DE1066680B - Process for the production of azo pigments - Google Patents

Description

GERMAN

I INTERNAT. KL. C 09 b

PATENT OFFICE

EXPLAINING PUBLICATION 1066 680

C 14475 IVb / 22a

REGISTRATION DATE: MARCH 2, 1957

NOTICE
THE REGISTRATION
AND ISSUE OF THE
EDITORIAL: OCTOBER 8, 1959

It is known that in the normal aqueous coupling of diazo compounds without water-solubilizing agents Groups with azo components that are also not water-solubilizing Groups have very often uneven results in terms of yield, purity or hue can be obtained. It is necessary in some cases, the clutch z. B. in very dilute solution to perform, which is technically disadvantageous. It has also already been proposed that the azo component be a solution or the reaction mixture, wetting and dispersing agents, protective colloids and / or similarly acting agents to add.

It can also be found that diazo compounds without solubilizing groups with double coupling Azo components without solubilizing groups (here generally the phenolic, coupling-related Hydroxyl groups are not considered as solubilizing groups because their effect is lost in the azo pigment) can hardly be brought to double coupling by the usual methods.

One of the aims of the invention is to remedy these inconveniences.

It has been found that azo pigments are made from diazo compounds and azo components, both of which are free from sulfonic acid groups, are advantageously produced can be if the coupling is practically anhydrous in the presence of organic diluents carried out in a concentrated reaction mixture with mechanical mixing.

For the preparation of the reaction batches, such diazo compounds can advantageously be used which can easily be isolated directly, such as the sulfate of a-diazoanthraquinone. With these and other difficult to dissolve Salts or double salts of diazo compounds, which occur as moist press cakes, can through The addition of water-binding substances removes the remaining water content. As such, sparingly soluble salts of diazo compounds come, for example, the salts with naphthalene mono- and disulfonic acids, e.g. B. naphthalene-1-sulfonic acid and naphthalene-l, 5-disulfonic acid, in consideration and as double salts z. B. the long-known zinc chloride double salts. To the distance of the remaining water content can in all cases advantageously be dehydrated or partially dehydrated inorganic Salts of a water-binding character, such as aluminum sulphate, can be used. The manufacture of such

Cl

Process for the production of azo pigments

> - NH- OC- H ₂ C-OC registrant: CIBA Aktiengesellschaft, Basel (Switzerland)

Representative: Dipl.-Ing. E. Splanemann, patent attorney, Hamburg 36, Neuer Wall 10

Claimed priority: Switzerland of March 7, 1956

Dr. Hans Gärtner, Basel,

and Dr. Henri Streiff, Birsfelden (Switzerland),

have been named as inventors

dry and relatively stable diazo compound is generally known and does not require any special explanation.

The azo components can generally be prepared in anhydrous form without difficulty. For example, they can contain a couplable ketomethylene group in an open chain, such as this with the acylacetyl compounds, e.g. B. the acetoacetyl or benzoylacetyl compounds is the case, or a couplable ketomethylene compound may also be present in a heterocyclic ring, e.g. B. a pyrazolone ring or in a barbituric acid ring. The 2-oxynaphthalene-3-carboxylic acid group has an important group of azo components. In general, such diazo and azo components can be used with advantage, as they are in the so-called Ice paint making are common.

According to the present process, such azo pigments can also be produced by twofold Coupling are to be made using double coupling azo components. Such azo components can also belong to the groups mentioned above, such as 4,4 '- (acetoacetylamino) -3,3'-dimethyl-l, l'-diphenyl, Terephthaloyl diacetic acid di- (o-chlorophenylamide) of the formula

Cl

4,4'-Di- (2 "-oxy-3" -naphthoylamino) -1, 1 '-diphenyl and the corresponding in 3,3'-position by chlorine atoms of Methoxy substituted products, 1,5-di- (2'-oxy-

> - CO - CH ₂ --CO - HN - <^>

3 '- naphthoylamino) - aminonaphthalene, 1,4 - di - (2' - oxycarbazole-3'-carboylamino) benzene and 4,4'-di- (3 "-oxydiphenyleneoxide-2" -carboylamino) -1,1'-diphenyl.

909 637/332

3 4

For the preparation of the reaction batches can, for example, To prepare the / ^ modification, the coloring is an azo component without sulfonic acid groups with substances such. B. as described for a single dye in an organic solvent such as pyridine, ethylene USA.-Patent 2 687 410, preferred glycol, polyethylene glycol or their ether, dimethyl, in the heat with organic solvents formamide, chlorobenzene or o- Dichlorobenzene added 5 treated. Solvents that can be used are above all to be mentioned until a high-boiling organic liquid that is difficult to knead or easy to knead, the mass is formed. If the solvent itself does not have the most varied of body classes, such as the class of the acid-binding properties, such amides, amines, esters or lactones, hydrocarbons, agents, e.g. B. sodium acetate, an alkali metal hydroxide, a halogen or nitro hydrocarbon, and alkaline earth metal hydroxide or another, appropriately not io, can also be miscible with water. It is advantageous to add foam-generating alkaline substances. aromatic solvents such as aniline are used. By adding a stabilized diazo compound, xylene, but preferably nitrobenzenes, mono-, di- or then the coupling can be set in motion, with trichlorobenzenes, α-chloronaphthalene or mixtures thereof, expediently by further adding a solvent The treatment of the dyes with the specified ensures that the reaction mixture is always kneadable 15 solvents, preferably in the heat, in the remains. generally made above 100 ⁰ C ₁ . The amount

Using a non-acid-binding solvent to be used can vary between very

A mixture of wide limits can also be varied by means of ethylene glycol. One can optionally

Azo component and stabilized diazo compound to use so much solvent that the dye in

processed in a kneadable approach. The coupling solution works for some time, if necessary until it is fully

In this case, treatment can be achieved by slowly adding a constant dissolution of the dye to the desired level

acid binding agent, e.g. B. an alkali hydroxide, in temperature, usually between 110 and about 18O ⁰ C,

Gear can be set. In this way of working, if necessary, changes under pressure, heat and let cool,

in the course of the reaction, the kneading volume is only slightly. As a rule, however, it is sufficient to carry out the conversion

The coupling is conveniently carried out at relatively low 2 $ storage heating with a very small amount

Temperatures of about 10 to 30 ° C carried out; to an aromatic compound such as nitrobenzene, o-di-

For this purpose, the kneading apparatus is advantageously chlorobenzene or α-chloronaphthalene, for a short time

intense, e.g. B. with the help of ice water, cooled, since a larger amount of the solvent can be used

the kneading work that is expended generates heat, which, if a certain cleaning effect is desired

in the event of insufficient discharge, the temperature will increase significantly,

would. The pigments obtained in this way are worked up

The mechanical treatment can according to the present invention by methods known per se by removing the

Process on apparatus of known construction through solvent used, e.g. B. by centrifugation,

be performed for the intensive mechanical distillation or washing out or by simple

Processing of relatively tough media are set up, such as 35 filtering. The pigments obtained in this way can

Mixers, roller mills and especially kneading organic or organic media, in bulk or

devices from the Werner-Pfleiderer system. Preparations made from various plastics, such as poly-

After the coupling reaction has taken place, the coupling vinyl chloride films, varnishes, spinning masses can be distributed,

mass for the purpose of removing the pulls for the clutch. They result in valuable staining, which in some cases

set auxiliaries such as pyridine, as well as the resulting 40 coloristically more valuable shades and better fastness properties

By-products, e.g. B. salts, with water, acidic and / or as those that can be obtained with corresponding,

alkaline agents. can receive untreated dyes.

The present process is suitable - as indicated at the outset in the examples below, provided

mentioned - in addition, in a very small space and under nothing else stated, the parts are parts by weight,

Use of minimal amounts of solvent, such as the percentages by weight, and the temperatures

they are necessary to achieve a kneadable mass, are given in degrees Celsius. 1 mole means how

all monoazo pigments without sulfonic acid groups are generally customary, those corresponding to the molecular weight

to create a fanatic and quick way of working. The Kupp number of grams,

development generally proceeds very quickly. It can e.g. B. Example 1
azo dyes are also produced that still have a free 50

Have carboxyl group and as intermediate products A small kneading apparatus according to Werner-Pfleiderer

serve, in which the carboxylic acid group in the carbon is charged with 0.05 mol of 3,3'-dichloro-4,4'-di- (2 "-oxy-

Acid halide group is converted to 3 "-naphthoylamino) -l, l'-diphenyl and 20 ecm pyridine.

End products, e.g. B. Arylamides or esters, processed It forms a plastic, fairly hard mass, which

to become. 55 ^x / ₂ hours is kneaded, the kneader through

Furthermore, according to the present method, it is possible to close a glass plate that has been placed on it and to remove it through in

otherwise difficult or incompletely cooled or its double jacket circulating ice water

unreliably feasible couplings with good ones.

Yields and can be carried out with good reproducibility. With the kneading machine running and continuously

If, according to the present process, immediately 60 cooling with ice water are now in the course of 1 ¹ _{2 2} hours

the desired pigments are created, they are scattered in small proportions to the modeling clay:

In some cases, 0.1 mol of diazotized l-amino-3-chlorobenzene in the form of the, which is unfavorable for pigment purposes

or even practically unusable form, the zinc chloride double salt, which is produced by adding

their characteristic X-ray diagram of aqueous aluminum sulphate to a content of 42.7 ° / ₀ ,

is drawn. This form of the dyes, which is calculated below based on the free base, has been adjusted. the

α-form is to be mentioned, can be carried out in a coupling known per se after each addition of diazo compound

Way in a quite useful as a pigment very quickly and without the evolution of nitrogen in

Form, which can be observed in the following / J-form of the mass. Only after about

is called, the latter 90 ° / ₀ of the total amount of the diazo compound is added a typically

provides a modified X-ray diagram. 70 can be used for less after each additional addition

5 6

Minutes a small excess of diazo compound in the work-up more favorable, softer form

Clay can be detected. During the addition and then taken up in water. By

The diazo compound becomes hot as the dyeing progresses, first with dilute mineral acid

Fabric formation makes the modeling clay drier and harder. Through and then with dilute sodium hydroxide solution

Gradual addition of a total of 40 ecm of pyridine will then remove all foreign materials to the pigment

At the end of the coupling it is achieved that the putty is removed (pyridine, pyridine chlorohydrate, inorganic

always a viscoplastic, fairly hard one and for the salts). After drying at 90 to 100 ^° C. in vacuo

Achieving an intensive kneading effect suitable Kon one obtains a scarlet pigment, which, under the

has persistence. Viewed from the diazo microscope after the last addition, from yellow-orange aggregates of

compound is kneaded for another ^{1 and} ₂ hours. While io up to about 2 μ in diameter with no discernible crystalline

the whole process is the temperature in which the mold is made. Rolled into polyvinyl chloride sheeting,

Modeling clay about 20 ° C. you get strong orange tones of moderate lightfast

The modeling clay is one after the other in water, 2n.

Hydrochloric acid and O, 2N sodium hydroxide solution, by heating this orange pigment, in z. B.

between each filtered and with hot water after- 15 o-dichlorobenzene, to about 140 to 170 ° C takes place, also in

washed and the filter cake obtained at the end in suspension, quickly and easily traced under the microscope,

Vacuum dried at 70 ° C. and pulverized. Conversion into long, light red needles is obtained

about 38 g of the alpha form of the disazo dye. crystallizing pigment instead; heating with the

The α-form of the dye obtained in this way is one in the organic solvent at the same time Aspect of bright red powder, consisting of irregular 20 extensive improvement of the solvent and the formed leaflets with orange translucent color in migration fastness. The crystallized pigment stains Microscope. When rolled in polyvinyl chloride, polyvinyl chloride film turns into lightfast, scarlet-red a film tones orange when viewed from above and through, and it has a coupling obtained from orange coloring with poor fastness to migration. pigment different X-ray spectrum.

1 g of the powder obtained is with 100 ecm o-dichloro 25 In the above example, the during the

benzene heated to the boil for 5 minutes and slowly decoupling drying of the putty

left to cool. The resulting, finely crystalline formation and the transition into a powdery one that can no longer be kneaded

the separation is filtered off, washed with methanol, and the product is prevented by the addition of further pyridine;

dries and powdered. The / 9 form of the dye, on the other hand, is tried, the kneading consistency by adding it

As a powder, shows a color very similar in aspect to maintaining small amounts of water so

the α-form, however, consists of beautifully formed, one again probably a kneadable homogeneous mass, the

fine crystal needles with violet-red see-through color. but has no inner tenacity. As a consequence of this

When rolling the /? - shape in polyvinyl chloride one remains the further absorption of diazo compound

Get foil that is a scarlet reflective color and practical to stand out, and the clutch doesn't end there

shows a purple-red see-through color and a good 35 can be performed. On the other hand, the kneading consistency can be without

Has migration fastness. The X-ray diagrams of the disadvantage with neutrally reacting and taking part in the

α and /} forms are different. Reaction of non-participating connections

Instead of o-dichlorobenzene, success can also be obtained with, as with glycols, alkyl ethers of mono-success Nitrobenzene, trichlorobenzene or α-chloronaph or diethylene glycol, diacetone alcohol, dimethylformthalene be used. 40 amide.

Example 3 Example 2

Are in the ice-water-cooled double bowl kneader

In a z. B. by circulating ice water ge 59.3 parts of 3,3'-dichloro-4,4'-di- (2 "-oxy-3" -naphthoylamino) -cooled and with a suitable ventilation system 45 Ι, Γ-diphenyl and 8 parts of NaOH containing quantity associated Doppelmuldenkneter known type 90 to 95 ° / _o sodium, powdered sodium hydroxide for from corrosion-resistant material, with the. B. Chromium-nickel- Achievement of good kneading consistency required amount of monostable, 59.3 parts of 3,3'-dichloro-4,4'-di- (2 "-oxy-3" - butyl ether of diethylene glycol are pre-kneaded to give naphthoylamino) -l , l'-diphenyl with which to achieve a homogeneous, tough kneading mass, in which the amount of pyridine 50 azo component required for a good kneading consistency is partially or completely pre-kneaded as naphtholate until a homogeneous kneading mass is present. If dry zinc chloride is sprinkled. The double salt of the diazo compound is then made in small portions from 25.5 parts of 1-amino from 25.5 parts of 1-amino-3-chlorobenzene by diazotizing 3-chlorobenzene in small portions by adding and converting the diazo compound into the zinc from further monobutyl ether of the diethylene glycol chloride double salt, sprinkled with the good kneaded minium sulphate dried product with partially dehydrated aluminum with constant circulation of ice water. To maintain consistency. By taking samples, maintaining the kneading consistency, the uptake of the diazo compound is constantly monitored, to the extent that more pyridine is added dropwise so that the kneading must be continuously coherent and as tough as the coupling, a small amount of pulverized depending on the acidity of the diazo salt remains possible. By intensive cooling of the kneader intersperse 60 caustic soda up to the finished coupling is ensured that the internal temperature does not have a neutral to weakly brillantgelbalkalische reaction 3O ⁰ C increases. The inclusion of the diazo compound is to be maintained.

very quickly; it can easily be done by spotting on filter paper. The reaction mixture is worked up

after rubbing a sample of the modeling clay with water, as in the previous example and results in an identical,

with a solution of 2-oxynaphthalene-3,6-disulfone-65 orange coloring pigment, and therefrom is obtained through

acid sodium. The coupling is heating with o-dichlorobenzene the corresponding critical

a few minutes after the last addition of the diazo salt, the scarlet-colored pigment crystallized,

completed. The same results are obtained if in advance

By slowly adding a little water, the horizontal example becomes the equimolecular instead of caustic soda

Putty is used in one for emptying the kneader and for 70 amount of caustic potash.

7 8

The replacement of the very weakly brilliant yellow-alkaline above remains also without influence. The consumption

used monobutyl ether of diethylene glycol to caustic potash depends in part on the acidity of the

by similar neutrally used diazo salt that is not involved in the reaction. As the clutch progresses

reacting diluents like other ethers, the kneading

Diethylene glycol, ethylene glycol, polyethylene glycol, 5 maintain consistency as far as necessary. The up

Monoethyl ether of glycol, o-dichlorobenzene, dimethyl processing of the putty takes place as in the previous

formamide; if doing a water immiscible example and leads to identical pigments.

If the diluent is chosen, the diluent can be used instead of the one used above

work can be facilitated by the fact that the modeling clay caustic potash can also be used with caustic soda; also can

initially with an organic water-soluble product, to which ethylene glycol as a coupling medium also through

such as ethanol, is extracted. similar, neutrally reacting and participating in the reaction

As in Example 2, the kneading consistency in the uninvolved compounds, such as polyethylene glycols, di-

In this case, too, the coupling does not run through methylformamide, monoalkyl ethers of diethylene glycol

The addition of water can be maintained, but only or the monoethyl ether of glycol can be replaced,

z. B. by connections of the type in the above 15

Example mentioned in section and suitable as kneading media ο

Diluents. In one chilled with circulating ice water

Beisoiel 4 double bowl kneader 59.3 parts of 3,3'-dichloro

^ 4,4'-di- (2 "-oxy-3" -napthoylamino) -l, l'-diphenyl and the

In the double trough kneader under ice water 20 8 parts of NaOH containing amount of 90 to 95%, cooling 59.3 parts of 3,3'-dichloro-4,4'-di- (2 "-oxy-3" -naph- powdered caustic soda with the necessary amount of water thoylamino) -l, l'-diphenyl and 41 parts pulverized, kneaded to a yellow, slightly moist powder, anhydrous sodium acetate with the necessary amount. The zinc chloride double salt is then diazo-dichlorobenzene in a homogeneous solid putty compound of 25.5 parts of l-amino-3-chlorobenzene in convicted. Then the dry zinc is slowly added in small portions. Through further additions The chloride double salt of the diazo compound made from 25.5 parts of powdered caustic soda is constantly becoming a weak one l-amino-3-chlorobenzene sprinkled in. Maintained by adding brilliant yellow alkaline reaction; as well additional o-dichlorobenzene is used for consistently good levels by adding small amounts of water to ensure that The kneading consistency is ensured, with the kneading mass always remaining moist and powdery during the period. In counter-coupling The acetic acid released is partly as a kneading set for the preceding examples works. would take the diazo connection much more slowly, and

The work-up of the modeling clay after it has ended is finally reached a stage in which none

Coupling can be done in two ways: More coupling takes place.

By successive extraction with alcohol, If the reaction mixture is still worked up,

dilute mineral acid and dilute sodium are obtained after extracting the excess

hydroxide solution, followed by hot rearrangement of the diazo compound with cold water and the other

orange modification, the same is crystallized, accompanying substances with hot diluted mineral acid and

scarlet pigment obtained, as in the previously heated dilute sodium hydroxide solution a poly-

going examples has been described. vinyl chloride film orange coloring product, similar to the

On the other hand, by directly heating in the 40 mentioned in the previous examples. By

Kneader or, after prior removal from the heating in o-dichlorobenzene, only one can use it

Kneader, in a different vessel, with or without a significantly smaller amount of crystallized pigment

thinning by additional o-dichlorobenzene, which Modi (scarlet red on polyvinyl chloride) are obtained as

Perform fication change, one with the above doing this from couplings in the presence of organic media

and the scarlet, crystallized 45 mentioned earlier is possible.

Pigments identical pigment is obtained, after which the coupling is also unsatisfactory

wearable by alcoholic and aqueous extraction aqueous medium, if instead of caustic soda z. B.

the accompanying foreign materials are withdrawn, other caustic alkalis are used; the same goes for

can. also for coupling in the presence of excess

In the example above, the alkali metal acetate or formate can be used with the same success, even when the temperature is increased

used sodium acetate by equimolecular amounts to 50 ° C.

other alkali acetates or replaced by alkali formates The table below shows further combinations, national options listed; which, expediently after

Likewise, other neutral reacting methods and one of the methods given in Examples 1 to 5,

Compounds that are not involved in the reaction, such as mono- 55, lead to pigments, which, in many cases, only after

alkyl ether of diethylene glycol, monoethyl ether of the modification change by heating in z. B. o-dichloro

Glycol, diacetone alcohol, dimethylformamide, instead of benzene, usable pigments of the specified color

of o-dichlorobenzene can be used. result. The type of stabilization of the diazo compound

. . only plays a certain role as the

Example 5 _6o acidity of the diazo salt in all couplings without excessive

Of course, the required pyridine is cooled with circulating ice water

Doppelmuldenkneter 59.3 parts of 3,3'-dichloro amounts of caustic alkalis or alkali acetates or

4,4'-di- (2 "-oxy-3" -naphthoylamino) -l, l'-diphenyl and formates and thus possibly also the cons

the dry zinc chloride double salt of the diazo compound affects the resistance of the putty (e.g. in cases where

of 25.5 parts of l-amino-3-chlorobenzene with the required 65 organic acids are released during the coupling

Amount of ethylene glycol to form a homogeneous mass).

kneaded. When coupling diazo salts at once, this is fine-tuned in very small portions

Powdered caustic potash with a content of about 90 to coupling azo components are a matter of course

95 ° / ₀ KOH sprinkled so slowly that the one with equimolecular amounts of diazo salt and azo component

Water-diluted sample detectable reaction always used 70.

ίο

As can be seen from the table, the azo component is not subject to any further restriction other than Freedom from sulfonic acid groups, since this process not only produces pigments itself but rather also intermediate products

for azo dyes and pigments; by appropriate work-up of the coupling mixture, the solubilities the kneading medium and the by-products and end products are taken into account.

Diazo salt Diazo Type of Azo component the same Shade in pigment component stabilization Polyvinylchloride the end 1-amino Zinc chloride 2- (2'-Oxy-3'-naphthoylamino) anthraquinone o-dichlorobenzoI 3-chlorobenzene double salt Terephthaloyl-diacetic acid-di- (o-chlorophenylamide) 3- (2'-Oxy-3'-naphthoylamino) pyrene Raw product yellow 1-amino the same 1 2-chlorobenzene the same 4,4'-di- (2 "-oxy-3" -naphthoylamino) -1, l'-diphenyl yellow Greenish 1-amino the same yellow 2 2-methyl- the same Greenish Greenish 5-chlorobenzene 3,3'-dimethyl-4,4'-di- (2 "-oxy-3" -naphthoyl- yellow yellow 3 1-amino sulfate amino) -l, 1'-diphenyl Greenish anthraquinone the same 3,3'-dimethyl-4,4'-di- (2 "-oxy-3" -naphthoylamino) - yellow yellow 1-amino Zinc chloride 1,1'-diphenyl 4th 3-chlorobenzene double salt Terephthaloyl-diacetic acid-di- (2,4-dimethoxy- yellow yellow the same the same 5-chlorophenylamide) 5 Terephthaloyl-diacetic acid-di- (2-methoxy-4-chloro- 4,4'-di (2 "-oxy-3" -naphthoylamino) -1,1'-diphenyl yellow Greenish l-amino-2-me- Naphthalene- 5-methylphenylamide) yellow 6th ethyl-5-nitro- 1,5-disulfone 3,3'-dichloro-4,4'-di- (2 "-naphthoyl-amino) - 1,5-di (2'-oxy-3'-naphthoylamino) naphthalene Greenish orange benzene acid 1,1'-diphenyl 3,3'-dichloro-4,4'-di- (2 "-oxy-3" -naphthoylamino) - yellow 7th the same the same 1,1-diphenyl orange the same the same 4,4'-di (2 "-oxy-3" -naphthoylamino) -1,1'-diphenyl scarlet 3,3'-dimethoxy-4,4'-di- (2 "-oxy-3" -naphthoyl- Red-brown 8th l-amino-3- Zinc chloride amino) -l, 1'-diphenyl 2- (2'-oxy-3'-naphthoylamino) chrysenic scarlet 9 chlorobenzene double salt 4,4'-di (2 "-oxy-3" -naphthoylamino) -1,1'-diphenyl Orange brown Orange red 1 -amino- Zinc chloride 10 2-methyl- double salt 3,3'-dichloro-4,4'-di- (2 "-oxy-3" -napthoylamino) - Orange red Scarlet fever 5-chlorobenzene 1,1'-diphenyl 11 1-amino
2-methyl-
3-chlorobenzene the same Scarlet fever the same Orange red 1 -amino- the same 12th 2-chlorobenzene the same Orange red orange 1 -amino- Brown orange 13th 2-methyl- the same orange 14th 4-chlorobenzene Brown orange scarlet the same 15th the same scarlet 1 -amino- Purple red 2-carboxylic acid Naphthalene- 16 methyl ester 1-sulfonic acid Purple red Brown orange 5-chlorobenzene 17th 1-amino Brown orange anthraquinone sulfate the same Red 1-amino the same 18th 2-methoxy Zinc chloride scarlet Brownish red 4-chlorine double salt Bluish tint 19th 5-methylbenzene Brownish red Red 20th 1-amino Bluish tint 2-methoxy Zinc chloride Red 4-chlorine double salt violet 5-methylbenzene 21 violet

909 537/332

Diaz <
Diazo
component 11 Azo component 12th on in
"Chloride foil
pigment
the end
o-dichlorobenzene 1-amino
2-methyl-
5-chlorobenzene > salt
Type of
stabilization 1,4-Di- (N-methyl-2'-oxycarbazole-3'-carboylamino) -
benzene Colors
Polyvinyl
Raw product Brown 22nd 1-amino
2-methyl-
4-chlorobenzene Zinc chloride
double salt 1,4-di (2'-oxycarbazole-3'-carboylamino) benzene Red-brown Brown 23 the same the same 1 - (3'-oxydiphenyleneoxide-2'-carboylamino) -
2,5-dimethoxybenzene Red-brown - 24 the same the same 4,4'-di- (3 "-oxydiphenylenoxyd-2" -carboylamino) -
1,1'-diphenyl Yellow-brown Yellow-brown 25th the same the same 4,4'-di (2 "-oxyfluoren-3" -carboylamino) -
1,1'-diphenyl Yellow-brown Brown 26th 1-amino
3-chlorobenzene the same 3-oxydiphenylene oxide-2-carboxylic acid Brown product 27 3-methoxy
4-amino-
l, l'-diphenyl-
amine the same 4,4'-di (2 "-oxy-3" -naphthoylamino) -1,1'-diphenyl Between blue 28 3-methoxy
4-amino-
l'-diphenyl-
amine Chlorohydrate 3,3'-dichloro-4,4'-di- (2 "-oxy-3" -naphthoylamino) -
1,1'-diphenyl blue Reddish
blue 29 the same Chlorohydrate 3,3'-dimethyl-4,4'-di- (2 "-oxy-3" -naphthoylamino) -
1,1'-diphenyl Reddish
blue Navy blue 30th 1-amino
2-methoxy
5-nitrobenzene the same 3,3'-dimethyl-4,4'-di- (2 "-oxy-4" -methyl-
1 "-benzoylamino) -1, 1 '-diphenyl Navy blue Deep brown 31 Zinc chloride
double salt Brown

Claims (5)

Patent claims: 1. Process for the production of azo pigments from Diazo compounds and azo components which are free from sulfonic acid groups, characterized in that that the coupling is carried out in a practically anhydrous medium with the addition of organic solvents carried out in a concentrated reaction mixture with intensive mechanical mixing and optionally the pigments obtained in a known manner by a heat treatment with high-boiling organic solvents. 2. The method according to claim 1, characterized in that one is tough for treatment Media set up apparatus, in particular a kneading apparatus, works. 3. The method according to any one of claims 1 and 2, characterized in that the diazo compounds used in stabilized, drained form. 4. The method according to any one of claims 1 to 3, characterized in that as organic Solvent pyridine used. 5. Use of the method according to any one of claims 1 to 4 for the production of disazo pigments from a twice coupling azo component. Considered publications:
U.S. Patent No. 2,687,410. When the registration was announced, three substance samples with a directory were displayed. © 909 637/332 9.