DE2126767A1 - New disazo pigments and processes for their production - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Asemann Dr.R. Koenigiberger - Dipl. Phys. R. Timber Construction «

Dr. F. Zumstein jun. 01? ß 7 ß 7

Patent attorneys ^tltu ' ^u '

8 Munich 2, Bräuhausstraße 4 / III

CIBA- GEIGY AG, BASELF SWITZERLAND)

Case 3-7052
DEUTÖCIIIJUJD

New dxsazo pigments and processes for their production.

It has been found that you can become new valuable

Disazo pigments of the formula

OH OH .

R ₁ -N = NR ₂ -CONH-R ₅ -OAOR ₅ -NHOC-R ₂ TN = NR ₁

10 9 8 4 9/1799

arrives, wherein R, the remainder of a diazo component, R ₀ a,

Naphthalene radical, in which the azo, hydroxy and -CO group

are in the 1,2,3-position, R _{x is} an aryl radical and A is a ^ ■ alkylene or arylene radical, if one

a) an azo dye carboxylic acid halide. the formula

OH

R ₁ -N = NR ₂ -COHaI
with a diamine of the formula

H ₀ NR _x -OAOR _x -HH ₀ . . .

condensed in a molar ratio of 2: 1, or

b) a diazo or diazoamino compound with a bis-naphthol

the form

OH

C (X IO

^VV \ j0Iffi-R, -0-A-0-R, -NH0C ' ^VV ^

in the Mp! ratio 2: 1 clutch.

Since the dyes according to the invention are pigments, water-solubilizing groups are 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

109849/1799

wherein X and Y H or halogen atoms are alkyl, alkoxy, aryloxy, Nitro, cyano, trifluoromethyl, carboxylic acid ester, Carboxamide, sulfonic acid ester, sulfonic acid amide or Acylamino groups, Z is an H or halogen atom, an alkyl or alkoxy group, X, an H or halogen atom, an alkoxy, Mean nitro or cyano group.

The azo dyestuff carboxylic acids on which the acid halides to be used according to the invention are based are obtained by coupling a diazotized amine, preferably an aminobenzene and in particular one of the formula X _γ

with a 2,3 ~ hydroxynaphthoic acid.

The following amines may be mentioned as examples: aniline,.

2-, 3- or 4-chloraniline
3,4-dichloroaniline
2,3-dichloroaniline
2,4-dichloroaniline.

2,5-dichloroaniline
2,6-dichloroaniline
2,4,5-trichloroaniline.

2,4,6-K? Ichloraniline. -

2,3,4-trichloro aniline

2-, 3- or 4-bromoaniline.

109 849/1799

. 2, 4-dibromoaniline
2,5-dibroraaniline
2.- _s J> - or 4-methylaniline 2, 4-dimethylaniline
2, 5-Dimethylanllin

2-methyl-5-chloroaniline 2-methyl-4-chloroaniline 2-methyl-4,5-dichloroaniline Ji- trifluoromethylaniline 2-chloro-5-trifluoromethylaniline 4-chloro-2-trifluoromethylaniline J) ₃ 5-ditrifluoromethylaniline 4-trifluoromethyl -2-aminobenzene-1-ethyl sulfone 2-, J> - or 4-nitroaniline 2,4-dinitroaniline

4-chloro-2-nitroaniline

2-chloro-4-nitroaniiine

4-methy1-2-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

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2- and 4-ethoxyaniline.

3-chloro-4-methoxyaniline 2-Nxtro-4 ~ methoxyaniline 2-N ^r itro-4-sulfoxyaniline 2-methoxy-5-nitroaniline 2-methoxy-5-chloroaniline 2 j 5-di-ethoxy-4-chloroaniline 2, 5-dimethoxy-4-bromaniline 2,4-dimethoxy-5-ehloraniline 2-methoxy-5-trifluoromethylaniline 2-methoxy-5-benzylsulfonyl-aniline 2-amino-4-trifliiormethy 1-4 ^f -chlorodiphenyl ether 2-amino- 4-trifluorinethyl-diphenylather 2-amino-4-chloro-diphenylether 2-amino-2 ^f , 4-dichloro-diphenylether, 2-araino ^ 4j 4'-dichloro-diphenylether 1-aminobenz oil-2-earboftsäuremethylster l- Amino-1-chlorobenzene-S-carboxylic acid methyl ester 2-Amino-5-nitrobenzoic acid methyl ester 1-amino-2-methylbenzene-5-carboxylic acid methyl ester 1-amino-2-chlorobenzene-5-carboxylic acid methyl amide 4-methyl-3-amine -benzoic acid amide 4-methyl-3-amine-p-benzoic acid anilide 2,4-dichloro-5-amino-benzoic acid amide 2,4-dichloro-5-amino-benzoic acid anilide ^ -Methoxy - ^ - aminO-benzaeic acid amld

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^ -MethOxy-jJ -amino-benzoic acid-J'-trifluoroethylanilide 1-amlnobenzene-3-sulfonic acid amide

1-aniinobenzene-3-sulfonic acid anilide

1-Aralnobenzo 1-5-sulfonic acid methyl araid l-aminobenzene-5-sulfonic acid ethylamide l-Amino-2-chlorobenzene-4-sulfonic acid amide, l-amino-2-chlorobenzene-5-sulfonic acid diethylamide 1-Amino-2-methylbenzene-5-sulfonic acid amide l-Amino-2-raethoxybenz oil-5-sulfonatedlme thy lamide 2-amino-naphtha1ine

1-aminoanthraquinone

2-aminoanthra quinone

l-amino-J-eiiloranthraquinone. -

The Azofarbstoffcarbonsäuren obtained are treated with agents that are capable of carboxylic acids into their 'halides such as the chlorides or bromides convert, so particular pentabromide, phosphorus oxyhalides and preferably with thionyl chloride with phosphorus halides such as phosphorus pentachloride or Phosphortrichlorld or.

The treatment with such acid-halogenating agents is expedient in inert organic solvents, such as dimethylformamide, chlorobenzenes, e.g. mono- or Dichlorobenzene, toluene, xylene or nitrobenzene carried out, in the case of the last 5, optionally with the addition of dimethylformamide.

In the preparation of the carboxylic acid halides 1st

1 Qi 843 / I

it is usually expedient to use those produced in an aqueous medium Azo compounds are first dried or azeotroped from water by boiling in an organic solvent to free. Azeotropic drying can, if desired be carried out immediately before treatment with the acid-halogenating agents,

According to the present process, the monocarboxylic acid halides obtainable in this way are condensed in a molar ratio 2: 1 with aromatic ^ diamines of the formula

H ₂ NROAOR ₃ -NH ₂
preferably with those of the formula

wherein A ^ is an alkylene group containing 2 to 6 carbon atoms and Y is an H or halogen atom, an alkyl or alkoxy. group means, and, in particular with those of the formula

in which Y, have the meaning given and η is a number from 2 to 4.

The following diamines are mentioned as examples! 1,2-di (4'-aminophenoxy) ethane,

1,2-di- (4'-amino-J5'-chlorophenoxy) -ethane 1,2-di- (4'-amino-3'-methylphenoxy) -ethane 1,2-di- (4'-amino-3'-methoxyphenoxy) -ethane

109 849/1799

. 1,2-di- (4'-amino-3'-ethoxyphenoxy) -ethane 1,2-di- (4'-amino-3'-isopropoxyphenoxy) -ethane 1,2-di (3'-aminophenoxy) ethane .l, 2-di (2'-aminophenoxy) ethane.

1,2-di- (2'-amino-4'-malorphenoxy) -ethane I ^ 2-di- (2'-amino-4'-methylphenoxy) -ethane 1,2-di- (2 * -amino- 4'-methoxyphenoxy-ethane 1, 2-di- (4'-aminonaphthoxy) -ethane 1,3-di- (4'-aminophenoxy) -propane 1,3-di- (4'-amino-3'- chlorophenoxy) propane 1,3-di- (4'-smlno-3'-methylphenoxy) propane I ^ 3-di- (4'-amino-3 ^T -methoxyphenoxy) propane 1,4-di- (4 * -aminop ^ enoxy) -butane 1,4-di- (4'-aminophenoxy) -benzene 1,4-di- (4'-amino-2'-chlorophenoxy) -benzene 1,4-di- (4 '-amino-2'-methylphenoxy) -benzene.1,4-di- (2 ¹ -aminophenoxy) -benzene 1,4-di- (2'-amino-4 -'-methyl-phenoxy) -benzene 1, 4-di- (3'-aminophenoxy) -benzene. 1,3 * -ϋ1- (4'-aminophenoxy) -benzene Ij 3-di- (4'-aiiiino-2 ^f -chlorophenoxy) -benzene.

The condensation between the carboxylic acid halides of the type mentioned at the beginning and the diamines are two-dimensional carried out in an anhydrous medium. On this condition it is generally surprisingly easy already at Temperatures that are in the boiling range of normal organic '

10 9849/1799

-Q-

Solvents such as toluene, monochlorobenzene, dichlorobenzene,

en /

Trichlorobenzene, nitrobenzene and similar / lie. To speed up For the implementation, it is generally recommended to use an acid-binding agent such as anhydrous sodium acetate or use pyridine. The dyes obtained are partly crystalline and partly amorphous and are mostly obtained in very good yield and in a pure state. It is expedient. to deposit the acid chlorides obtained from the carboxylic acids for the time being. In some cases, however, you can do without Damage to a separation of the acid chlorides are dispensed with and the condensation immediately afterwards the preparation of the carboxylic acid chlorides take place.

For embodiment b) of the invention Process is preferably used as starting materials Diazo or diazoamino compound of an amine of the formula

wherein X, Y and Z have the meaning given.

The bis.- to be used as coupling components. Naphthols are known per se by condensation of a corresponding 2,5-hydroxynaphthoic acid with a diamine

the formula -

H ₂ NR, -0-A-0-R, -NH ₂

in the presence of an acid chlorinating agent such as phosphorus trichloride manufacturable. Bisnaphthols of the formula are preferably used

109849/1799

wherein X., Y, and A, have the meaning given.

The coupling takes place by gradual addition the aqueous-alkaline solution of the coupling component for , acidic solution of the diazonium salt instead. The solution to the Coupling component to be used amount of alkali metal hydroxide is expediently calculated so that it is necessary for the neutralization the mineral acid released during the coupling from the diazonium salt is sufficient. The clutch is useful at

a ρ ,, - value from h to β. The p "value becomes ti η ·

advantageously adjusted by adding a buffer. As the buffer, for example, the salts, in particular alkali metal salts' of formic acid, phosphoric acid or especially acetic acid: in consideration! The alkaline solution of the coupling component suitably contains a wetting, dispersing or emulsifying agent, for example an aralkyl sulfonate such as dodecyl benzalsulfonate or the sodium salt of 1,1'-naphthyl methanesulfonic acid, polycondensation products of alkylene oxides / - "such as the action product of ethylene oxide to p-tert-octylphenol, also allyl esters of sulforicinoleates, for example n-butylsulforicinoleate

Coupling component can also be advantageous protective collars, for example 'methyl cellulose, or smaller amounts of inert ,.

• ■ ■ -

10Ö849 / 1799

organisßhar less soluble or insoluble in water Contain solvents, for example optionally halogenated or nitrated aromatic hydrocarbons, such as benzene, toluene, xylene, chlorobenzene or dichlorobenzenes Nitrobenzene, as well as aliphatic halogenated hydrocarbons, such as hydrocarbon tetrachloride or triehloroethyleneJ also water-miscible organic solvents such as acetone, ethylene glycol monoraethyl ether, methyl ethyl ketone, Methanol, ethanol or isopropanol.

One can also use the clutch advantageously in the catfish perform that an acidic solution of the diazonium salt with an alkaline solution of the coupling component in a mixing nozzle continuously combined, with an immediate Coupling of the components takes place. It is important to ensure,.

that diazo component and coupling component in squimoleculars Quantities are present in the mixing nozzle, with '■ a small excess of coupling component as a pre-. showing part. The easiest way to do this is to check the p "value of the liquid in the mixing nozzle. There is also in the mixing nozzle for a strong vortex ' of the two solutions to worry about. The resulting dye dispersion is continuously withdrawn from the mixing nozzle and the Dye was separated off by filtering. "- ·. ■

The coupling can also be carried out in the manner that one diazoamino compound containing the radical H, with demBLsnaphthol of the type mentioned , in an organic solvent, optionally in one aqueous organic solvents, preferably in counter- • wait an acid. 1 0 9 8 A 9/1 7 9 9

The aryldiazo to be used according to the process - Amides are obtained by known processes by condensation an aryldiazonium salt with a primary or, preferably, with a secondary amine. For this purpose A wide variety of amines are suitable, for example aliphatic Amines, such as methylamine, ethylamine, ethane-plamine, 'Propylamine, butylamine, kexylamine and especially dimethyl-' amine, diethanolamine, methylethanolamine, dipropylamine or dibutylamine, aminoacetic acid, methylaminoacetic- ' acid, butylaminoacetic acid, aminoethanesulfonic acid, methyl- ' aminoethanesulfonic acid, guanylethanesulfonic acid., ß-aminoethylsulfuric acid, alicyclic amines such as cyclohexylamine, N-methylcyclohexylamine, Dicyclohexylamine, aromatic amines, such as ^ -Aminobenzoic acid, sulfanilic acid, 4-sulfo-2-aminobenzoic acid, (^ -Sulfophenyl) -guanidine, ty-N-methylaminobenzoic acid, · 4-ethylaminobenzoic acid, l-aminonaphthalene-4-sulfonic acid l-aminonaphthalene-2, ^ - disulfonic acid, heterocyclic amines such as piperidine, morpholine, pyrrolidine, dihydroindole 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 Reaction medium are separated. In many cases, the moist press cake can be used for further implementation ' Will. In individual cases it can prove to be expedient to carry out the diazoamides beforehand

109849/1799

Vacuum drying or, after slurrying the moist presscake in a solvent, the water through remove azeotropic distillation.

The coupling of the diazoamino compound with the Napththol is made 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 compatible with water "'" • are miscible, "it is not necessary to use the diazoamino compounds to be used in anhydrous form. For example, the watery, moist filter cake can be used. The the Cleavage of the diazoamino compound prior to coupling takes place in an acidic medium. If you use neutral solvents, the addition of an acid, for example hydrogen chloride, sulfuric acid, formic acid or acetic acid, is required

The coupling is expediently carried out in the heat, preferably at temperatures between 80 and 180 ° C., and is generally very rapid and complete . constantly .: '.- -''. ■ ·.

... · Thanks to their insolubility, the Pigments can be isolated from the reaction mixtures by filtering off. Since the by-products remain in solution, The pigments obtained fall in excellent purity at. Post-treatment with organic solvents

109849/1799

in the case of pigments obtained via the aqueous coupling route is displayed. Another advantage of the invention Process is the high yield, the pigment-technically favorable form and the constancy of the properties of the obtained Pigments.

The new dyes are valuable pigments, which can be used in finely divided form for pigmenting high molecular weight organic material, e.g. cellulose ethers and esters, super polyamides or super polyurethanes or polyesters, acetyl cellulose, nitrocellulose, natural resins or synthetic resins, e.g. aminoplasts, in particular Urea and melamine formaldehyde resins, alkyd resins, Phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, Polyacrylic acid ester, rubber, casein, silicone and Silicone resins, individually or in mixtures. It does not matter whether the high molecular weight compounds mentioned as plastic masses, melts or in the form of spinning solutions, lacquers 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. The new pigments are characterized by the high fastness properties, in particular an excellent one Light and migration fastness.

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

109849/1799

Example 1.

1 part of the dye, which is obtained by coupling diazotized 2,5-dichloroaniline to 2, J3-hydroxynaphthoic acid, is heated in 150 parts by volume of o-dichlorobenzene with 15 parts of thionyl chloride to 110-120 ° for 3 hours. The dye acid chloride, which crystallizes in shiny red needles after cooling, is filtered off, washed with benzene and then with petroleum ether and dried in vacuo at 40-45. About j> k parts of the acid chloride are obtained, corresponding to 89.7 % of theory.

7.6 parts of the dye acid chloride thus obtained are stirred in 250 parts of ρ-dichlorobenzene »to this solution a solution of 2.44 parts of 1,2-di (4'-aminophenoxy) ethane is added at room temperature in 100 parts of o-dichlorobenzene and 0.2 parts of pyridine. The mixture is then heated over the course of 2 hours to 14o-145 ° and stirred for 6 hours at this temperature. Then it is allowed to cool to 10.0 °, filtered and washed with 120 ° warm o-dichlorobenzene until the filtrate runs off practically colorless. Then with methanol and finally washed with hot water. After drying in vacuo at 90-95 °, 9.1 parts are obtained, corresponding to 98% of theory of a red pigment of the formula

ei ■■■ * .- ei

CMC> -NH0 10984 9/1799

Rolled into polyvinyl chloride , brilliant yellowish red colorations with excellent migration and lightfastness are obtained with this pigment.

The following table contains other • pigment dyes., which are produced in the specified way. can, if the diazo compound in the column I listed amines to the specified in column II-2,5-hydroxynaphthoic acid coupled, the azo dyestuff carboxylic acids obtained are converted into ilire acid chlorides and these

condensed with the diamines specified in column III in a molar ratio of 2: 1. Column IV characterizes the nuance of with. polyvinyl chloride film colored with the pigments.

109849/179 9

I. - 17 - I. 2126767 III IV 2,4-diehloraniline 2,3-hydroxy
naphthoic acid 1,2-di- (4'-amino-
¹ phenyl) ethane Red 1 . 2-chloro-5-tri-
fluoromethy! aniline Il It
ι orange 2 4-tri fluoromethy1-
2-aminobenzο1-1-
benzyl sulfone It It ge Ib-
orange Nitro-2-trifluoro
me thy 1-aniline Il It blue
Red 4th 4-chloro-2-nitro-
aniline Il Il Brown 5 4-trifluoromethyl
2-amino-4'-chloro-
diphenyl ether Il ir Crowd
laugh β 4-chloroaniline It ir blue red 7th 2,4,5-Triehlor-
aniline It ti Red 8th 4-chloro-2-nitro-
aniline Il I ₃ 2-di- (4'-methy1-
2 ^! -aminopheny1) -ethane blue
Red 9 2,4-dichloroaniline * It Il Red 10 2 ~ chlorine-5-tri-
fluoromethylaniline Il tr scharrr -.
laugh 11 4-trifluoromethyl
2-nitroaniline It ir Red 12th 2,5-dichloroaniline Il It Red 13th 2,4,5-trichloro
aniline It 1,2-di- (4 ^l -amino-1'-
naphthol) ethane Brown 14th m-amino-henzo-
trifluoride η - tr Brown 15th 4-methy1-5-amino-
benz oe acid-3 ^f -
trifluoromethyl
anilide η l _J 2-di- (4'-amino-
phenyl) -ethah sharp
läeh 16

1098A9 / 1799

I ' II III IV 17th 2,5-dichloroaniline 6-bromo-2 _J , 3-
hydroxy
naphthic acid 1,2-di ~ (4'amino-
pheny1) ethane Red 18th 2,4,5-trichloro
aniline H Il blue
Red 19th It 6-methoxy-2,>
hydroxy ^
■ naphthoic acid H blue
Red 20th It 6-nitro-2 _Ä>
hydroxy
naphthioic acid It Red
Brown 21st II 6-cyan-2.5-
hydroxy
naphthoic acid if Red 22nd 4,4 -'- Dielilor->
aminodiphenyl
sulfide 2, ^ -hydroxy
naphthoic acid 2-methyl-5-methex3
1,4-phenylenedi amir bordeaux 23 H - η - 2,5-dimethyl-1,4
phenylenedi amine II 24 4-chloro-4-i-methyl
3- amine-diphenyl-
sulfide ti Il η 25th Il If 4, 6-dichloro-l ^ 3-
phenylenediamine. blue
Red

9849/1799

Dye prescription

65 parts of stabilized polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 parts of the gemass Example 1, paragraph 2, the dye obtained are stirred together and then on a two / alkene calender Rolled back and forth at 140 for 7 minutes. You get a red colored film of very good light and migration fastness.

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Claims (1)

- 20 claims. . f Disazo pigments of the formula
Ή R ₁ -N = NR ₂ -CONH-ROAOR-NHOC-R ₂ -N = NR ₁ where R, the remainder of a diazo component, R _? a naphthalene radical in which the azo, hydroxyl and -C0 groups are in the I, 2,, j5 position, R ^, an aryl radical and A an alkylene "or arylene radical. * Diazo pigments according to claim 1 of the formula N- X. OH OHH- ■ 7 ' 71 N Il . N HO I ■> _ _Μοσ ΛΑΛ ₂ wherein X and Y H or halogen atoms, alkyl, alkoxy, aryloxy, nitro, cyano, trifluoromethyl, carboxylic acid esters, carboxamide, sulfonic acid esters, sulfonic acid amide or acylamino groups, Z is an H or halogen atom, an alkyl or Alkoxy 'group, X _{1 is} an H or halogen atom, an alkoxy ,. "Nitro or cyano group, Y ₁ denotes an H or halogen atom, an alkyJL ^ or alkoxy group and A ₁ denotes an alkylene group containing 2-6 carbon atoms or a phenylene group. ~ $. Disazo pigments according to claim 2 of the formula 109849/1799 wherein X, Y, Z and Y have the meaning given - and n means a number from 2 to 4. 4. Process "for the production of disazo pigments Formula OH I I R ₁ -N = NR ₂ -CONH-R ₃ -OA-0-R-NHOC-R ₂ -N = NR ₁ wherein R-. the rest; a diazo component, R _{p is} a naphthalene radical in which the azo, hydroxy and -CO groups are in the 1,2,3-position, R ^ is an aryl radical and A is an alkylene or arylene radical, characterized in that a) an azo dye carboxylic acid halide of the formula OH
R ₁ -N = NR ₂ -CQHaI with a diamine of the formula, H ₂ NR ₃ -OAOR ₃ -NH ₂ condensed in a molar ratio of 2: 1, or b) a diazo or diazoamino compound with a bis the formula IN HO 109849/1799 couples in a molar ratio of 2: 1. 5. The method according to claim 4, characterized in that that one of an azo dye carboxylic acid chloride of the formula X ^ Έ- " H
OH where X and Y are H or halogen atoms, alkyl, alkoxy, aryloxy, nitro, cyano, trifluoromethyl, carboxylic acid ester, carboxamide, sulfonic acid ester, sulfonamide or acylamino groups, Z is an H or halogen atom, an alkyl or alkoxy group, X ₁ denotes an H or halogen atom, an alkoxy, nitro or cyano group. 6. "The method according to claim 5 3, characterized in that γοη a carbanic acid chloride of the formula JOGI v / orin X ^ Y and E have the meaning given, ^ erissahrßn according to requirements 4 to 6 _S dadureh ge et ,, / e ± νοη that no exerts mainiii 1038 43/1799 starts out, above all in A, an alkylene group containing 2 to 6 carbon atoms or a phenylene group and Y, an H or halogen atom, represents an alkyl or alkoxy group. 8. The method according to claim J _3, characterized in that one of a diamine of the formula starts out, where Y has the meaning given and η a Number in the value from 2 to 4 means. * · 9. The method according to claim 4b, characterized in that one of a diazo or diazoamino compound of an amine of the formula starts, in which X, Y and Z have the meaning given. 10. The method according to claims 4b and 9 * thereby characterized in that 'one of a bisnaphthol of the formula starts out, where X ,, Y, and A, have the meaning given 11. A method for pigmenting high molecular weight organic material, characterized by the use of the dyes according to Claims 1 to 4. 109 84 9/17 9-9- 12. The geraäss claim 11 obtained pigmented Material. 109849/1799