-4'-methoxyphenylamide, 1-amino-2-methylbenzene-5-sulfonic acid-4'-chloro-2'-phenylamide, 1-amino-2-methylbenzene-5-sulfonic acid -4'-chloro-5'-phenylamide, l-amino-2-methylbenzene-5-sulfonic acid-3 ^! -trifluoromethylphenylamide, l-amino-2-methylbenzene-4-sulfonic acid-4'-chloro-2'-methylphenylamide, l-amino-2-methylbenzene-4-sulfonic acid-4'-phenyl-phenylamide, l-amino-2- methylbenzene-4-sulfonic acid-Ν, Ν'-diphenylamide, l-amino-2-methylbenzene-4-sulfonic acid-N-benzylamide, l-amino-2-methylbenzene-4-sulfonic acid-N-methyl-phenylamide, l-amino ^ -methylbenzene ^ -sulphonic acid-phenylamide, l-amino-4-methylbenzene-5-sulphonic acid-phenylamide, l-amino-2-methoxybenzene-4-sulphonic acid-4'-chlorophenylamide, l-amino-2-methoxybenzene-4-sulphonic acid 4'-methylphenylamide, 1-amino-2-methoxybenzene-4-sulfonic acid-N-methyl-N-phonylamide, 1-amino-2-methoxybenzene-4-sulfonic acid-phenylamide, 1-amino-2-methoxybenzene-5-sulfonic acid -N-methylphenylamide, 1-amino-2-methoxybenzene-5-sulfonic acid-phenylamide, l-amino-2-phenoxybenzene-4-sulfonic acid-N-methyl-N-phenylamide, l-amino-2-phenoxybenzene-4-sulfonic acid -phenylamide, l-amino-2-phenoxybenzene-5-sulfonic acid-N-methyl-N-phenylamide, l-amino-2-phenoxybenzene-5-sulfonic acid-phenylamide, 1-aminobenzene-2,4-disulfonic acid re-phenylamide, 1-aminobenzene-2,5-disulfonic acid-N-methy1-N-phenylamide,

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l-aminobenzene ^^ - disulfonic acid phenylamide, l-aminonaphthalene-5-sulfonic acid-phenylamide, l-aminonaphthalene-4-sulfonic acid phenyl amide, l-aminonaphthalene-5-sulfonic acid-phenylamide, l-aminonaphthalene-6-sulfonic acid-phenylamide, 1-aminonaphthalene-7-sulfonic acid phenylamide.

The Azofarbstoffcarbonsäuren obtained are treated with agents Λ, which are capable of carboxylic acids, chlorides bromides odör convert into their halides, for example, so in particular with Phosphorphalogeniden such as phosphorus pentachloride or pentabromide or Phosphortriehlor.id, phosphorus oxyhalides and preferably with thionyl chloride.

Treatment with such acid-halogenating

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Means becomes expedient in indifferent organic Solvents such as dimethylformamide, chlorobenzenes, ζ.3. Mono- or dichlorobenzene, toluene, xylene or nitrobenzene carried out, in the case of the last 5, optionally with the addition of dimethylformamide.

When preparing the carboxylic acid halides, it is generally expedient to use those prepared in an aqueous medium Azo compounds are initially dried or azeotroped by boiling in an organic solvent

• Free water . The azeotropic drying can, if desired, be carried out immediately before the treatment with the acid-halogenating agents.

According to the present process, the monocarboxylic acid halides obtainable in this way are condensed with aromatic diamines in a molar ratio of 2: 1. It is preferred to use diamines of the benzene series, in particular 1,4 -Oi ~

' aminobenzenes of formula'

tr

"3

wherein X ₂ and X are hydrogen or halogen atoms. or, preferably, alkyl, alkoxy or tri fluorine thylgruppeaboneaken.

Also very good dyes v; c-rdor. »With amines of the diphenyl

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BATH ORIGINAL

series, especially those of the formula

Y ₁

wherein the Y, hydrogen or halogen atoms / alkyl or alkoxy groups, achieved.'As examples, the following amines may be mentioned ι * '-

1,4-diaminobenzene """'.""' · Ä

1,5-diaminobenzene

1,5-diamino-4-methylbenzene "" ■

1 y 5-diamino-4,6-dichlorobenzene 1 i 5-diamino-4-chlorobenzene 1,5-diamino-2j 5-dichlorobenzene * l _J 4-diamino-2-chlorobenzene I ₃ 4-diamino-2-bromobenzene. 1,4-diamino-2 _i 5-dichlorobenzene

1, K- diamino-2-methylbenzene _{1,4-diarnino-2 J} 5-dimethylbenzene 1,4-diamino-2-methoxybenzene

1,4-diamino-2,5-diethoxybenzene ■

6-dimethylbenzene

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ü-Trii'luoromethyl-1,4-phenylenediamine 2-chloro-5-methyl-1,4-phenylenediamine ^ -chloro-S-methoxy-1,4-phenylenediamine 2-methyl-5-methoxy-1,4-phenylenediamine 4,4'-diaminodiphenyl
3,5'-DiChlor- ¹ 1,4'-diaminodiphenyl '3,3'-Dimethyl-4,4'-diaminodiphenyl 3,3'-dimethoxy-4,4'-diaminodiphenyl

'I5, 5' -Tetrachlor-4,4. ' -diaminodiphenyl 2, .2 ', 5,5'-tetrachloro-4,4'-diaminodiphenyl ■ 3,3'-dichloro-5,5'-dimethyl-4,4'-diaminodiphenyl 4,4'-diaminodiphenyl ketone, 4 , 4-Diaminodiphenylmethane, 4,4I-Diaminodiphenylsulfon, 4,4'-Diaminodiphenyläther, 2,8-Diaminochrysen

4,11-diaminofluoranthene 2,6- or 1,5-diaminonaphthalene diaminob'enzothiazoles, such as 2- (4'-aminophenyl) -6-amtt \ abovezthiazole.

The condensation between the carboxylic acid halides !! of the type mentioned at the outset and the amines carried out in anhydrous medium. Under this condition it generally occurs surprisingly easily at Temperatures that are in the boiling range of normal organic solvents such as toluene, monochlorobenzene, dichlorobenzene, Trichlorobenzene, nitrobenzene and the like. To speed up It is generally recommended for implementation

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an acid binding agent, such as anhydrous sodium acetate-oder Use pyridine. The dyes obtained are partly crystalline and partly amorphous and are usually very good yield and pure condition obtained. It is useful to use the acid chlorides obtained from the carboxylic acids to be deposited for the time being. In some cases, however, it is possible to dispense with the separation of the acid chlorides without damage and the condensation take place immediately after the production of the carboxylic acid chlorides.

According to a modified embodiment of the inven-

The process according to the invention leads to the new dyes, ™ if a diazo or diazoamino compound of an amine of the formula H ₂ NR ₁ -SO ₂ NR ^ R with a 2,3-hydroxynaphthoic acid arylide of the formula

Jjti

ν / 2

couples in a molar ratio of 2il.

The required for this purpose are 2,3-Hydroxynaphthoesäurearylide according to per se known method from a optionally in the 6-position substituted 2,3-hydroxynaphthoic acid and an arylenediamine in anhydrous medium, such as toluene, xylene, chlorobenzene, etc. under the influence of a condensing agent, can be produced like phosphorus trichloride.

The coupling takes place by gradually adding ■ the aqueous-alkaline solution of the coupling component to

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/ acidic solution of the diazonium salt instead. The solution to the Coupling component to be used amount of alkali hydroxide v / ird expediently so dimensioned / that it is necessary for the neutralization which is sufficient in the coupling from the diazonium salt released mineral acid. The clutch is useful at. a p "value of 4 to 6 carried out. The p "value is

η rl

advantageously adjusted by adding a buffer. Suitable buffers are, for example, the salts, in particular alkali salts, of formic acid, phosphoric acid or, in particular, of acetic acid! The alkaline solution of the coupling component contains advantageously a wetting, dispersing or emulsifying agents, for example, a "'Ar Dodeoyl alkylsulfonates such as benzenesulfonate or the sodium salt · the Ι, Ι'Naphthylmethan--sulfonic polycondensation products of alkylene oxides, such as, the contact product of ethylene oxide to p Tert- octylphenol, also alkyl esters of sulforicinoleates, for example n-butyl sulforicinoleate. The dispersion of the coupling component can also advantageously contain protective colloids, for example methyl cellulose or smaller amounts of inert organic solvents that are sparingly soluble or insoluble in water, for example optionally halogenated or nitrated aromatic hydrocarbons, such as Benzene, toluene, xylene, chlorobenzene, dichlorobenzenes or nitrobenzene, as well as aliphatic halogenated hydrocarbons, such as hydrocarbon tetrachloride or trichlorethylene,

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also organic solvents which are miscible with water, such as acetone, ethylene glycol monomethyl ether, methyl ethyl ketone, Methanol, ethanol or isopropanol.

The coupling can also advantageously be carried out by continuously combining an acidic solution of the diazonium salt with an alkaline solution of the coupling component in a mixing nozzle, the components being coupled immediately. It is important to ensure that the diazo component and coupling component in secular äquimoie- A amounts are present in the mixing nozzle, whereby proves · a small excess of the coupling component to be advantageous. The easiest way to do this is to check the p "value of the liquid in the Misoh nozzle. It is also necessary to ensure that the two solutions are strongly swirled in the mixing nozzle. The resulting dye dispersion is continuously drawn into the mixing nozzle and the dye is separated off by filtration.

The coupling can also be carried out in the V / eise, that a diasoamino compound containing the radical R. with a naphthol of the formula

OH HQ ''.

^x C0NH-R -NHCCf

in an organic solvent, optionally in an aqueous organic solvent, preferably in counter

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wa an acid, heated.

The aryldiazoamides to be used according to the process are obtained by known processes by condensation of an aryldiazonium salt with a primary or, preferably, with a secondary amine. A wide variety of amines are suitable for this purpose, for example aliphatic amines, such as methylamine, ethylamine, ethanolamine, propylamine, butylamine, hexylamine and, in particular, dimethylamine, diethylamine, diethanolamine, methylethanolamine, dipropylamine or dibutylamine, aminoacetic acid, methylaminoacetic acid, butylaminoacetic acid, butylaminoacetic acid " aminoäthansulfonsäure, Guanyläthansulfonsäure, SS Aminoäthylschwefelsäure, alicyclic amines such as cyclohexylamine, N-methyl · cyclohexylamine, dicyclohexylamine, aromatic amines such as 4-aminobenzoic acid, SuIfanilsäure, 4- ^ ^{uifo-2-aminooenzoesäure;} (4-sulfophenyl) -guanidine, 4-N «methylaminobenzoic acid, ■ '4-ethylaminobenzoic acid, l-aminonaphthalene-4-sui' onic acid,"'l-aminonaphthalene-2,4-disulfonic acid, heterocyclic amines such as piperidine, morpholine, pyrrolidine, dihydroindci. and finally also sodium cyanamide or dicyandiamide.

Usually the obtained are diazoamino compounds Slightly soluble in cold water and can optionally after salting out in crystallized form from the The reaction medium is separated off / grounded. In many cases, the moist press cake can be used for further implementation Will. In some cases it can turn out to be excessive prove the diazoamides prior to implementation

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2Ö0Ü298

To dewater vacuum drying or to remove the water by azeotropic distillation after slurrying the moist presscake in a solvent.

The coupling of the diazoamino compound with the naphthol takes place in an organic solvent, for example chlorobenzene, o-dichlorobenzene, nitrobenzene, pyridine, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, dimethylformamide, formic acid or acetic acid. When using solvents that are miscible with water, it is not necessary to use the diazoamino compounds in anhydrous form. For example, the water-moist filter cake can be used. The cleavage of the diazoamino compound preceding the coupling takes place in an acidic medium. If neutral solvents are used, it is necessary to add an acid, for example hydrogen chloride, sulfuric acid, formic acid or acetic acid. . \

The coupling is expediently carried out in the heat, preferably at temperatures between 80 ° to 180 ° C. and generally proceeds very quickly and completely. - ""

. . Thanks to their insolubility, the pigments obtained can be isolated from the reaction mixtures by filtration. Since the by-products remain in solution, the pigments obtained are of excellent purity. Post-treatment with organic solvents

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BATH

in the case of pigments that are obtained by dor, aqueous coupling is displayed. Another advantage of the invention Process is the high yield, the pigment technology favorable form and the constancy of the properties of the pigments obtained.

The pigments obtainable according to the process can, thanks to their favorable properties, be used for a wide variety of Pigment applications can be used, e.g. in finely divided form for dyeing rayon and viscose or • Cellulose ethers and esters or of super polyamides or. Super polyurethanes or polyesters in the spinning pulp, as well for the production of colored lacquers or lacquer formers, solutions or products made from acetyl cellulose, nitrocellulose, natural resins or synthetic resins, such as polymerization resins or condensation resins, e.g. aminoplasts, alkyd resins, Phenoplasts, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, Rubber, casein, silicone and silicone resins - In addition, they can be advantageous in the production of "printing inks, colored pencils, use cosmetic preparations or laminating plates.

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

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BATH ORIGINAL Example 1.

14.5 parts of the dye carboxylic acid, which one by Coupling of diazotized ^ -amino - ^ - methoxy-benzenesulfonic acid phenylamide with 2,5-hydroxynaphthoic acid are obtained in 150 parts by volume of chlorobenzene with 2.4 parts by volume of dimethylformamide and 4.5 parts by volume of thionyl chloride heated to 55 tiis βΟ for 12 hours. Then let it cool down and the uniformly crystalline dyestuff carboxylic acid chloride is filtered off, washed with a little benzene and dried it. 11.7 parts are obtained ($ 90.5 of theory).

6.5 parts of this chloride are used together with 1.09 parts of 2,5-dimethoxy-1,4-phenylenediamine in 150 parts by volume Chlorobenzene heated to 155 for 12 hours. then the pigment formed is filtered off hot, with hot o-dichlorobenzene, with dimethylformamide, then with methanol and Water washed and dried. 5 parts of a dull violet powder are obtained, the polyvinyl chloride in burgundy Clay colors. The coloration is very resistant to migration and light. The pigment has the formula

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OCH_. OCH,

3 ι

Il S0 ₉ N

N N

I OH HO j

CXX _T>

CONH- ^ T> -NHOC

CH ₃ O

The table below describes other disazo dyes obtained by condensation of 1 mole of the diamine mentioned in column III with 2 moles of the acid chloride of the monoazo dye, which is passed through Coupling of the diazo compound of the amine mentioned in column I with the naphthol mentioned in column II is obtained. Column IV denotes the hue of a polyvinyl chloride film colored with the pigment obtained.

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I. 1 ^ -Chlor-jJ-amino-
benzenesulfonic acid
(2 ¹ , 5 '- (UChIOr) -
phenylamide II 1
III ί IV
i j board
] eaux I. 2 Il 2,3-hydroxy
naphthoic acid 2,5-diraethyl-
1,4-diaminobenzene ! Gray
t 1
L.
ί 3 It It 2,5-dimethoxy
1,4-diaminobenzene orange • 4th M. It k, k '-diamino-1,1'-
diphenyl It ! 5 Il It
• 3,3'-DiChIOr- ¹ M ¹ -
diamino-1,1'-di
phenyl board
eaux 6th H ti S-chloro-S-methoxy-
1,4-diaminobenzene ■ board
eaux 7th 4-chloro-5-amino-
benzenesulfonic acid
(3'-trifluoromethyl) -
phenylamide 6-methoxy
2,3-hydroxy
naphthoic acid 2,5-dichloro-1,4
diaminobenzene Red
Brown 2,5-hydroxy
naphthoic acid
ί '- - "■ 2,5-dichloro-1,4
diaminobenzene

J Γ

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I. 8th 4-methoxy-3-amino
benzenesulfonic acid
phenylamide It II III IV 9 If ^ J-chlorine-3-ami no-
benzene su If on acidic
phenylamide 2,5-hydroxy
naphthoic acid 1,4-diaminobenzene ruby 10 It ti ti 2-chloro-5-methoxy
1,4-diaminobenzene blue
Red 11th Il 4-chloro-5-amino-
benzenesulfonic acid
α-naphthylamide It 2,5-di-methyl-
1,4-diaminobenzene board
eaux 12th 6-bromo-2,5-
hydroxy
naphthoic acid 2,5-dimethoxy
1 _, 4-diaminobenzene board
eaux 15th 6-methoxy
2,5-hydroxy
naphthoic acid Il board
eaux 14th 2,5-hydroxy
naphthoic acid 2,5-dimethyl
1,4-diaminobenzene board
eaux 15th Il 2, 5-dimethoxy
1,4-dimethylamide board
eaux ti It board
eaux
i

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200028

" ^I. 16 4-chloro-3-amino-
benzenesulfonic acid
(4'-chior) -pheny1-
amide II III IV 17th 4-methyl-3-amino
benzenesulfonic acid
phenylamide 2,3-hydroxy
naphthoic acid 2,5-dimethyl
■ 1,4-diaminobenzene board i
eaux
I.
t
i
! 18th ti It " board
eaux 19th 4-methy1-3-amino-
benzenesulfonic acid
(2 ', 5'-dichloro) -
phenylamide Il 2 , 5-dimethoxy
1,4-diaminobenzene board
eaux 20th Il 2,5-dimethyl
1,4-diaminobenzene board
eaux 21 ^ -Phenoxy - ^ - amino-
benzenesulfonic acid
phenylamide ti 5,3'-DiChIOr - ^, 4'-
diamino-1,1 ¹ -di
phenyl Crowd
laugh 22nd H It 2,5-dimethyl,
1,4-dietninobenzene Red 23 ti Il 2-methoxy
1, 4-diaminobenzene It It 3,3'-DiChIOr-
4,4'-diamino
1,1'-diphenyl Crowd
laugh

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M Λ

I. 24 4-methyl-3-amino
benzenesulfonic acid
benzylamide II III 'IV ^! : red J
\ s blue
! pithy
Red 25th Il
i 2,3-hydroxy
naphthoic acid 1,3-diamino-4,6-
dichlorobenzene 1,5-naphthylene-j ";
diamine: j Crowd
laugh
! 26th Il It 2,5-dimethyl-1,4) blue-,;
diaminobenzene i red ϊ
I. red j 27 ι · Il 2,5-dimethoxy
1,4-diaminobenzene I j
Crowd
laugh
1 28 n Il 2-methoxy-5-chloro
1,4-diaminobenzene t
bordeaux 29 Il Il 2-methoxy-5-methyl-
1,4-diaminobenzene 30th ti Il 2-chloro-1,4-di-
aminobenzene blue
Red 31 4-methoxy-3-ami.no-
benzenesulfonic acid
benzylamide It 2,5-dimethyl-1,4
diaminobenzene Brown 32 w Il 2,5-dimethoxy
1,4-diaminobenzene 33 II. Il 2-methoxy-5-chloro
1,4-diaminobenzene 1-amino-5-chloro
benzene-2,4-disul-
fonsäurephenyl-
amide Il 2,5-dimethyl
1,4-diaminobenzene It

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I. 55
ι
I.
1
t l-amino-5-chloro
benzene-2,4-disul-
fonsäurephenyl-
amide II III IV ; 56 4-chloro-5-amino-
benzenesulfonic acid
(2 ¹ -chlor) -phenyl-
amide 2,5-hydroxy
naphthoic acid 2-chloro-1,4-diamino
benzene Brown 57 Il It 1.4. -Diaminobenzene orange 58 4-chloro-5-amino-
benzenesulfonic acid
^ '- chlorO-phenyl-
amide ti 4,4'-diamino-5 _> 5'-
dichloro-1, I ¹ -di
phenyl sharp
laugh 59
.
ι 4-methoxy-5-amino-
benzenesulfonic acid
(2'-chloro) -phenyl-
amide It
- 2,5-dichloro ~ l, 4-
diaminobenzene Crowd
laugh 40
i Il It 1,5-dichloro
diaminobenzene blue
Red 41
i Il !! 5-chloro-2-methyl-
1,4-diaminobenzene It 42 Il It 2-methoxy-1,4
di aminobenzene board
eaux 45 Il Il 2,5-dimethyl-1,4
diaminobenzene ti i 44
L. Il M. 1,4-diaminobenzene sharp
laugh j 4 ₅ 4-methoxy-5-amino-
benzenesulfonic acid
(4 ^f -Chlor) -phenyl-
amide Il ? -Chlor-1,4-di-
arninobenzene board
eaux ti 1,4-diaminobenzene orange

009330/16 ,. -

«
I. 46 4-methoxy-3-amino
benzenesulfonic acid
(2,5'-dichloro) -
phenylamide II III IV 47 Il 2,3-hydroxy
anphthoic acid 1,3-diamino-4,6-
dichlorobenzene blue
Red 48 It Il 4,4 ^f -diamino-5,3'-
dichloro-l, l'-di-
phenyl Crowd
laugh 49 4-methoxy-3-amino
benzenesulfonic acid
(2 ' _J 4 ^l , 5'-trichlor) -
phenylamide Il 5-chloro-2-methyl-
1,4-diaminobenzene board
eaux 50 Il It 1,4-diaminobenzene Crowd
laugh 51 Il Il 4,4'-DIaHiInO -),) * -
dichloro-l ^ l'-di-
phenyl orange 52
ί. 4-methoxy-3-amino-
benzenesulfonic acid
(N-methyl) -phenyl-
amide M. 1,5 diamino
naphfchalin Crowd
laugh 53 4-methoxy-3-a! Fiino-
ben zol sulfone a'ur e-
(N, N) -dipheny] amide ti 1,4-diaminobenzene board
eaux ! 54 4-methy1-5-amino-
benzenesulfonic acid
phenylamide Il It It 55 4-methyl-J-arnino-
benzolsu] foi; s ^: .iure
(2'-chloro) -phenyl-
amide If 1,5 diamino
naphthalene blue- ^
Red ti 2,5-dimethyl-1,4
diaminobenzene board
eaux
!
(
i

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I. 56 4-methyl-3-anri.no-
benzenesulfonic acid
(4'-chloro) -phenyl-
"Arr.id II III IV ί
■
i 57 4-Kethyl-> amino-
bensol sulfonic acid
2 ^! , 5 ^! -dichlor-
phenylamide 2,3-hydroxy
naphthoic acid I 4,4'-diamino-3 _J 3 ^l -
3 dichloro-1, I ¹ -di
phenyl orange 58 4-methyl-3-amino
benzenesulfonic acid
(2 ', 4', 5'5- ^ iChOr)
-phenylamide Il 2-chloro-1,4-diamino
benzene sharp
laugh I.
j 59 4-methyl-3-amino
benzenesulfonic acid
(N-ethyl) phenyl
amide Il I 2,5-DiChIOr -,! ^ -
diaminobenzene Il
I. 60 Il Il 4,4'-diamino-3 _J 3'-
diohlor-l, l'-di- ·
phenyl orange 61 2,5-dimethoxy-4-
aminobenzenesulfone
acid (N-ethyl) -
phenylamide Il 1,5 diamino
naphthalene Il 62 4-methoxy-3-amino
^ enzenesulfonic acid
phenylamide. Il 1,4-diaminobenzene violet 63 4-methyl-3-amino
benzenesulfonic acid
dibenzylamide ti 4,4'-diarhino-2,2'-
dichloro-1,1 ¹ -di
phenyl ruby * 64 ■ η It 2-methoxy-5-chloro
1,4-phenylenediamine Red 65 4-methoxy-3-amino
benzenesulfonic acid,
phenylamide Il 2, 5-dimethoxy-l, 4-
phenylenedi amine Brown-
prickly
Red Il 4 _i 4'-diaminodi-
phenyl, sharp
laugh

009830/1625

Example 2.

5.85 parts of ^ -amino - ^ - methoxybenzene-sulfonic acid phenylamide are heated to 70 with 200 parts of water and 7.5 parts by volume of 30% hydrochloric acid and cooled. It is diazotized with 5.25 parts by volume of 4N nitrite solution at 0 to in the usual way and filtered. At 0 to 5, 1.9 parts of borax in aqueous solution are added to the diazo solution.

On the other hand, 5.08 parts of bis (2-hydroxynaphthalene-3-carboxylic acid) -2 ', 5'-dimethoxy-1', 4'-phenylenediamine in 200 parts of water and 6 parts by volume of 30 # iger Sodium hydroxide solution dissolved at room temperature and filtered. Diazo and coupling components are used if necessary made to equal volume by dilution with water.

The two solutions are fed continuously to a mixing nozzle, whereupon _{the components are coupled immediately at 15 to 20 and at a P H} value of 8.5 to 9 * 0. The resulting pigment suspension is filtered off and the filter residue is washed out thoroughly with hot water. The moist pigment press cake is dehydrated with 200 parts by volume of nitrobenzene azeotropically while stirring and then boiled for a further 2 hours. At 100 the pigment is filtered off and washed first with hot nitrobenzene and then with cold methanol and dried at 40 to 50; it is identical to that obtained in Example 1, paragraph 2.

009830/1625

The table below describes further pigments which are obtained if one follows the above Details of two molecules of the diazo compound from the in column I. said amine with the bis (2-hydroxy-5-naphthoyl) compound of the diamine mentioned in column II. Column III there the hue of the polyvinyl chloride film colored with the pigment obtained at.

009830/1625

I. 1 jJ-amino-4-methoxybenzene-
1-sulfonic acid-phenylamide II III CXI 3-amino - ^ - methoxybenzene-
l-sulfonic acid- (2 ', 4'-
dimethylphenyl) amide 2,5-dimethyl
1,4-diaminobenzene bordeaux 5 ^ -Amino - ^ - methoxybenzoi-
1-sulfonic acid- (4'-chloro-,
phenyl) amide Il . ·· 4th 5-amino-4-methoxybenzene
1-sulfonic acid-phenylamide It Il 5 3-amino-4-methylbenzene
1-sulfonic acid- (4'-phenyl-
phenyl) amide 2,5-dichloro
1,4-diaminobenzene blue red 6th 4-chloro-3-amino-benzene-
sulfonic acid- (2 ', 5'-di-
chlorine) phenylamide Il bordeaux 7th Il It Il 4,4'-DIaIrJLnO-J ^ J ¹ -
dichloro-1,1? -di
phenyl \ Red

0 09830/1625

Example 5-6 parts of the diazoamino compound of the formula

N — N = N - <^ \

(prepared by coupling diazotized! 4-methyl-3-aminobenzenesulphonic acid anilide on piperidine in an alkaline medium) and 5.82 parts of bis- [2'-hydroxy ~ 3'-naphthoyl] -2,5-dimethyl-1,4-phenylenediamine are suspended in 130 parts of σ-dichlorobenzene, heated to 70 to 80 and treated with 10 parts of glacial acetic acid. The mixture is heated to 120 ° and stirred for 2 hours at 120 to 125 °. After this time, the cleavage of the diazoamino compound and the coupling are complete. The red pigment is filtered off while hot, washed with hot o-dichlorobenzene, methanol and hot water. After drying in vacuo at 80, 6.44 parts of the disazo dye of the formula are obtained

009830/1625

OX

N ^ου 2

I OH

CONH-

which is difficult to insoluble in the usual solvents and polyvinylchiride films in red tones are excellent Light, varnish and migration fastness colors.

009830/1625

- 51 -

Example 4.

65 parts stabilized polyvinyl chloride, Parts of dioctyl phthalate and 0.2 part of the dye obtained in Example 1, paragraph 2, are stirred together and then rolled back and forth on a two roll calender for 7 minutes at 140. You get one Bordeaux-colored film with very good light and migration fastness.

009830/1625

Claims (1)

Claims. Disazo pigments of the formula / 4 R ₁ -SO ₀ N | 1 2 \ N ^R 5 4 \ NSO ₀ -R ₁ ² I. OH HO I N Π N - ^V GONH- -HNOC in which R 1 denotes an aryl radical in which the sulfonamide group is in the m- or p-position to the azo group, R ₂ denotes a naphthalene radical in which the azo, hydroxy and CO groups are in the I2,3-position, R a Arylene radical, Rr is an aralkyl or aryl radical and Rp is a hydrogen atom, an alkyl, aralkyl or aryl radical. Disazo pigments according to claim 1 of the formula wherein X is a hydrogen or halogen atom, 009830/1625 a cyano, nitro or an alkoxy ^ group, X, a hydrogen or halogen atom, an alkyl, Alkoxy, phenoxy or sulfonic acid amide group, R ,, R ^ and R have the meaning given. 3. Disazo pigments according to claim 2, wherein R 1 denotes a phenylene or diphenylene radical. 4. Disazo pigments according to claim 2, wherein R is a radical of the formula ³ pp denotes in which X ₂ and X, hydrogen or halogen atoms, 'denote alkyl or alkoxy groups. 5- disazo pigments according to claims 2 to 4, wherein Xp and X are alkyl or alkoxy groups. 6. Disazo pigments according to claim 2, wherein R is a radical of the formula denotes in which Y represents a hydrogen or halogen atom, an alkyl or alkoxy group steadifc. 00.9830 / 1625 7. Process for the production of disazo pigments of formula λ. n. / 4 4 \ R-SO ₀ N NSO ₀ -R ₁ | 1 2 \ / 2 | 1 N ^R 5 5 N " ? OH HO? ■ CONH R "^ HNOC where R, denotes an aryl radical in which the sulfonamide group is in the m- or p-position to the azo group, Rp denotes a naphthalene radical in which the azo, hydroxy and -CO groups are in the 1,2,3-position, R, an arylene radical, R ^, an aralkyl or aryl radical and R ^. a hydrogen atom, an alkyl, aralkyl or aryl radical, characterized in that one
a) a carboxylic acid halide of the formula R ₅ S Tan CO-HaI 009830/1625 - 55 - condensed with an arylenediamine in a molar ratio of 2: 1, or b) a diazo or diazoamino compound of an arylamine of the formula HpN-R ₁ -SOgNRj. R ^ with a 2,3-hydroxynaphthoic acid arylide of the formula • ^0Η CONH- HO NHOC couples in a molar ratio of 2: 1. 8. The method according to claim 7, characterized in that that one of a carboxylic acid chloride of the formula X COCl where X is a hydrogen or halogen atom, a cyano, nitro or an alkoxy group, X is a hydrogen or halogen atom, an alkyl, alkoxy, phenoxy or sulfonic acid amide group, Rjj and R ₁ - have the meaning given. Method according to claims 7 and 8, thereby 009830/1625 - 56 - characterized in that a phenylenediamine or a diaminodiphenyl is used as the arylenediamine. 10. The method according to claim 9t, characterized in that there is a diamine of the formula Γ> used, in which Xp and X are hydrogen or halogen atoms, Mean alkyl or alkoxy groups. 11. The method according to claim 10, characterized in that a diamine of the formula given is used wherein the X "and X represent alkyl or alkoxy groups. 12. The method according to claim 9, characterized in that there is a diamine of the formula Y Y 009830/1625 - 57 - used, wherein Y is a hydrogen or halogen atom, a Denotes alkyl or alkoxy group. 15. Process for pigmenting high molecular weight organic material, characterized by the use of the dyes according to claims 1 to 6. Ik. The pigmented material obtained according to claim 15. 009830/1625