DE2011043A1 - New polyazo pigments and processes for their production - Google Patents

Description

DR. BERG DIPL .-. Mä. STAFF

PATENTANWÄLTE O Λ 1 1 Π / O

TO Il Uh 0

CIB-A AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6695 / E
Germany

Attorney's file 19 253 Munich, March 9, 197o

New polyazo pigments and processes for their production.

It has been found that new valuable poly azo pigments of the formula

R ₁ -N = NR ₀ -CONH. ·

. ^d R- [NHCOR ^ -N = N-Rj / ö 5 η

R-N = N-R ^ -CONH

where R, R, and R, - the residues of diazo components, Rp, R ^ and Rg hydroxynaphthalene residues, in which the azo, Hydroxy and -CO groups are in the 1,2,5-position, or the Residues of enolized or enolizable Ke.tomethylene compounds ^ R is an organic radical free of azo groups and η is one Whole number means ..if you have one mole of a polyamine of the formula

^H 2 ^N

condensed with 1 mol each of a carboxylic acid halide of the formulas R ₁ -N = NR ₂ -COHaI and RN = NR ^ -COHaI and with η mol of a carboxylic acid halide of the formula R ^ -N = N-Rg-COHaI.

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

Dyes of the formula are of particular interest

R ^ -N = N-R ,, CONH

^ A-X-

5 ^J m

wherein R ,, R _2, R ,, R ₂ ,, R ₁ -. Rg and the "specified

Have meaning, A and B aryl radicals, X a direct bond or a bridge member other than an azo group and m the Number 1 or 2, and in particular those of the formula

NO

009840/1890

wherein R ,, R ₅ and R- 'have the meaning given above, Y is a hydrogen or halogen atom, an alkoxy, nitro or cyano group and Z is an -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-, -SOC -OSOg-, -SOgNH-, -NHSOg- or NH- group, or a -0- or -S- atom, X, Y. and Z ₁ hydrogen or halogen atoms, alkyl or alkoxy groups mean.

Dyes of the formula are also of interest

NILE

I ^X R - N

H ⁵ I.

OH N

HO

?1

wherein R ₁ , R _x , Ä _K and Y have the meaning given and Z, a

¹ ■ * ■ ⁵ ! Hydroxy ^ /

Hydrogen or halogen atom, an alkyl or alkoxy group

means·

. From the series of dyes containing residues of enolizable ketomethylene compounds, for example acetoacetic acid arylide or pyrazolone residues, those of the formula are in particular those of the formula

I. N

CH _x COCHCONmUCONH |

^y ' ^V ^ -XB ENHCOR ^ NHCOCHCOCH,]

CH ^ COCHCONHRgCONH

MR,
called, 009840/1890

where R ₁ , R 1, R 1 -, A, B, X and m have the meaning given and R ₁₇ , Rn and R _{Q are} benzene radicals, or those of the formula NR

NV ^N

I ^x i "

CH-COCKCONffiUCONH I

7 ^ k _:

-NHCOR ^ NHCOCHCOCH,

CH., COCHC0NHR _o C0NH 3 ι 8

_ _ - '(~ \ vllVv VIA17

in which R 1, R 1, R, - and X. have the meaning given and R ₇ , Rn and Rq are benzene radicals.

The ones on which the carboxylic acid halides are based Carboxylic acids are obtained by coupling the diazo compound of an amine, especially an arylamine, for example an aminobenzene or aminonaphthalene with a 2,3-hydroxy

naphthalenecarboxylic acid or an enolized or enolizable ceto ^)
^ methylene compound, for example an acetoacetic acid arylide

or pyrazolones. Examples of diazo components are the called the following amines:

Aniline,

2-, 3- or 4-chloroaniline, 3,4-dichloroaniline, 2,2-dichloroaniline, 2,4-dichloroaniline, 2,5-dichloroaniline, 2,6-dichloroaniline, 2,4,5-trichloroaniline,

009840/1890

• 2,4,6-triohlöraniline,
2-, 5- or 4-bromoaniline 2,4-dibromaniline

• 2,5-dibromaniline

2-, 3- or 4-methylaniline 2,4-dimethylaniline
2,5-dimethylaniline

2-methyl-5-chloroaniline 2-methyl-4-chloroaniline

• 2-methyl-3-chloroaniline 2-chloro-5-trifluoromethylaniline 2-, 3- or 4-nitroaniline 2,4-dinitroaniline η

3-trifluoromethylaniline J>, 5-bis-trifluoromethylaniline, 2-chloro-5-trifluoromethylaniline, 4-chloro-2-nitroaniline

2-chloro-4-nitroaniline

4-methyl-2-nitroaniline 4-methyl-3-nitroaniline 2,4-dimethyl-3-nitroaniline 2-methyl-5-nitroaniline 2-ethyl-5-nitroaniline 2-methyl-4-nitroaniline 2-nitro-4-trifluoromethylaniline 4-nitro-2-trifluoromethylaniline 2- and 4-methoxyaniline

0Q984Q / 189Q

3-chloro-4-methoxyaniline 2-nitro-4-methoxyaniline 2 Nitro-4-ethoxyaniline, 2-methoxy-5-nitroaniline, 2-methoxy-5-chloroaniline 2,5-dimethoxy-4-chloroaniline, 2-methoxy-5-benzylsulfonylaniline

2-methoxy-5-trifluoromethylaniline k 2-ethylsulfonyl-5-trifluoromethylaniline 2-Amino-4- trifluoromethyl 1-4'-chlorodiphenyl ether 2-amino-4-trifluoromethyl-diphenyl ether 2-amino-4-chloro-diphenyl ether 2-amino-2 ', 4-dichloro-diphenyl ether 2-amino-4,4'-dichloro-diphenyl ether 1-aminobenzene-2-carboxylic acid methyl ester Ethyl l-aminobenzene-2-carboxylate

Methyl l-aminobenzene-2-chloro-5-carboxylate ρ 2-amino-5-nitrobenzoate methyl l-amino-2-methylbenzene-5-carboxylate 1-amino-2-chlorobenzene-5-carboxylic acid methyl amide 4-methyl - ^ - aminobenzoic acid amide 4-chloro-3-aminobenzoic acid amide 2,4-dichloro-5-aminobenzoic acid amide Jf-methoxy-jJ-aminobenzoic acid amide 4-methyl-35-aminobenzoic acid-2 ^l -chlor-5 ^l -trifluoromethylanilide 4-chloro-3-aminobenzoic acid-2 ', 5'-dichloroanilide,

009840/1890

4-chloro-3-aminobenzoic acid-2'-chloro-5'-carbomethoxyanilide 4-chloro-3-aminobenzoic acid-3 ^l -chloroanilide 2, ^ dichloro-S-aminobenzoic acid - ^ ', 5'-dichloroanilide 2,4-dichloro -5-aminobenzoic acid-3 ^f -trifluoromethylanilide 2,4-dichloro-5-aminobenzoic acid-3'-chloroanilide 5- Amlno-4-methoxy-2-chlorobenzoic ^{acid-3 I} -trii'luorme thylanilide 4-methoxy-2-arninobenzoic acid -3 ^f -chloranilide 4-methoxy * 3'-atninobenzoic acid-2 ^l , S'-dichloroanilide ^ -Carbomethoxy-J-aminobenzoic acid anilide ^ -Methoxy-J-aminobenzoic acid- ^ ¹ -trifluoromethylanilide ^ -Carbäthoxy-J-aminobenzoic acid- ^ ^! , 5'-dichloroanilide 4-aminobenzoic acid-2 ^f , 4'-dichlorophenylamide 4-aminobenzoic acid-2- ^t -chloro-5 ^l -trifluoromethylphenylamide 4-amino * 3-methylbenzoic acid 3'-trifluoromethylphenylamide 4-amino-3-n-ethy 1-benzoic acid-4'-chlorophenylamide 4-araino-3-nitrobenzoic acid-2 ', 5'-dichlorophenylamide 1-aminobenzene-3-sulfonic acid amide 1-aminobenzene-3-sulfonic acid methylamide 1-aminopbenzene-3-sulfonic acid ethylamide 1-aminobenzene-3-sulfonic acid dimethyl l-aminobenzene-3-sulfonic acid diethylamide

1-aminobenzene-3-sulfonic acid phenylamide 1-aminobenzene-3-sulfonic acid morpholide l-aminobenzene-3-sulfonic acid piperidide 1-aminobenzene-4-sulfonic acid amide 1-aminobenzene-4-sulfonic acid methylamide l-aminobenzene-4-sulfonic acid ethylamide

009840/1890

l-aminobenzene-4-sulfonic acid dimethylamide l-aminobenzene-4-sulfonic acid diethylamide l-aminobenzene-4-sulfonic acid phenylamide l-aminobenzene-4-sulfonic acid-N-methyl-N-phenylamide 1-amino -S-chlorobenzene - ^ - sulfonic acid amide 1-amino ^ -ehlorbenzol - ^ - sulfonic acid methylamide l-amino ^ -chlorobenzene ^ -sulfonic acid-dimethylamide 1-amino-2-chlorobenzene-4-sulfonic acid-diethylamide l-amino-2-chlorobenzene-4-sulfonic acid-phenylamide l-amino-2- chlorobenzene-5-sulfonic acid dimethylamide l-amino-2-chlorobenzene-5-sulfonic acid diethylamide 1-amino-2-chlorobenzene-5-sulfonic acid morpholide l-amino-2-chlorobenzene-5-sulfonic acid-phenylamide l-amino 2,5-dichlorobenzene-4-sulfonic acid amide, l-amino-2,5-dichlorobenzene-4-sulfonic acid dimethylamide, l-amino-2,5-dichlorobenzene-4-sulfonic acid phenylamide, l-amino-2-methylbenzene-5-sulfonic acid amide l-Amino-2-methylbenzeneT5-sulfonic acid methylamide l-amino-2-methylbenzene-5-sulfonic acid-dimethylamide l-amino-2-methylbenzene-5-sulfonic acid-phenylamide l-amino-2-methylbenzene-5-sulfonic acid-piperidide l- Amino-2-methylbenzene-5-sulfone acid-benzylamide l-amino-2-methylbenzene-5-sulphonic acid-phenylamide l-amino-2-methylbenzene-5-sulphonic acid-N-methyl-N-phenylamide l-amino-2-methylbenzene-5-sulphonic acid-2 ^l - chlorophenylamide 1-amino-2-methylbenzene-5-sulfonic acid-4'-chlorophenylamide 1-amino-2-methylbenzene-5-sulfonic acid-2 '_#4'-dichlorophenylamide

009840/1890

l ~ 'Amino-2-methylbenzene-5 ~ sulphonic acid-2 ^l -methylphenylamide, l-aminO-2-methylbenzene-5-sulphonic acid-4 ^f -methylphenylamide l-amino ^ -methylbenzene-S-sulphonic acid ^' - methoxyphenyl amide i-Amino-2-methylbenzene-5-sulfonic acid-4'-chloro-2'-methyiamide l-amino »2-methylbenzene-5-sulfonic acid-4 ^f -chlor-j5'-methylamide 1-amino-2- methylbenzene-5-sulfonic acid-3 ¹ -trifluoromethylphenylamide 1-amino-2-methylbenzene-4-sulfonic acid-4'-chloro-2'-methylphenylamide 1-amino-2-methylbenzene-4-sulfonic acid-4'-phenyl- phenylamide l-amino ~ 2-methylbenzene-4-sulfonic acid dimethylamide 1-amino-2-methylbenzene-4-sulfonic acid diethyramide l-amino-3-methylbenzene-4-sulfonic acid dimethylamide l-amino-2-methylbenzene 4-sulfonic acid phenylamide 1-amino-4-methylbenzene-5-sulfonic acid amide 1-amino-4-methylbenzene-5-sulfonic acid dimethylamide

• Pi. . . "

l-amino-2-methoxybenzene-4-sulfonic acid amide 1-amino-2-methoxybenzene-4-sulfonic acid methylamide l-amino-2-methoxybenzene-4-sulfonic acid-dimethylamide l-amino-2-methoxybenzene-4-sulfonic acid-phenylamide l- Amino- _i 2-methoxybenzene- "4-sulfonic acid-4'-methylphenylamide 1-amino-S-methoxybenzene-S'-sulfonamide 1-amino-2-methoxybenzene-5-sulfonic acid-dimethylamide 1-Afflino ^ -methoxybenzoi -S-sulfonic acid-phenylamide, l-amino-2-phenoxybenzene-4-sulfonic acid amide, l-amino-2-phenoxybenzene-4-sulfonic acid-dimethylamide, 1-amino-2-phenoxybenzene-4-sulfonic acid-phenylamide, l-amino-2-phenoxybenzene -5-sulfonic acid amide 1-amino-2-phenoxybenzene-5-sulfonic acid dimethylamide

00984071890

- ίο -.

1-Amino-2-phenoxybenzene-5-sulfonic acid-phenylamide l-aminobenzene-2,4-disulfonic acid amide l-aminobenzene-2,4-disulfonic acid dimethylamide l-aminobenzene-2,5-disulfonic acid amide l-aminobenzene-2,5-disulfonic acid dimethylamide 1-aminobenzene-2,5-disulfonic acid phenylamide

1-aminonaphthalene

1-amino-4-phenoxynaphthalene 1-Amino-8-chloronaphthalene 1-aminonaphthalene-3-sulfonic acid amide l-aminonaphthalene - ^ - sulfonic acid methylamide l-aminonaphthalene-3-sulfonic acid dimethylamide 1-aminonaphthalene-J-sulfonic acid phenylamide 1-aminonaphthalene-4-sulfonic acid amide 1-aminonaphthalene-4-sulfonic acid methylamide 1-aminonaphthalene-4-sulfonic acid dimethylamide 1-aminonaphthalene-4-sulfonic acid phenylamide 1-aminonaphthalene-5-sulfonic acid amide l-aminonaphthalene-5-sulfonic acid dimethylamide 1-aminonaphthalene-5-sulfonic acid phenylamide l-aminonaphthalene-6-sulfonic acid amide, l-aminonaphthalene-7-sulfonic acid aniide 2-aminona phthalene

2-aminonaphthalene-5-sulfonic acid amide 2-aminonaphthalene-5-sulfonic acid dimethylamide 2-aminonaphthalene-5-sulfonic acid phenylamide 2-aminonaphthalene-6-sulfonic acid amide 2-aminonaphthalene-6-sulfonic acid phenylamide

^ 009840/1890

OWÖJNAL INSPECTED

S-aminonaphthalene-T-sulfonic acid amide

2-aminonaphthalene ~ 8-sulfonic acid amide

2-aminonaphthalene-5,7-disulfonic acid amide 2-aminonaphthalene-6,8-disulfonic acid amide 1-aminoanthraquinone

2-aminoanthraquinone.

The obtained azo dye carboxylic acids are with Agents treated that are capable of converting carboxylic acids into their Halides, e.g. the chlorides or bromides., See above especially with phosphorus halides such as phosphorus pentachloride or phosphorus trichloride or pentabromide, phosphorus oxyhalides and preferably with thionyl chloride,.

The treatment with such acid- halogenating agents is expediently carried out in inert organic solvents such as dimethylformamide, chlorobenzenes, for example mono- or dichlorobenzene, toluene, xylene or nitrobenzene, with the latter 5 optionally with the addition of dimethylformamide. In the preparation of the carboxylic acid halides, it is usually advisable to dry the azo compounds prepared in an aqueous medium or to free them azeotropically from water by boiling them in an organic solvent be made · .

The obtained azo dye carboxylic acid halides are with polyamines of the formula

0098Ä0 / 1Ö90

ORiGlNALlNSPECTED

H ₂ N

J; R- (NH)
^H 2 ^N

wherein R is an organic radical free of azo groups, in particular an aromatic radical, and η an integer, preferably one in the value of 1-2, meaning condensed. Polyamines of the formula are of particular interest

^H 2 ^N \

_A _X-.B- (NH ₂ ) _m

H ₂ N

wherein Λ and B are aryl radicals, X is a direct bond or another Bridge member as an azo group and m denotes the number 1 or 2, and in particular triamines of the formula

wherein Z is a -HHCO-, -CONH-, -NHCONH-, -COO-, -OCO-, -SO 0-, -0SO ₀ -, -SO ₀ IIH-, -NHSO ₀ - or -NH group or a 0 or S atoms, VY-j and Z .. denote hydrogen or halogen atoms, alkyl or alkoxy groups.

Triaminobenzenes, especially those of the formula, are also of interest

X,

009840/1890

wherein X _{1 is} a hydrogen or halogen atom, an alkyl, hydroxy or alkoxy group, and triamines of the formula

wherein Y ₁ and Z _{1 have} the meaning given.

The following polyamines may be mentioned as examples: 1 * 3 * 5-triaminobenzene
2,4,6-triaminotoluene
2> 4 ^, 6-triaminophenol
2,4,6-triamino ^{-chlorobenzene 3 * 4 f} , 5-triaminobenzoic acid anilide ^ »^ SS-triaminobenzoic acid anilide 3 * 3 ^f * 5-triamino-4'-methoxy-benzoic acid anilide 3 * 4- ¹ ₃ 5- Triamino-2 ^J ₁ 5'-dichloro-benzoic anilide 3 * 4 ', 5-triamino-2', 5 '-dimethyl-benzoic anilide 3i4 ¹ , 5-ti * iamino-2', 5- ^t -dimethoxy-benzoic anilide 2,4 , 4 ^l -Triamino-benzoic anilide * '

2 ', 4 * 4 ^ triamino-benzoic acid ^{anilide 3' * 4,5 f} -Triamino-benzoic acid anilide 3, 5,5'-triamino-benzoic acid-1'-naphthylamide

Ö09840 / 189Q

3,3 ', 5'-triamino-naphthoic acid anilide 3,5,4 · '-Triamino-dipheny lather 2,4,4'-triamino-diphenyl ether 2,4,3'-triamino-diphenyl ether.

3,5,4 ^! -Triamino-diphenyl sulfide 2,4,4'-triamino-diphenylamine.

2,4,4'-triamino-2 ', 5'-dichloro-diphenylamine 3,5, ^' - triamino-benzoic acid-phenyl ester 3,3 ^l , 5-triamino-benzoic acid-phenyl ester

3.4 ^! , 5-Triamino-3'-methyl-benzoic acid phenyl ester 3,4 ', 5-triamino-3'-chlorobenzoic acid phenyl ester * 2,4,4'-triamino-benzoic acid phenyl ester ^{2,4,4' 1 -triaminobenzenesulf} acid anilide 2,3 ' » 4-triaminobenzenesulfonic anilide 2,4,4'-triamino-2', 5'-dichlorobenzenesulfonic anilide 2,4,4'-triamino-2,5'-dimethy1-benzenesulfonic anilide 2,4,4 ' -Triamino-benzenesulfonic acid-phenyl ester 2,3 ', 4-triamino-benzenesulfonic acid-phenyl ester 2,4,4'-triamino-3'-methyl-benzenesulfonic acid-phenyl ester 2,4,4'-triamino-diphenylurea 2,4,3 '-Triamino-diphenylurea 2,4,4'-triamino-2', 5 ^! -dichlorodiphenylurea 2,4,6-tris- [4 ^I -amino-2 ^l , 5'-dichloro-phenylimino] -l, 3,5-tpiazine

2,4,6-tris- [4'-aminophenoxy] ^{-1,3,5-triazine 2,4,6-tris- [3 l} -amino-phenyliminoJ-1,3,5-ti'iazine

2,4,6-Tris- [4'-amino-2 ', 5'-dichlorophenoxy] -1, 3,5-triazine 3j3 ^! , 5j5'-tetraminobenzoic acid anilide

009840/1890

OWGJNAL INSPECTED

^ ', j ^ VS-tetraminobenzoic anilide and bis- (3 ^t , 5 ^I -diaminobenzoyl) -2,5-dichloro-1,4-diaminobenzene <.

The condensation between the carboxylic acid halides of the type mentioned at the outset and the amines are expediently carried out in an anhydrous medium. On this condition it is generally surprisingly easy even at temperatures which are in the boiling range of normal organic solvents such as toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, and the like. To speed up For the implementation, it is generally recommended to use an acid-binding one Agents such as anhydrous sodium acetate or pyridine

to use. The dyes obtained are partly crystalline and partly amorphous and are usually in very good yield and preserved in a pure state. It is advisable to first remove the acid chlorides obtained from the carboxylic acids. In some cases, however, a separation of the acid chlorides can be dispensed with without damage and the condensation takes place immediately subsequent to the preparation of the carboxylic acid chlorides jj take place. *

Depending on whether you match the polyamine with the appropriate Number of moles of a uniform carboxylic acid halide or condensed with different carboxylic acid halides, one arrives at 2u symmetrical or asymmetrical dyes.

009840/1890

The new dyes are valuable pigments which, in finely divided form, are used for pigmenting high molecular weight organic material can be used, e.g. cellulose ethers and esters, super polyamides or super polyurethanes or polyesters, acetyl cellulose, nitrocellulose, natural resins or synthetic resins such as polymerization resins or condensation resins - e.g. aminoplasts, in particular Urea and melamine fprmaldehyde resins, alkyd resins, Phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, Polyacrylic acid esters, rubber, casein, silicone and silicone resins, individually or in mixtures.

It does not matter whether the high molecular weight compounds mentioned are in the form of plastic masses, melts or in the form of spinning solutions, lacquers or printing inks. Depending on the intended use, it proves to be advantageous to use the new pigments as toners or in the form of preparations.

In the following examples, the parts

Unless otherwise indicated, parts by weight, percentages percentages by weight, and temperatures are in degrees Celsius specified.

009840/1890

Example 1.

'20.5 parts of the azo dye carboxylic acid obtained by coupling diazotized! Aniline obtained with 2,3-hydroxynaphthoic acid are mixed with chlorobenzene in 100 parts. 1.5 parts of dimethylformamide and 7 parts by volume of thionyl chloride heated to 100 ° to 105 ° for 2 hours. It is then allowed to cool and the crystalline dyestuff carboxylic acid chloride is filtered off, washed with a little benzene and dried in vacuo at 50-60. 17.5 parts (80.6 % of theory) are obtained.

15 parts of the acid chloride thus prepared are stirred with 900 parts of o-dichlorobenzene and treated at 50 ° with a hot solution of 4 parts of 3,4 ', 5-triamino-2 ^! , 5 ^! -dimethy1-benzoic anilide added in 500 parts of o-dichlorobenzene. The mixture is heated to 140 ° with stirring and condensed for 14 hours at 140-145 °. The reaction mixture is filtered hot, washed with hot o-dichlorobenzene, then with methanol and then with water. After drying in vacuo at 95-100 °, 15 * 1 parts of a soft-grained red pigment powder which dyes plastics such as polyvinyl chloride and paints in brilliant scarlet shades of excellent migration, overcoating and lightfastness are obtained. The pigment has the following structural formula .

009940/1890

The table below lists further dyes which are obtained when the amine given in column I is diazotized by the process of this example, coupled with the 2,3-hydroxynaphthoic acid mentioned in column II, the azo carboxylic acid obtained is converted into the acid chloride and the latter in Molar ratio J: 1 with the triamine mentioned in column III or in a molar ratio of 4: 1 with the tetramine mentioned in column III. Column IV denotes the hue of a polyvinyl chloride film colored with the pigment obtained .. /;

009840/1890

I. II » 0 III IV 1 aniline 2,3-hydroxy
naphthoic acid Il 3,4 ', 5-trlamino-benzoic acid
anilide Sharlaeh 2 H Il Il 3,3 ' * 5-triamino-benzoic acid * -
anilide Red 3 ti It 3,3 *, 5-triamino-4'-methoxy-
benzoic acid ani11d orange 4th Il ti 3,4 ', 5-triainino-2', 5 '-di-
chlorobenzoic acid anilide Red orange 5 It It , 4 ^l , 5-TrlaraiTio-2 ^l - _f 5 ^! -dimethoxy-
benzoic acid anilide Red 6th Il It 2,4-, 6-triaminotoluene Red 7th Il η 3,4 ', 5-triaminobenzoic acid
phenyl ester Scarlet fever 8th M. It 3,3 ', 5-triaminobenzoic acid
phenyl ester It 9 It W. 3,4 ·, 5-triamino-3'-methy1-
benzoic acid phenyl ester Il 10 It , It
* 2,4,4'-triamino-dlpheny1-
urea Red 11 ti 6-bromo-2,3-
hydroxyhaph-
thoic acid Ϊ " ¹ , 4,4 '-TriaminobenZoesaure-
anilide Red 12th It 2,3-hydroxy
naphthoic acid 3, 5,5 '-Triaininobenzoic acid-
1-naphthylamine Red ^15th It ti 2,4,6-Tris [4-amtno-2,5-di-
chlorophenylimino] - - · Scarlet fever 14th Il 3.4 ■ ·, 5-triamino-2 ', 5 ^L dichloro
benzoic acid anil Red 15th ti To ~ (3 '* 5'-diaminobenzoy1) -
2,5-dlchlor-lj4-diaminobenzene Scarlet fever 16 o-chlorine-
aniline 3j 4 ', 5-triaminobenzoic acid
anilide orange Γ9840/1890

20110Λ3

I. II 0 . * III IV ' 17th o-chlorine-
aniline 2,3-hydroxy
naphthoic acid 3,4 ', 5-triamino-2', 5 '-dichlor-
benzoic acid anilide light brown 18th If Il 3,3 ' ) 5-triamino-benzoic acid
anilide orange 19th If Il 3,4 ', 5-triamino-2', 5'-dimethyl-
benzoic acid ailide Red orange 20th o-methyl
aniline Il Il " Red 21
ι ti It 3,4 ', 5-triamino-2' -chlorobenzoe-
acid anilide Red 22nd If Il 3,3 '* 5-triaminobenzoic anilide Scarlet fever 25th p-chlorine
aniline It Il bluest,
Red 24 Il • Il 3.4 ^! , 5-triaminobenzoic acid anilide Scarlet fever. 25th p-methyl
aniline It ti Red 26th Il Il 3 * 3 ' » 5-triaminobenzoic anilide Red 27 2.5 Di
chloraniline Il 3,4 ', 5-triaminobenzoic acid anilide orange 28 5-chloro-2-
methoxyanil ti
in Il ruby 29 2,4,5-tri-
chloraniline •
It π Scarlet fever 30th m-chlorine
aniline It η light brown 31 ß-naph-
thylamine η η bluish tint
Red 32 H It 3,4 ', 5-triamino-2', 5'-dimethyl-
benzoic anilide Il 33 Il Il 3ί3 ' * 5-triaminobenzoic anilide ruby 09840/1890

COPY

. I. II III IV 34 ■ α-naphthyl
• amine " 2,3-hydroxy
naphthoic acid 3 * 3 '* 5-triaminobenzoic acid
anilide violet 35 fl ti 3 * 4 ', 5-thiaminobenzoic acid
anilide violet 36 If If 3,4 ', 5-triamino-2', 5-dimethyl
benzoic acid anilide Il 37 p-chlorine
aniline Il Bis- (3 ', 5'-diaminobenzoyl) -
2,5-dichloro-1,4-diaminobenzene reddish
Brown 38 2,5 dichloro
aniline tr 1,2,4,5-tetraaminobenzene orange 39 ti ft 2,4,6rTris- [4'-aminophenoxy] - It 40 4-nitrone
methyl ani
lin It Il Scarlet fever

009840/1890

CX) PY

- 22 -

Example 2.

0.94 part of the acid chloride of the formula A and 0.42 part of the acid chloride of the formula B

N-

Il

(A) ^ Ly * (B)

- Both dye acid chlorides, prepared according to the method described in Example 1, - are with 100 parts Stirred o-dichlorobenzene and at 30 with a solution of 0.36 parts of 3,4 ', 5-triaminobenzoic anilide in 60 parts o-dichlorobenzene added.

The mixture is heated to 140 with stirring and condensed for 14 hours at 140-145. The reaction mixture becomes hot filtered, washed with hot o-dichlorobenzene, then with methanol and then with water. After drying in a vacuum at 95-100 °, 1.66 parts of a soft-grained red pigment powder, the plastics such as polyvinyl chloride, are obtained

and paints in brilliant dark red shades of excellent migration, overcoating and lightfastness. Of the Pigment dye has the presumed structural formula '

009840/1890

PH

ONH CO

I.
H·

QNH- <~~> -NHC

009840/1890

Claims (1)

Claims. 1. Polyazo pigments of the formula R ₁ -N = NR ₂ -CONH R ₃ -N = NR 1 -CONH R- [NHCOR ^ -N = NR ₁ -] ο p ⁿ wherein R-, R-. and R ₁ . the residues of diazo components, R_, R ^, and R / - Hydroxy na phthalinres te, in which the azo, hydroxy and -CO groups are in the 1,2,> -position or the residues of enolized or enolizable ketomethylene compounds, R one organic radical free of azo groups and η denotes an integer.
2. Polyazo pigments of the formula R ₁ -N = NR ₂ CONH R-N = N-R ^ CONH -X-B- £ NHCOR ^ -N = N-RJ wherein R ,, R _p , R ^, R ^ ,, R ^ and R ^ have the meaning given in claim 1, A and B are aryl radicals, X is a direct bond or a bridge member other than an azo group and m is the number 1 or 2 .means.'
5 · polyazo pigments of the formula I ^λ Rp-N N ⁵ I. I OH N X rv λ y \ - ^ NHCO ^^^^ 9 / t / MTTfX JQ. ^ X. I X XlXlWV XÄ. Ϊ 0OHH ' _N " ^z \ A ^3H NO. 009840/1890 " ¹ p Wherein R ,, R ^. and R ₁ - have the meaning given in claim 1 * Y a hydrogen or halogen atom, an alkoxy, nitro or cyano group and Z a -NHCO-, -CONH-, -NHCONH-y -COO- / -OCO- , -SO ₂ O-, -OSO ₂ -, -SO ₂ NH-, -NHSO ₂ - or -NH- group, or a -0- or -S-atom, X-, Y ^ and Z, hydrogen or Mean halogen atoms, alkyl or alkoxy groups. 4. Polyazo pigments of the formula H-N ⁵ H - I NV HO I. ■ NHC ( where R ,, R ,, Rp. and Y have the meaning given and Z-, ° ° *%} * & hydroxy- / %} y a hydrogen or halogen atom, alkyl-jforalkoxy group means. 5. Polyazo pigments according to Claims 1 to 4, in which the radicals R 1, R 1 and R_ represent benzene or naphthalene radicals. 6. Polyazo pigments according to claim 5 »wherein the radicals R ₁ ^ R, and Rc of the formula 009840/1890 in which X ₂ and Y _{2 are} hydrogen or halogen atoms, alkyl, alkoxy, phenoxy, nitro, cyano, carboxylic acid ester, alkanoylamino or trifluoromethyl groups and Z _{p is} a hydrogen or halogen atom, or a carboxamide group. 009840/1090 OWGlNAL INSPECTED 2Ö11ÖA3 ■ - ■■? 7 .- * 7 · * Process for the production of polyazo pigments the formula R ₁ -N = NR ₂ -CONH ■> * ■■■ ' ⁶ ~ 5 η R ₃ -N = NR ^ -CONH ^, wherein R ₁ , R, and R ₁ . the residues of diazo components, R_., R ^ and R ₆ hydroxynaphthalene residues, in which the azo, hydroxy and -CO groups are in the 1,2,5-position, or the residues of enolized or enolizable ketomethylene compounds, - ^{■■■■■:} -. ■ ■■■■ - ■■ ■■ - ■ ■■ ■■ - ■ .- ■■■■ - ■ '■: ■■ R is an organic radical free of azo groups, and ^ η denotes an integer, characterized in that one mole of a polyamine of the formula H ₂ N condensed with 1 mol of a carboxylic acid halide of the formulas R ₁ -N = NR ₂ -COHaI and R ₃ -N = NR ^ -COHaI and with η mol of a carboxylic acid halide of the formula Rc-N = NR ₆ -COHaI, 8. The method according to claim 7 * characterized in that »a polyamine of the formula :> A- _X -B- (NH ₂ ) _m ^H 2 ^N * where A and B are aryl radicals, X is a direct bond or a bridge member other than an azo group and m is the number 1 or 2. 0098A0 / 1890 9. The method according to claim 8, characterized in that that one of a triamine of the formula starts, where Z is a -NHCO-, -CONH-, -NHCONH-, -COO-, -OCO-, -SOgO-, -OSO ₂ -, -SOgNH-, -NHSO ₂ - or -NH- group or a - 0 or -S atom, Y ₁ and Z. mean hydrogen or halogen atoms »alkyl or alkoxy groups. 10. The method according to claim 7, characterized in that one of a triamine of the formula JC ft, where X _{1 is} a hydrogen or halogen atom, an alkyl, hydroxy or alkoxy group. 11. The method according to claims 7 to 10, characterized in that one mole of the polyamine with 1 mole of one Carboxylic acid halides of the formula N I OH N and . I OH OCl OCl 009840/1890 20T1QA3 and η mol of a carboxylic acid halide of the formula KHEL ■ N OH JL ^v fAAAc where R ,, R ^ and Rp. have the meaning given and Y is a hydrogen or halogen atom, an alkoxy, nitro or cyano group. ■ a 12. The method according to claims 7 and 11, characterized in that one starts from carboxylic acid halides of the formulas given in which R ,, R ^ and R ₁ - benzene or naphthalene radicals. IJ. Process according to claims 7 and 11, characterized in that one starts from carboxylic acid halides of the formulas given, in which R ,, _: 'R-, and R ^ radicals of the formula where Xp and Y _{2 represent} hydrogen or halogen atoms, alkyl, alkoxy, phenoxy, nitro, cyano, carboxylic acid ester, alkanoylamino or trifluoromethyl groups and Zp is a hydrogen or halogen atom or a carboxamide group. mean. 14. Process for pigmenting high molecular weight organic material, characterized by the use of the dyes according to claims 1 to 6. "-, ■ 0098AO / 1890 15 · The pigmented material obtained according to claim 14. 009840 / 189TJ