DE2418299A1 - NEW DISAZOPIGMENTS AND METHODS FOR THEIR PRODUCTION - Google Patents

Description

αΟΛ ΠΠΓΪΥ I J> / ~ V "" ~~ vJiL-IvJ I

Dr. F. Zumstein Sr. - Dr. E. Assmann Dr.R.Koenigübsrger - Dipl. F-hys.R. Timber builder

Dr. F. Zurr.sieiri jan.

Patent attorneys

8 Munich 2, Bräuhausstraße 4 / III

Case 3-8742 +
GERMANY

New disazo pigments and processes for their production

It was found that new valuable disazo pigments of the formula

0OR X

COOR

CHoCOCHCONH

^J ^ '\ NHOCCHCOCH ₃

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arrives ,,

worm

R is an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical,

X is a hydrogen or halogen atom, an alkyl or ' Alkoxy group containing 1 to 4 carbon atoms, a nitro, cyano, trifluoromethyl or carboxylic acid ester group, and

Y is a hydrogen or halogen atom, an alkyl or An alkoxy group containing 1 to 4 carbon atoms, a nitro, cyano, trifluoromethyl or carboxylic acid ester group mean if you have a diazo or diazoamino compound of an amine of the formula

CH,

COOR

with a bis-acetoacetyl-phenylenediamine of the formula

CH-COCH ₉ CONH - \ (~

^{J z} ^ t- ^ NHOCCH-OCCHß Y ^Z

couples in a molar ratio of 2: 1.

Disazo pigments of the formula are of particular interest

CH ₃

Ch ₃ COCHCONH-

COOR ₁

NHOCCHOCCH

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wherein R, one optionally substituted by halogen atoms or alkoxy groups containing 1-4 carbon atoms Alkyl group containing 1-6 carbon atoms, a cycloalkyl group containing 5-6 carbon atoms, an aralkyl group or optionally containing halogen atoms, alkyl or alkoxy groups 1-4 carbon atoms or alkoxycarbonyl groups containing 1-6 carbon atoms or alkanoy! Amino groups, containing 1-4 carbon atoms substituted phenyl group,

X, a hydrogen or halogen atom, an alkyl or alkoxy group containing 1-4 carbon atoms and Y, a hydrogen or halogen atom, an alkyl or alkoxy group containing 1-4 carbon atoms means.

The diazo components used are preferably those of the formula

wherein R ^ has the meaning given.

Examples are:

3-Amino-4-methyl-benzoic acid methyl ester 3-Amino-4-methyl-benzoic acid ethyl ester 3-Amino-4-methyl-benzoic acid n-propyl ester 3-Amino-4-methyl-benzoic acid iso-propyl ester 3-Amino-4-methyl-benzoic acid n-butyl ester 3-Amino-4-methyl-benzoic acid tert-butyl ester 3-Amino-4-methyl-benzoic acid-ß-chloroethyl ester 3-Amino-4-mechylbenzoic acid 7-chloropropyl ester

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CIBA-GElGY AG - 4 -

3-Amino-4-methyl-benzoic acid acrylic ester 3-Amino-4-methyl-benzoic acid phenyl ester 3-Amino-4-methyl-benzoic acid 2'-chlorophenyl ester 3-Amino-4-methyl-benzoic acid 3'-chlorophenyl ester 3-Amino-4-methyl-benzoic acid 4'-chlorophenyl ester ■ 3-Amino-4-methyl-benzoic acid 4'-bromophenyl ester S-Ammo ^ -methyl-benzoic acid ^ ', 4'-d.ichlorophenyl ester 3-Amino-4-methyl-benzoic acid 3 ', 4'-dichlorophenyl ester • 3-Amino-4-methyl-benzoic acid-2 ', 4', 5 '-trichlorophenyl ester

3-Amino-4-methyl-benzoic acid 2 ', 4', 6'-trichlorophenyl ester

3-Amino-4-methyl-benzoic acid-2 ', 3', 4 ', 5', O ¹ -pentachlorophenyl ester

3-Amino-4-methyl-benzoic acid-2'-methyl-phenyl ester 3-Amino-4-methyl-benzoic acid-3'-methyl-phenyl ester S-Amino - ^ - methyl-benzoic ^{acid- ^ 1} -methyl-phenyl ester 3- Amino-4-methyl-benzoic acid 3 ', 5' -ditnethyl-phenyl ester 3-amino-4-methyl-benzoic acid-4'-tert-butyl-phenyl ester 3-amino-4-methyl-benzoic acid-4'-iso- ainyl-phenyl ester 3-amino-4-methyl-benzoic acid-2'-methoxy-phenyl ester 3-amino-4-methyl-benzoic acid-4 ^f -methoxy-phenyl ester 3-amino-4-methyl-benzoic acid-2'-methyl- 4'-chloro-phenyl ester

3-Amino-4-methyl-benzoic acid-2'-methyl-6'-chlorophenyl ester

3-Amino-4-methyl-benzoic acid 3'-raethyl-4 ¹ -chlorophenyl ester

3-Amino-4-methyl-benzoic acid 3 ^f -methyl-6'-chlorophenyl ester

3-Amino-4-methyl-benzoic acid 4-acetylaπlino-phenyl ester 3-Amino-4-methyl-benzoic acid benzyl ester 3-Amino-4-methyl-benzoic acid 4'-methoxy-benzyl ester 3-Amino-4-methyl-benzoic acid-α-naphthyl-ester 3-Amino-4-methyl-benzoic acid-β-naphthyl-ester

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CIBA-GEIGYAG - 5 -

3-Amino-4-methyl-benzoic acid tetrahydro- / 3-naphthyl ester

3-Amino-4-methyl-benzoic acid 3'-oxy-pyridine ester 3-Amino-4-methyl-benzoic acid 4'-phenyl-phenyl ester.

The coupling components used are preferably those of the formula

CH ₃ COCH ₂ CONH (C)) NHOCCH ₂ COCH ₃

wherein X, and Y, have the meaning given.

These are known compounds that one by the action of diketene or acetoacetic esters on the corresponding phenylenediamines such as:

1,4-phenylenediamine 2-chloro-1,4-phenylenediamine 2-cyano-1> 4-phenylenediamine 2-Methy1-1,4-phenylenediamine, 2-methoxy-1,4-phenylenediamine 2-phenoxy-1,4-phenylenediamine, 2-nitro-1,4-phenylenediamine-2-Me thoxycarbonyl-1,4-phenylenediamine, 2-ethoxycarbonyl-1,4-phenylenediamine 2,3-dichloro-1,4-phenylenediamine 2,5-dichloro-1,4-phenylenediamine 2,6-dichloro-1,4-phenylenediamine 2-chloro-5-methyl-1,4-phenylenediamine 2-chloro-5-methoxy-1,4-phenylenediamine 2,5-dimethyl-1,4-phenylenediamine 2-methyl-5-methoxy-1,4-phenylenediamine

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2,5-dimethoxy-1,4-phenylenediamine

2> 5-diaethoxy-1,4-phenylenediamine 2-methoxy-5-ethoxy-1,4-phenylenediamine . 2,3,5-trichloro-1,4-phenylenediarain. 2,3,5,6-tetrachloro-1,4-phenylenediamine 2,5-dimethyl-3,6-dichloro-1,4-phenylenediamine-1,3-phenylenediamine 4-chloro-1,3-phenylenediamine 2-methy1-1,3-phenylenediamine 4-methyl-1,3-phenylenediamine 4-methoxy-1,3-phenylenediamine 2,4-dichloro-1,3-phenylenediamine 2,5-dichloro-1,3-phenylenediamine 4,6-dichloro-1,3-phenylenediamine 4,6-dimethyl-1,3-phenylenediamine 2,6-dimethyl-1,3-phenylenediamine 1,4-naphthylenediamine .1,5-Naphthylenediamine 2,6-Naphthylenediamine 2,3,5,6-tetramethyl-1,4-phenylenediamine.

The coupling takes place preferably in a weakly acidic medium, expediently in the presence of common, the coupling promoting means. As such, dispersants may be mentioned in particular, for example aralkyl sulfonates, such as dodecylbenzenesulfonate or 1,1'-dinaphthylmethane-2,2'-disulfonic acid or polycondensation products of alkylene oxides. The dispersion of the coupling component can also advantageously contain protective colloids, for example methyl cellulose or smaller amounts of inert ones, in water Contain sparingly soluble or insoluble organic solvents, for example optionally halogenated or nitrated aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene or nitrobenzene as well as aliphatic halogenated hydrocarbons

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substances such as carbon tetrachloride or trichlorethylene, also water-miscible organic solvents such as acetone, methyl ethyl ketone, methanol, ethanol or isopropanol. The coupling can also be carried out advantageously in such a way that an acidic solution of the Diazonium salt with an alkaline solution of the coupling component continuously combined in a mixing nozzle, the components being coupled immediately. Care must be taken that the diazo component and coupling component are in equimolecular amounts in the Mischdlise are present, it proves to be advantageous, a small excess of the diazo component to use. The easiest way to do this is to check the value of the liquid in the mixing nozzle. There is also a mixing nozzle for a strong vortex of the two solutions to worry about. The resulting dye dispersion is continuously withdrawn from the mixture and the dye was separated off by filtration.

Thanks to their insolubility, the pigments obtained can be isolated from the reaction mixtures by filtering them off. It proves to be advantageous to post-treat the pigments obtained with a, preferably above 100 ⁰ C boiling organic solvent. Benzenes substituted by halogen atoms, alkyl or nitro groups, such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene and pyridine bases such as pyridine, picoline or quinoline, and ketones such as cyclohexanone, ethers such as ethylene glycol monomethyl or monoethyl ether, prove to be particularly suitable. Amides, such as dimethylformamide or N-methyl! -Pyrrolidone, and sulfoxone.

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The after-treatment is preferably carried out by heating the pigment in the solvent at 100 to 150 ⁰ C ₅ wherein in many cases a grain coarsening occurs, which has a favorable effect on the light and migration fastness of the pigments obtained.

Finally, the coupling can also be carried out in such a way that the amine to be diazotized with the coupling component suspended in an organic solvent in a molar ratio of 2: 1 and with a diazotizing Agents, especially an ester of nitrous acid, such as methyl, ethyl, butyl, amyl or octyl nitrite treated.

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, such as ethyl cellulose, Cellulose acetate, cellulose butyrate, natural resins or synthetic resins, such as polymerization resins or condensation resins, e.g. aminoplasts, especially urea and melamine-formaldehyde resins, alkyd resins, Phenoplasts, polycarbonates, polyesters, polyamides or polyurethanes, polyolefins such as polyethylene or Polypropylene, polyvinyl chloride, polystyrene, polyacrylonitrile, polyacrylic acid ester, rubber, casein, silicone and Silicone resins, individually or in mixtures.

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

In addition to the pure pigment, the preparations can, for example, also contain natural resins, for example abietic acid or its Esters, ethyl cellulose, 'gelulose acetobutyrate, alkaline earth salts of higher fatty acids, fatty amines, for example Stearylamine or rosinamine, vinyl chloride-vinyl acetate copolymers, Polyacrylonitrile or polyterpene resins or water-soluble dyes, for example Contain dye sulfonic acids or their alkaline earth salts.

The dyes according to the invention stand out from the closest comparable dyes of DT-OS 2 103 765 substances through a greater color strength.

In the examples below, the parts mean, unless otherwise stated, parts by weight, the Percentages by weight and the temperatures are given in degrees Celsius.

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CIBA-GEIGYAG. - Jf -t \ J example 1

6.6 parts of 3-amino-4-methyl-benzoic acid methyl ester are concentrated in 200 parts by volume of glacial acetic acid with 10 parts by volume. Stirred hydrochloric acid, whereby the hydrochloric acid of the base. forms. It is then cooled to -5 ° by adding 300 parts of ice and diazotized by adding 10.5 parts by volume of 4N sodium nitrite. The yellow diazo solution is stirred at 0-5 ° until only traces of nitric acid can be detected. The diazo solution is then clarified by filtration with the addition of some decolorizing charcoal. The filtrate is brought to p "4 by adding 48 parts of anhydrous sodium acetate,
ti

At the same time, 6.2 parts of 2-methoxy-5-chloro-1,4-bisacetoacetylaminobenzene are dissolved with 38 parts by volume of 4 % sodium hydroxide solution in 150 parts of water and 2 parts of n-butyl sulforicinoleate are added. This solution is clarified by filtration with 0.5 part of decolorizing charcoal and then added dropwise to the diazo solution over a period of 1–1 1/2 hours with thorough stirring. The temperature of the reaction mixture rises to 15-20 °. After the end of the dropwise addition, no more diazo compounds can be detected in the mixture. The mixture is stirred for one hour at room temperature, then heated in 1 hour to 80-85 °, filtered hot and washed salt-free with hot water. After drying at 95-100 ° in vacuo, 11.9 parts of a yellow dye of the formula are obtained

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COOCH

CH ₃ COCHCONh-

^0CH

Cl

NHOCCHOCCH,

COOCH,

10 parts of the pigment thus obtained are in 200 parts by volume of Cellosolve for 18 hours at 145-150 ° misled. The dye takes on a uniform crystalline form. You can see it under the microscope fine yellow particles with a length of 5 / U. It is filtered at 140 °, washes with boiling cellosolve until the filtrate is colorless, then displaces the cellosolve with dimethylformamide and washes again at the end with ethanol. After drying, 8 parts of a bright yellow pigment dye are obtained. He colors Plastics such as PVC in greenish yellow tones excellent migration fastness. The treatment in the organic solvent can also be carried out directly with the moist filter cake can be made without prior drying. So can the moist press cake in picoline stirred at 100 - 120 °, filtered, washed with methanol and then with dilute hydrochloric acid, or the moist press cake is stirred in chlorobenzene, o-dichlorobenzene or nitrobenzene and azeotroped Freed from water by distillation and then worked up as described above.

The table below describes other dyes that are obtained by coupling the diazotized bases of the Column I with the bisacetoacetic arylides of the diamines

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Column II can be obtained. Column III indicates the color of the PVC film colored with 0.2% of these pigments.

E.g
No. Diazo base Bis-acetoacetylver-
binding of diamines j 0.2% staining
in PVC 2 3-amino-4-methyl-.
benzoic acid
methyl ester 1,4-phenylenediamine yellow 3 Il
• 2-chloro-1,4-pheny-
lenediamine It 4th Il 2-cyano-1,4-pheny-
lenediamine It 5 It 2-methy1-1,4-pheny-
lenediamine It 6th Il 2-methoxy-1,4-pheny
lenediamine Il 7th Il 2-nitro-1,4-phenylene-
diamine Il 8th It 2,5-dichloro-1,4-phe
ny lenediamine Il 9 Il 2,6-dichloro-1,4-phe
ny lenediamine π 10 Il 2-chloro-5-methy1-1,4-
phenylenediamine Il 11 Il 2,5-dimethyl-1,4
phenylenediamine ti 12th Il 2-Methy1-5 -methoxy-
1,4-phenylenediamine orange 13th Il 2,5-dimethoxy-1,4-
phenylenediamine It 14th It 2,3,5,6-tetrachloro;
1,4-phenylenediamine yellow 15th Il 1,3-phenylenediamine; It 16 It 4-chloro-1,3-pheny-;
diamine! ti 17th It I.
4-methyl-1,3-pheny
lenediamine dd 18th II 4-methoxy-1,3-pheny
lenediamine II

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Continuation of the table

E.g. Diazo base I Bis-acetoacetylver-
binding of diamine 0.2% coloring *
in PVC 19th 3-amino-4-methyl-
benzoic acid ethyl
ester 1,4-phenylenediamine light yellow : 20th M. 2-chloro-1,4-pheny-
lenediamine yellow 21 11 2-methyl-1,4-pheny-
lenediamine Il 22nd It 2,5-dichloro-1,4
phenylenediamine green yellow 23 Il 2-chloro-5-methoxy-
phenylenediamine yellow 24 Il 2-chloro-5-methyl-
1,4-phenylenediamine Il 25th It 2,5-dimethyl-1,4-
phenylenediamine reddish
yellow 26th It 1,3-phenylenediamine yellow 27 3-amino-4-methyl-
benzoic acid-n-
propyl ester 1,4-phenylenediamine Il 28 Il 2-chloro-1,4-pheny-
lenediamine It 29 Il 2-Me thy1-1,4-pheny-
lenediamine Il 30th η 2,5-dichloro-1,4
phenylenediamine Il 31 ti 2-chloro-5-methoxy-
1,4-phenylenediamine Il 32 Il 2-chloro-5-methy1-
1,4-phenylenediamine It 33 Ii 2,5-dimethy1-1,4-
phenylenediamine reddish.
yellow 34 3-amino-4-methyl-
benzoic acid iso-
propyl ester 1,4-phenylenediamine yellow 35 Il 2-chloro-1,4-pheny
lenediamine Il 36 Il 2-cyano-1,4-pheny
lenediamine Il

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Continuation of the table

E.g. Diazo base Bis-acetoacetylver- ■ 2-chloro-1,4-pheny- 0.27o staining No. binding of diamine Diamine in PVC .37 3-amino-4-methyl - 2-methy1-1,4-pheny- 2-chloro-5-methoxy- yellow benzoic acid iso- lenediamine 1,4-phenylenediamine 38 propyl ester 1,4-phenylenediamine 38 Il 2-methoxy-1,4-pheny- It lenediamine 39 II 2-nitro-1,4-pheny- ti lenediamine 40 It 2,5-dichloro-1,4 ti phenylenediamine 41 Il 2,6-dichloro-1,4. It • phenylenediamine 42 Il 2-chloro-5-methyl- Il . 1,4-phenylenediamine 43 ti 2-chloro-5-methoxy- Il phenylenediamine 44 II 2,5-dimethyl-1,4- orange- phenylenediamine yellow 45 Il 2-methyl-5-methoxy yellow 1,4-phenylenediamine 46 Il 2,5-dimethoxy-1,4 orange phe ny1enediamine 47 II 2,3,5,6-tetrachloro yellow 1,4-phenylenediamine 48 Il 1,3-phenylenediamine Il 49 II 4-chloro-1,3-pheny- II lenediamine 50 II 4-methyl-1,3-pheny- 'ti Diamine 51 ti 4-methoxy-1,3-pheny- Il lenediamine 52 3 -Amino-4-niethy 1- 1,4-phenylenediamine Il benzoic acid-n- butyl ester 53 Il ti 54 Il ti 55 3-amino-4-methyl- Il benzoic acid tert. buty! ester

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Continuation of the table

E.g.
No. Diazo base Bis-acetoacetylver-
binding of the diarain. 0.27o staining
in PVC 56 3-amino-4-methyl-
benzoic acid tert.
butyl ester 2-chloro-1,4-phenylene
diamine yellow 57 Il 2-chloro-5-methoxy-
1,4-phenylenediamine II 58 Il 1,3-phenylenediarain Il 59 3-Amino-4-me thy I-
benzoic acid -ß-
chloroethyl ester 1,4-phenylenediamine Il 60 Il 2-chloro-1,4-pheny
lenediamine Il 61 II 2-Me thy1-1,4-pheny
lenediamine Il 62 Il 2,5-dichloro-1,4
phenylenediamine It 63 II 2-chloro-5-methoxy-
1,4-phenylenediamine Il 64 II 2-chloro-5-methyl-
1,4-phenylenediamine Il 65 Il 2,5-dimethyl-1,4
phenylenediamine orange 66 3-amino-4-methyl-
benzoic acid-7-
chloropropyl ester 1,4-phenylenediamine yellow 67 Il 2-chloro-1,4-pheny
lenediamine yellow 68 Il 2-Me thy1-1,4-pheny
lenediamine yellow 69 II 2,5-dichloro-1,4
phenylenediamine yellow 70 It 2-chloro-5-methoxy-
1,4-phenylenediamine Il 71 Il 2-chloro-5-methyl-1,4
phenylenediamine II 72 Il 2,5-dime thy1-1,4-phe
nylenediamine Il 73 Il 1,3-phenylenediamine Il

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Continuation of the table

E.g..
No. Diazo base 74 3-amino-4-methyl-
allyl benzoate 75 C! 76 !1 77 3-amino-4-methyl-ben-
phenyl zoate 78. 11 79 Il 80 Il 81 Il 82 Il 83 Il 84 ti 85 Il 86 Il 87 Il 88 Il 89 Il 90 11 91 π 92 ι; 93 Il

Bis-acetic acid compound of diamine

0.2% staining in PVC

1,4-phenylenediamine

2-chloro-1,4-phenylenediamine

2-chloro-5-methoxy-1,4-phenylenediamine

1,4-phenylenediamine

2-chloro-1,4-phenylenediamine

2-cyano-1,4-phenylenediamine

2-methyl-1,4-phenylenediamine

2-methoxy-1,4-phenylenediamine

2-nitro-1,4 "
phenylenediamine

2,5-dichloro-1,4-phenylenediamine

2,6-dichloro-1,4-phenylenediamine

2-chloro-5-methyl-1,4-phenylenediamine

2-chloro-5-methoxy-1,4-phenylenediamine

2,5-dimethyl-1,4-phenylenediamine

2-methyl-5-methoxy-1,4-phenylenediamine

2,5-dimethoxy-1,4-phenylenediamine

2,3,5,6-tetrachloro-1,4-phenylenediamine

1,3-phenylenediamine

4-chloro-1,3-phenylenediamine

4- methyl-], 3- \ hrny-1cndiamine

yellow

orange yellow

Il

orange

yellow

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Continuation of the table

E.g.
No. Diazo base ι Bis-acetoacetylver-
binding of the diamond 0.27o staining
in PVC 94 3-amino-4-methyl-benzene-
acid phenyl ester 4-methoxy-1,3-pheny
lenediamine orange 95 3-amino-4-methyl-benzoe-!
acid-2'-chlorophenyl-
ester 1,4-phenylenediamine yellow 96 Il 2-chloro-1,4-pheny-
lenediamine It 97 Il 2-chloro-5-methoxy-
1,4-phenylenediamine Il 98 π 1,3-phenylenediamine Il 99 3-amino-4-methyl-benzene-
acid-3'-chlorophenyl-
ester 1,4-phenylenediamine ti 100 11 2-chloro-1,4-pheny
lenediamine It 101 Il ' l-chloro-S-methoxy-
phenylenediamine It 102 Il 1,3-phenylenediamine It 103 3-amino-4-methyl-benzene-
acid-4'-chlorophenyl-
ester 1,4-phenylenediamine It 104 M. 2-chloro-1,4-pheny
lenediamine Il 105 Il 2,5-dichloro-1,4-
phenylenediamine Il 106 Il 2-chloro-5-methoxy-
1,4-phenylenediamine Il 107 Il 2-chloro-5-methyl-
1j 4-phenylenediamine Il 108 Il 1,3-phenylenediamine Il 109 3-amino-4-methyl-benzene-
acid-4'-bromophenyl-
ester 1,4-phenylenediamine Il 110 Il 2-chloro-1,4-pheny
lenediamine Il 111 It 2-chloro-5-methoxy-
1,4-phenylenediamine It

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Continuation of the table

E.g.
No. Diazo base Bis-acetoacetylver-
binding of diamine - 0.27o staining
in PVC 112 3-amino-4-methylben-
zoic acid 2 ', 4'-dichloro
phenyl ester 1,4-phenylenediamine yellow 113 Il 2-chloro-1,4-pheny-
lenediamine Il 114 Il 2,5-dichloro-1,4
.phenylenediamine Il 115 ti 2-chloro-5-methoxy-
1,4-phenylenediamine H 116 M. 2-chloro-5-methyl-
1,4-phenylenediami-n II 117 Il 1,3-phenylendin Il 118 3-amino-4-methyl-ben-
zoic acid-2 ', 4', 5'-tri-
chlorophenyl ester 1,4-phenylenediamine light yellow 119 Il 2-chloro-1,4-pheny
lenediamine II 120 Il 2-methyl-1,4-pheny-
lenediamine Il 121 Il 2-methoxy-1,4-pheny
lenediamine reddish
yellow 122 Il 2,5-dichloro-1,4-phe
nylenediamine yellow 123 It 2-chloro-5-methoxy-
1,4-phenylenediamine It 124 Il 2-chloro-5-methy1-
1,4-phenylenediamine It 125 Il 2,5-dimethyl-l ₅ 4-
phenylenediamine Il 126 Il 2-methyl-5-methoxy
1,4-phenylenediamine Il 127 ti 2,5-dimethoxy-l ₃ 4-
phenylenediamine orange 128 Il 1,3-phenylenediamine yellow 129 Il 4-chloro-1,3-pheny-
lenediamine Il 130 3-amino-4-methyl-
benzoic acid-2 ', 4', 6'-
trichloropheny ester 1,4-phenylenediamine ti

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is

Continuation of the table

E.g.
No. üiazobase j Bis-Acetoacety! Ver
binding of diamine 0.27o staining
in PVC 131 3-amino-4-methyl-ben-
zoic acid-2 ', 4', 6'-tri-
chlorophenyl ester 2-chloro-1,4-pheny-
lenediamine yellow 132 ti 2-chloro-5-methoxy-
1,4-phenylenediamine Il 133 It 1,3-phenylenediamine ti 134 3-amino-4-methyl-ben-
zoic acid-2 ', 3 ^f , 4', 5 ',
6'-pentachloro-phenyl-
ester 1 j 4-phenylenediamine Il 135 Il 2-chloro-1,4-pheny-
lenediamine Il 136 Il 2-cyano-1,4-pheny-
lenediamine ti 137 ti 2-methyl-1,4-pheny-
lenediamine It 138 11 2-methoxy-1,4-pheny-
lenediamine reddish
yellow 139 Il 2-nitro-1,4-pheny-
lenediamine yellow 140 ti 2,5-dichloro-1,4
phenylenediamine It 141 Il 2,6-DiChIOr-I ^ -
phenylenediamine Il 142 It 2-chloro-5-methyl-
phenylenediamine Il 143 Il 2-chloro-5-methoxy-
1,4-phenylenediamine ti 144 Il 2,5-dimethyl-1,4-
phenylenediamine It 145 π 2-methyl-5-methoxy
1,4-phenylenediamine ti 146 Il 2,5-dimethoxy-1,4-
phenylenediamine orange 147 Il 2,3,5,6-tetrachloro
1,4-phenylenediamine It 148 ti 1,3-phenylenediamine Il 149 Il 4-chloro-1,3-pheny
lenediamine Il

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Continuation of the table

E.g.
No. Diazo base Bis-Acetoacety! Ver
binding of diamine 0.27o staining
of PVC 150! I.
3-amino-4-methyl-ben-
zoic acid-2 ', 3', 4 ', 5',
6'-pentachloro-phenyl- 4-Me thy1-1,3-pheny-
lenediamine orange 151 ester _n 4-methoxy-1,3-pheny-
lenediamine π 152 3-amino-4-methyl-ben-
zoic acid-2'-methyl-
phenyl ester 1,4-phenylenediamine Il 153 Il 2-chloro-1,4-pheny-
'Lenediamine 11 154 Il 2,5-dichloro-1,4
phenylenediamine 11 155 Il 2-chloro-5-methoxy-
1,4-phenylenediamine Il 156 II. 2-chloro-5-methyl-
1,4-phenylenediamine 11 157 Il 1,3-phenylenediamine 11 158 3-amino-4-methyl-ben-
zoic acid 3'-methyl-
phenyl ester 1,4-phenylenediamine Il 159 Il 2-chloro-1,4-pheny
lenediamine Il 160 Il 2-chloro-5-methoxy-
1,4-phenylenediamine Il 161 Il 1 j 3-phenylenediamine Il 162 3-amino-4-methylben-
zoic acid-4'-methyl-
phenyl ester 1,4-phenylenediamine 11 163 11 2-chloro-1,4-pheny-
lendiarnin Il 164 Il 2-chloro-5-methoxy-
1,4-phenylenediamine Il 165 Il 1,3-phenylenediamine 11 166 3-amino-4-methylben-
zoic acid-3 ', 5'-di
me thy1-phenyl ester 1,4-phenylenediamine It 167 Il 2-chloro-1,4-pheny
lenediamine Il

409845/0971

CLBA-GEIGY AG

-We-

Continuation of the table

E.g. Diazo base Il 409 pounds Bis-acetoacetylver- 0.27o staining ·· It No. binding of diamine of PVC: 168 3-amino-4-methyl Il 2-chloro-5-methoxy- yellow ti benzoic acid-3 ', 5'- 1,4-phenylenediamine dimethy1-phenyl- It Il 169 ester _n 1,3-phenylenediamine M. 170 3-amino-4-methyl- π 1,4-Ph.enylenediamine Il Il benzoic acid 4'-tert butyl phenyl ester Il reddish 171 ! I 2-chloro-5-methyl- H yellow Il 1,4-phenylenediamine 172 11 2-chloro-5-methoxy- It 1,4-phenylenediamine 173 Il 2,5-dimethoxy-1,4- orange phenylenediamine 174 Il 1,3-phenylenediamine yellow 175 3-amino-4-methyl- 1,4-phenylenediamine Il benzoic acid-4'-iso- amyl phenyl ester 176 Il 2-chloro-5-methyl- Il ¹ 1,4-phenylenediamine 177 Il 2-chloro-5-methoxy- It 1,4-phenylenediamine 178 II 2,5-dirnethoxy-1,4- orange phenylenediamine 179 ti 1,3-phenylenediamine Il 180 3-amino-4-methyl- 1,4-phenylenediamine Il benzoic acid-2 '- me thoxy-phe ny1- ester 181 2-chloro-1,4-pheny Il lenediamine 182 2-methyl-1,4-pheny lenediamine 183 2,5-dichloro-1,4-phe nylenediamine 184 2-chloro-5-methoxy- 1,4-phenylenediamine 185 2-chloro-5-methy1- .1,4-phenylenediamine 186 2,5-dimethyl-1,4-phe- nylenediamine 45/0971

CIBA-GEIGY AG

Continuation of the table

E.g.
No. Diazo base Bis-acetoacetylver-
binding of diamine 0.2% staining
of PVC 187 3-amino-4-methyl-ben-
zoic acid-4'-methoxy-
pheny! ester 1,4-phenylenediamine reddish-
yellow 188 II 2-chloro-5-methyl-
1,4-phenylenediamine Il 189 It 2-chloro-5-methoxy-
1,4-phenylenediamine Il 190 Il 2,5-dimethoxy-1,4
phenylenediamine orange 191 Il 1,3-phenylenediamine yellow 192 3-amino-4-methyl-ben-
zoic acid-2'-methyl-
4'-chloro-phenyl ester 1,4-phenylenediamine yellow 193 Il 2-chloro-1,4-pheny-
lenediamine Il 194 Il 2-methyl-1,4-pheny-
lenediamine - Il .195 Il 2,5-dichloro-1,4
phenylenediamine Il 196 M. 2-chloro-5-methoxy-
1,4-phenylenediamine It 197 Il 2-chloro-5-methyl-
1,4-phenylenediamine Il 198 II 2,5-dimethyl-1,4
phenylenediamine reddish
yellow 199 3-amino-4-methyl-ben-
zoic acid-2'-methyl-6 '-
chlorophenyl ester 1,4-phenylenediamine 200 Il 2-chloro-5-methyl-
1,4-phenylenediamine Il 201 Il 2-chloro-5-methoxy-
1,4-phenylenediamine Il 202 Il 2,5-dimethoxy-1,4
phenylenediamine orange-
yellow 203 It 1,3-phenylenediamine Il 204 3-amino-4-methylben-
zoic acid 3'-methyl-
4 ^f -chlorophenyl ester 1,4-phenylenediamine Il 409845 fO971

CIBA-GEIGY AG

Continuation of the table

E.g.
No. Diazo base Bis-acetoacetylver-
binding of diamine 0.27o staining
of PVC 205 3-amino-4-methyl-ben-
zoic acid 3'-methyl-
4'-chloro-phenyl ester 2-chlorof-5-methyl- '
1,4-pheny lendin orange-
yellow 206 I! 2-chloro-5-methoxy-
1,4-phenylenediamine Il 207 Il 2,5-dimethoxy-1,4
phenylenediamine Il 208 It 1,3-phenylenediamine yellow 209 3-amino-4-methyl
benzoic acid 3'-
methyl-6'-chloro-
phenyl ester 1,4-phenylenediamine Il 210 Il 2-chloro-5-methoxy-
1,4-phenylenediamine Il 211 Il 2-chloro-5-methyl-
1,4-phenylenediamine Il 212 Il -2,5-dimethyl-1,4
phenylenediamine reddish
yellow 213 Il 1,3-phenylenediamine yellow 214 3-amino-4-methy 1-
benzoic acid-4'-
acetylamino-phenyl-
ester 1,4-phenylenediamine 11 215 Il 2-chloro-5-methyl-
1,4-phenylenediamine 11 216 Il 2-chloro-5-methoxy-
1,4-phenylenediamine 11 217 Il 2,5-dimethoxy-1,4
phenylenediamine reddish
yellow 218 Il 1,3-phenylenediamine yellow 219 3-amino-4-methyl-
benzoic acid benzyl
ester 1,4-phenylenediamine Il 220 Il 2-chloro-1,4-pheny-
lenediamine Il 221 Il 2-methyl-1,4-pheny-
lenediamine II 222 Il 2-methoxy-1,4-pheny-
lenediamine Il

409845/0971

CIBA-GEIGYAG

Continuation of the table

E.g.·
No. Diazo base Bis-acetoacetylver-
binding of diamine 0.27o coloring '
of PVC 223 3-amino-4-meth.yl-ben-
benzyl benzoate 2,5-dichloro-1,4-pheny-
lenediamine yellow 224 It 2-chloro-5-methoxy-
1,4-phenylenediamine yellow 225 Il 2-chloro-5-methyl-1,4
phenylenediamine Il 226 ti 2,5-dimethyl-1,4-phe-
nylenediamine orange
yellow 227 It 2-Me thy1-5-methoxy-
1,4-phenylenediamine yellow 228 It 2,5-dimethoxy-1,4-
phenylenediamine orange 229 It 1,3-phenylenediamine yellow 230 ti 4-chloro-1,3-phenylene
diamine 11 231 3-amino-4-methyl-ben-
zoic acid-4'-methoxy-
benzyl ester 1,4-phenylenediamine It 232 It 2-chloro-1,4-phenylene
diamine ti 233 It 2-methy1-1,4-phenylene
diamine It 235 It 2,5-dichloro-1,4-pheny-
lenediamine ti 236 Il 2-chloro-5-methoxy-1,4
phenylenediamine ti 237 Il 2-chloro-5-methyl-1,4
phenylenediamine ti 238 Il 2,5-dimethyl-1,4-phe
ny lenediamine reddish,
yellow 239 3-amino-4-methyl-ben-
zoic acid-a-naphthyl-
ester 1,4-phenylenediamine yellow 240 ti 2-chloro-5-methyl-1,4-
phenylenediamine II 241 M. 2-chloro-5-methoxy-1,4
phenylenediamine Il 242 ti 2,5-dimethoxy-1,4-
phenylenediamine orange

409845/0971

- a * -IS *

E.g. '
No. . Diazo base Bis-acetoacetylver- ₍
binding of diamine 0.2% coloring '
of PVC: 243 3-amino-4-methyl-
benzoic acid-a-
naphthyl ester 1,3-phenylenediamine yellow
ι 244 3-amino-4-methyl-
benzoic acid-ß-
naphthyl ester 1,4-phenylenediamine ti 245 II 2-chloro-5-methoxy-
1,4-phenylenediamine ' Il. 246 Il 2-chloro-5-methoxy-
1,4-phenylenediamine π; 247 Il 2,5-dimethoxy-1,4-
phenylenediamine It 248 Il 1,3-phenylenediamine 249 3-amino-4-methyl
benzoesMure-tetra
hydro- / 3-naphthyl esters 1,4-phenylenediamine ti 250 Il 2-chloro-5-methyl-
1,4-phenylenediamine It 251 Il 2-chloro-5-methoxy-
1,4-phenylenediamine »Ι 252 Il 2,5-dimethy1-1,4-
phenylenediamine Il 253 Ii 1,3-phenylenediamine ti 254 3-amino-4-methyl-
benzoic acid-3'-oxy-
pyridyl ester 1,4-phenylenediamine It 255 It 2-chloro-1,4-pheny
lenediamine Il 256 It 2-methyl-1,4-pheny
lenediamine Il 257 It 2,5-dichloro-1,4
phenylenediamine ti 258 ti 2-chloro-5-methoxy-
1,4-phenylenediamine ti 259 Il 2-chloro-5-methyl-
1,4-phenylenediamine it 260 ti 2,5-dimethyl-1,4
phenylenediamine reddish
yellow 261 Il 1,3-phenylenediamine yellow 262 3-amino-4-methyl-
benzoic acid-4'-
phenyl-phenyl ester 1,4-phenylenediamine Il
■ 409 845/0971

ί Ex.

! No. ;

Diazo base ■ Bis-acetoacetyl compound of the diamine

Ό, 27o coloring of PVC

263 j3-Amino-4-methyl-j 2-chloro-1,4-phenylene-yellow [benzoic acid-4'-I diamine iphenyl-phenyl ester j

264!

265 266 267 268 269

If

11

ti

It is 2-methyl-1,4-phenylene-j "diamine

2,5-dichloro-1,4-phenyj lendianiine

2-chloro-5-methoxy-1,4-phenylenediamine

2-chloro-5-methyl-1,4-phenylenediamine

2,5-dimethyl-1,4-phenylenediamine

1,3-phenylenediamine

It

409845/0971

orange

Il

65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 parts of the dye obtained according to Example 1, paragraph 2, vzerden stirred together and then rolled back and forth on a two-roll calender for 7 minutes at 140 °. A yellow colored one is obtained Film with very good light and migration fastness.

Example 271

1.00 g of the pigment prepared according to Example 1 is mixed with 4.00 g of the printing varnish of the composition

29.4% linseed oil stand oil (300 poise), 67.2 % linseed oil stand oil (20 poise), 2.1% cobalt octoate (8% Co) and

1.3% lead octoate (24 % Pb)

Finely rubbed on an EngeIsmann grinding machine and then on with the help of a cliché in the letterpress process

1 g / m printed on art paper. You get a strong, pure orange-tinged yellow with good transparency and gloss. In three or four color printing you can produce very brilliant shades of green by overprinting on blue.

The pigment is also suitable for other printing processes, such as Gravure printing, offset printing, flexographic printing and also gives very good results here.

409845/0971

Claims (8)

Claims wherein R is an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical, X is a hydrogen or halogen atom, an alkyl or alkoxy group, containing 1 to 4 carbon atoms, a nitro, cyano, tri fluorine thy 1 or carboxylic acid ester group, and Y is a hydrogen or halogen atom, an alkyl or alkoxy group, containing 1 to 4 carbon atoms, a nitro, cyano, trifluoromethyl or carboxylic acid ester group. 2. Disazo pigments according to claim 1 of the formula CH, COOR ₁ Ch ₃ COCHCONH- COOR ₁ NHOCCHOCCH wherein R ^ is an optionally substituted by halogen atoms or alkoxy groups, containing 1-4 carbon atoms, substituted alkyl group containing 1-6 carbon atoms, containing a cycloalkyl group 5-6 carbon atoms, an era group or an optional by halogen atoms, alkyl or 409845/0971 Alkoxy group η containing 1-4 carbon atoms or Alkoxycarbonyl groups containing 1-6 carbon atoms or alkanoyl amino groups containing 1-4 carbon atoms substituted phenyl group, Χ, a hydrogen or halogen atom, an alkyl or Alkoxy group containing 1-4 carbon atoms and Y, a hydrogen or halogen atom, an alkyl or alkoxy group containing 1-4 carbon atoms mean. 3. Process for the preparation of disazo pigments of the formula CHo
\ X CHo
+ J ρ x ^ -y.
N \ COOR - ^ !
Ν - <^> PTT ΓΉΡΤΤΡΠΜΤΤ Y N ^X C00R L «ri ο o UL> n.L> UiN ti ^ NHOCCHOCCHo wherein R is an alkyl, cycloalkyl, aralkyl, aryl or heterocyclic Rest, X is a hydrogen or halogen atom, an alkyl or alkoxy group containing 1 to 4 carbon atoms, a nitro, cyano, trifluoromethyl or carboxylic acid ester group, and Y is a hydrogen or halogen atom, an alkyl or An alkoxy group containing 1 to 4 carbon atoms, a nitro, cyano, trifluoromethyl or carboxylic acid ester group mean, characterized in that one has a diazo or diazoamino compound of an amine of the formula H ₂ N (Cf) \
COOR with a bis-acetoacetyl-phenylenediamine of the formula 409845/0971 CH ₀ COCH ₀ CONH
^{3 2} NH0CCH ₉ C0CH " couples in a molar ratio of 2: 1. 4. The method according to claim 3, characterized in that one of a diazo compound of an amine of the formula COOR emanates from what R, an optionally substituted by halogen atoms or alkoxy groups, containing 1-4 carbon atoms substituted alkyl group containing 1-6 carbon atoms, a Cycloalkyl group containing 5-6 carbon atoms, an aralkyl group or one optionally containing halogen atoms, alkyl or alkoxy groups 1-4 carbon atoms or alkoxycarbonyl groups containing 1-6 carbon atoms or alkanoylamino groups, containing 1-4 carbon atoms is a substituted phenyl group. 5. The method according to claims 3 and 4, characterized in that that you have a coupling component of the formula ^X l (Cj used where 409845/0971 CIBA-GEIGY AG. £ # Χ, a hydrogen or halogen atom, an alkyl or Alkoxy group containing 1-4 carbon atoms and Y, a hydrogen or halogen atom, an alkyl or alkoxy group containing 1-4 carbon atoms mean. 6- Process according to claims 3- 5, characterized in that the pigments obtained are a Subsequent to post-curing with organic solvents. 7. Process for pigmenting high molecular weight organic Material characterized by the use of a dye according to claims 1-2. 8. High molecular weight organic material containing a dye according to claims 1-2. 409845/0971