DE1644117A1 - Process for the production of disazo pigments - Google Patents

Description

CIBA AKTIENGESELLSCHAFT, BASEL (SWITZERLAND)

Case 6009 / E

Germany

Process for the production of disazo components.

So far, no technically useful process for the preparation of disazo dye pigments by coupling diazotized amines with bis [2-hydroxynaphthoyl- (3)] arylenediamines, which are particularly sparingly soluble in water, has been described in the patent literature. The great difficulty of producing such pigments by the coupling route in an aqueous medium has been repeatedly stated in the literature, for example in the article "New organic pigment dyes and their use" by M. Schmid in Deutsche Farben-Zeitschrift 9, page 253 (1955), in the DAS

009844 / $ 144

No. 1 066 680, in DBP No. 921 225 and in the article "Les pigments organiques "by J. Lenoir in Peintures Pigments Vernis, 36, page 714 (1960)

To circumvent these difficulties, for example in Swiss patents No. 3 ^ 3 044 and No. 565 469 couplings by kneading or stirring of stabilized diazo compounds with the bis [2-hydroxy-

b naphthoyl- (3) J-arylene-diamines in anhydrous organic Solvents described. However, you get the Dyes in a modification unsuitable for pigment purposes. The conversion of these pigments into a pigmentary one usable form requires additional labor, again being an organic solvent is needed.

The one described in Belgian patent specification 587 115 Coupling of diazo compounds to the Mannich

) bases of bis [2-hydroxynaphthoyl- (3)] - arylendiamines although the advantage of running in an aqueous medium. However, the manufacture of the Mannich bases requires another Operation. In addition, due to the sensitivity of the Mannich bases when carried out in technical scale great difficulties.

Finally, the Swiss patent describes 397 913 die'Kupplung of diazotized amines with bis [2- · hydroxynaphthoyl- (3)] - arylendiamines in aqueous suspension with the addition of dispersants and larger amounts

0 0S84 4 / U4 5

organic solvents using grinding forces, as they are produced in ball or sand mills, high-speed agitators, high-pressure mills or ultrasonic devices. The disadvantage of this process is that when the aqueous solution of the diazonium salt is added, the coupling component fails and therefore a heterogeneous one in the coupling System is present, which has a very detrimental effect on the speed of the clutch. Also requires this process requires a large amount of equipment and is therefore hardly possible to be carried out on a large-scale more advantageous than the previously described coupling method »

Compared to the synthesis route known as the condensation process (see German patent specification 921 223, gases 2814) the inventive method has the advantage that Diazo components can be used for the formation of azo dye carboxylic acid chlorides are unsuitable, such as e.g. Aminoberizol-carboxamides, aminobenzene-sulfonamides, aminobenzene-sulfo-arylamides etc. The new, simple process therefore not only allows efficient production per se known color bodies, but it also enables the synthesis of new, valuable disazo pigments.

It has now been found to be beneficial Way to get the desired disazo dyes, if you the aqueous acidic solution of a diazonium salt with a aqueous-alkaline solution of a bis (2-hydroxynaphthoyl- (3) 1-arylene diamine continuously mixed with a strong vortex and the resulting pigment suspension is continuously drawn off.

Diazo compounds to be used as process-compliant diazotized amines come into consideration, apart from the diazonium group have no further water-solubilizing groups, in particular diazo compounds of aminobenzenes, which are preferably substituents in the phenyl radical, such as halogen atoms, alkyl, alkoxy, trifluoromethyl,

009844/1445

Nitro, cyano, carbon alkoxy, carbamido, sulfonamido, Have alkylsulfonyl or acylamino groups.

Particularly suitable azo components are those of the formula

Uli ÜU

xxx m

where R is an optionally substituted by halogen atoms, alkyl or alkoxy groups substituted phenylene or biphenylene radical and X represents a hydrogen or halogen atom or an alkoxy group.

-.- Since the alkali salts of these azo components in Water are very sparingly soluble, it is advisable to yourself to use a solubilizer. As such are suitable with Wassa? miscible organic solvents, e.g. Alcohols such as methanol, ethanol or isopropanol, diacetone alcohol, Ethers such as ethylene glycol monomethyl or monoethyl ether or dioxane, bases such as pyridine, mono- or diethanolamine, also dimethylformamide or dimethyl sulfoxide. It is advisable to use at least 2 parts of this per 1 part the azo component.

The components are conveniently combined in a mixing nozzle. This is to be understood as a device in which the liquids to be mixed on

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relatively small spaces are combined with one another, wherein at least one liquid, preferably under increased pressure, is supplied through a nozzle.

The mixing nozzle can for example be constructed and operate according to the principle of the water jet pump, whereby the supply of one liquid in the mixing nozzle, the water supply in the water jet pump and the supply of the other Liquid in the mixing nozzle corresponds to the connection to the vessel to be evacuated in the water jet pump and, if necessary, this latter supply of liquid also takes place under increased pressure.

The quantitative ratio of the reaction liquids

must be dimensioned in such a way that 1 mole of the coupling component

the / ■

component 2 mol / diazo component come.

The solutions of the diazo and coupling components are expediently diluted with the addition of water to such an extent that that there are no significant deposits of the azo component comes, which has an adverse effect on the coupling speed and on the purity of the dye to be produced would affect. In general, it proves to be advantageous to use a maximum of 20%, preferably about 10% Solutions to work.

In the present process, the coupling occurs as a result of the intensive mixing of the reactants occurs before one of the components fails, therefore itself both the diazo and the coupling component in time

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point of the coupling are in solution, we have a homogeneous system. In one such is the coupling speed only dependent on the ion concentration, so that the coupling occurs within a large p "range

ri

can be done, even in highly acidic areas, for example. wisely at p "4 to 5 or in the alkaline range,

Π.

for example at p “9.

ti

In many cases it proves to be expedient, one in time and / or in terms of location during the merging of the reaction components occurring excess of acidic or alkaline compounds by buffering to mitigate effective aids. Compounds with a buffering effect include salts of acetic acid, formic acid, Carbonic acid, benzoic acid, boric acid, phosphoric acid and salts of other weak or medium-strength acids, as well Weak base salts such as mixtures of pyridine bases or triethanolamine are suitable.

When carrying out the process according to the invention, it is advantageous to carry out the coupling in the presence of Auxiliaries, such as wetting agents, dispersants, emulsifiers, urea or naphthalenesulfonic acid, as this improves wetting and refinement as well as prevention the precipitation of the components is caused. In addition, the shape of the resulting primary particles of the pigment positively influenced. The unusual color · »"

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material can be isolated by Atoftitrieren "-It proves check expedient same _s for the removal of small amounts of impurities with an organic solvent," for example, to treat or Aethylenglycolmonomethyläther AethylenglykolmonoMthyläther The dyestuff obtained has a very low Konrgrösse on. In many cases it is desirable to perform a post-treatment with a suitable organic solvent _S such as chlorobenzene, o-Dichlorbenzolf, nitrobenzene * _£ pyridine or picoline Chlnolin, wherein a grain coarsening

occurs. "This treatment often has a beneficial effect on the patient Fastness to light and migration of the pigments obtained.

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

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Example 1.

16.2 parts of 2-amino-6-chlorotoluene are customary

Vol .- / VoIa = /

Way in 100 / parts of 15 # strength hydrochloric acid and 50 / parts of 4N sodium nitrite solution diazotized at 5 ° and filtered cold. On the other hand, 28.5 parts-4,4 * -Bis- [2 "-hydroxy-

naphthoyl- (5 ") - amino] -diphenyl at 20 ° in 100 parts of ethylene

VoI .- /

Glycölmonomethylather and 20 / parts of 30 # sodium hydroxide solution dissolved and filtered. The two solutions will be, if necessary after dilution with water, continuously fed to a mixing nozzle, where an immediate coupling of the components takes place. By regulating the supply of the solutions and · by buffering with a small amount of acetic acid ensured that the p "value in the mixing nozzle between 4,5 and 5 lies. The temperature should be between 25 to 40 °. lie. This can be done by adding water to the solutions of the components are regulated. The resulting dye suspension is filtered off and the filter residue is washed out.

The dyestuff press cake is then heated to 115 ° with stirring with 20 parts of ethylglycol monoethyl ether, whereby water and part of the ethylene glycol monoethyl ether are distilled off. This is followed by 0.1 part of 50 # strength sodium hydroxide solution added and the whole thing filtered. The filter residue is first with Ethyleneglycolmonoäthyläther and then with

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Methanol washed. The product can also be treated through treatment refined with other solvents': be.

A particularly good distribution of pain on the obtained Dye is obtained if the solution of the diazo component or the coupling component is anionic or not ionic wetting agent, for example the sodium salt of N-Benzyl ^ -heptadecylbenzimidazole-disulfonic acid adds.

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Example 2.

17 parts of 2-amino-6-chlorotoluene are dissolved with 300 parts of dimethylformamide, with 160 parts by volume of hydrochloric acid 30% and 18 parts of sodium nitrite 100% at approx. 5 ° diazotized and filtered cold.

On the other hand, there are 26.2 parts of 4,4'-bis [2 "-hydroxynaphthoyl- (3") -amino] -diphenyl at 20 ° in 250 parts of ethylene glycol monoethyl ether and 40 parts by volume) 0 # iger Dissolved sodium hydroxide solution and filtered. A further 30 parts of benzoic acid and 20 parts are used as a buffer and solubilizer Pyridine base mixture and 50 parts of urea are added when mixing the two components, delay rapid precipitation of the sparingly soluble coupling component help. If necessary, after dilution with water, the two solutions are fed continuously to a mixing nozzle, where the components are immediately coupled. By regulating the supply of the solutions and by buffering it is ensured that the p "value of the Mixing nozzle is between 6.5 and 7. The temperature should be between 25 and 40. This can be done by adding warm water to the solutions of the components regulated will. The resulting dye suspension is filtered off

the end/
and the filter residue / washed.

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Then the dye press kitchen is stirring dehydrated azeotropically with 10 parts of dichlorobenzene and then boiled under reflux for 15 hours Filtration is the PiIterrUckstand with methanol and Water covered * '

Instead of o-dichlorobenzene, one can use the azeo-

.propene dewatering also chlorobenzene, nitrobenzene or Use Hlcolin.

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Example 3.

55.0 parts of anthranilic acid methyl ester are added

Vol .- / the usual way with 2 parts acetic acid, 100 / parts salt

VoI. - /

acid (50%), with ice and 55 / parts sodium nitrite solution

* ■

(4n) diazotized at 5 ° and filtered cold. On the other hand will be 52.5 parts of 4,4'-bis [2 "-hydroxynaphthoyl- (5") amino] diphenyl at about 20 ° in 190 parts of ethylene glycol monoethyl ether and 100 parts by volume of 50 # sodium hydroxide solution dissolved and filtered. The two solutions, if necessary after dilution with water, are fed continuously to a mixing nozzle where an immediate coupling of the components takes place.

the flow rate / finds. By regulating / of the solutions ensured that the _pH value lies in the mixing nozzle from 4.5 to 5. The temperature should be between 25 and 40 °. This can be regulated by adding warm water to the components. The resulting dye suspension is filtered off and the filter residue is washed out.

Then the press cake is refined by treatment with solvents as in example 1 or 2, - ■ - '■■

The table below is a number of more Listed disazo pigments that are obtained when 2 moles of the diazo compound of the amine mentioned in column I with a Mol of the azo component mentioned in column = 11 according to the information

00984A / 1U5

164 A 11 7

this example couples. Column III indicates the hue of the polyvinyl chloride dye obtained with the dyes.

1 2,5-dichloroaniline II III I. 2 Il Bis- (2-oxynaphthalene-3-carbon
acid e-) 1 ', 4' -phenylenediamide yellow
prickly
Red 5 Il Bis- (2-0xynaphthalene-3-carbon-
Acid) -2 ^! -chior-1 *, 4'-phenylene
diamid blue-
prickly
Red 4th 2-chloroaniline Bis- (2-oxynaphthalene-3-carbon
acid) -4 ', 4 "-diphenyl-diamide It 5 5-chioraniline Bis- (20xynaphthalene-5-carbon
acid ) -y Y3 ^u -dichlor-4 ·, 4 '^ di-
phenyl diamide orange 6th 2-chloro-5- ^ rI. * 'V-
if lourmet hylani 1 in Bi s- (2-oxynaphthalene-3-carbon-
acid) -3 ^l , 3 "-dichloro-4,4'-di
phenyl -dl amide
r ·. ; ι ' sharp
laugh Bis- (2-oxyna ^ thalin-3-carbon
acid)-! ', 4'-phenylenediamide Crowd
laugh

0 09844/144 5

1 6 UU 11 -7

I. 7th 3,5-di-trifluoro-
methyl-1-amino-
benzene II Ill 8th 4-trifluoromethyl
2-amlno-4'-chlorine-
diphenyl ether Bis- (2-0xynaphthalene-> earbon
acid) -3 *, 3 "-dichlor-4 ^f , 4" -
diphenyl diamide orange 9 4-chloro-2-nitro-
aniline Bis- (2-0xynaphthalene-3-
carboxylic acid) -l'4'-phenylene-
diamid sharp
laugh 10 4-chloro-2-nitro-
aniline Bis- (2-0xynaphthalene-3-
carboxylic acid) -2'-chor-1 ', 4 * -
phenylenediamide Red
prickly
Brown. 11th 2-amino-benzene-
acid methyl ester Bis- (2-0xynaphthalene-3-
carboxylic acid) -2 ', 5'-dimethyl -
1 ^f , 4'-phenylenediamine Brown 12th 2-methyl-3-chloro
aniline Bis- (2-0xynaphthalene-3-
carboxylic acid) -4 ', 4 "-diphenyl-
diamid Red 13th 2-methyl-5-chloro
aniline Bis- (2-0xynaphthalene-3-
carboxylic acid) -4 ', 4 "-diphenyl-
diamid Red 14th 2-methoxy-4-
chloro-5-methyl-
1-amlnobenzene U Red I! rub in

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I. 15th 6-methoxy -} - sulfonic acid
diethylamido-1-amino-
benzene II III 16 S-methoxy-S-carbamido-
1-aminobenzene Bis- (S-oxynaphthalene -} -
carboxylic acid) -2 ', 5 * -di
methyl-l ', 4'-phenylene-
diet violet 17th 2-Nltro-4-carbamido-
1-aminobenzene « bordeaux 18th l-amine p-4-methyl-
sulfonyl benzene Bis- {a-oxynaphthalene - ^ -
carboxylic acid 4-2'-chlorine-
1'j 4- '-phenylenediamide maroon 19th l-amino-2-methoxy-5-
sulfonamido-benzene Bis- (2-0Xyrtaphthalene-3-
carbonic acid) -) ', 5 "-di
chloro-4 ' _J 4 "diphenylamide orange 20th l-amino ~ 2-chloro-5-
carbonamidobenzene Bis- (2-0xynaphthalene-5-
carboxylic acid) -2 '/ 5 * -di
methyl -1 ', 4'-phenylene
diamid bordeaux 21 l-amino-2-methoxy-
4-nitrobenzene Bis- (2 ~ 0xynaphthalene-3-
carboxylic acid) -2'-chloro-
1 '* 4'-phenylenediamide Scarlet fever 22nd 4-methy1-3-amino-
benzoic acid methyl
ester Bis- (2 ~ 0xynaphthalene-3-
carboxylic acid) -! ', 4'-
phenylenediamide. . maroon 2} 4-methyl-3-amino
benzoic acid p-enyl
ester Bis- (2-0xynaphthalln-5-
carboxylic acid) -2 '>5'-di
me thy 1-1 ', 4'-phenylene-'
diamid Red Bis- (2-0xynaphthalene-5-
carboxylic acid} -2 ', 5'-di-
methoxy-1 ^f , 4'-phenylene
diamid blue
prickly
Red

0.098 4 4 / .U 4 5-

II III Bis- (2-0xynaphthalene-3-
carboxylic acid-2 ', 5'-di
methoxy-1 ' , 4'-phenylene
diamid blue
prickly
Red Bis- (2-0xynaphthalene-3-
carboxylic acid) -l ', 4'-
phenylenediamide Red Bis- (2-0xynaphthalene ~ 3-
carboxylic acid) -2 ' , 5'-di-
methoxy-1 ' , 4' -phenylene
diamid Il Bis- (2-0xynaphthalene - 5-
carboxylic acid) -2 ', 5'-di
methyl-1 ', 4'-phenylene-
dlamid Brown Bis- (2-0xynaphthalene-3-
carboxylic acid) -2 ', 5' - ^ i-
methoxy-1 ', 4'-phenylene
diamid blue-
prickly
Red Il Bis- (2-0xynaphthalene-3-
carboxylic acid) -2 ', 5'-di-
chloro-1 ' , 4'-phenylene
diamid Red Bis- (2-0xynaphthalene-3-
carboxylic acid-6-methoxy) -
2 ', 5'-dimethyl-l' _i 4 ^I -
phenylenediamide violet Bis- (a-oxynaphthalene - ^ -
cart> onsaure) -3 ', 3 "-di
chloro-4 ', 4 "-diphenyl-
diamid orange I. 24 4-methoxy-3-amino-
benzoic acid (4'-chlorine)
phenyl ester 25 4-chloro-5-amino-
benzoic acid- (4'-
chlorine) phenyl ester 26 4-methyl-3-amino-
benzoic acid
phenyl ester 27 4-amino-3-nitro-
benzoic acid ethyl
ester 28 4-methyl-3-amino-
benzoic acid- (4'-
methyl) phenyl ester 29 4-methyl-3-amino
benzoic acid- (4'-
methoxy) -phenyl-
ester 30 4-chloro-5-amino-
benzoic acid- (4'-
phenyl) phenyl ester 31 4-methyl-3-amino-
benzoic acid-phenyl
ester 32 4-ethylsulfone-3-
amino-benzotrifluoride

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I. 55 4-amino-5-methyl-
benzoic acid- (4'-chloro-
phenyl) ester II III Bis- (2-oxynaphthalene- 1> -
carboxylic acid) -2 ^f , 5'-di
methyl-1 ' , 4-phenylene-
diamid Brown

009844 / U-A 5

Example 4.

17.5 parts of 2,5-dichloroaniline are mixed with 100 parts Water melted at 60 and 50 parts by volume with thorough stirring 30 $ hydrochloric acid added, with ice and 27.5 Part 4N sodium nitrite solution diazotized in the usual way at 0 ° and filtered cold.

On the other hand, there are 24.1 parts of bis (2-oxynaphthalene- -3-carboxylic acid) -2'-Chlor-I ', 4 -'-phenylenediamine in 400 parts by volume of diacetone alcohol and 20 parts by volume of 50 # sodium hydroxide solution and 1000 parts Dissolved water at room temperature and filtered. The two solutions, if necessary after dilution with water, are fed continuously to a mixing nozzle, where the components are immediately coupled. By regulating the supply of the solutions and by buffering with NapBjiP "solution (Borax) it is ensured that the p" value in the mixing nozzle is between 8.5 and 9. The temperature should fluctuate between 15 to 20 °. This can be regulated as described in Example 1. The resulting pigment suspension is filtered off and the filter residue is washed out thoroughly. Then, the pigment press cake is heated with stirring with 3OOV0I.-parts of nitrobenzene to 1 J) O

until all the water has distilled off. The suspension is then held at 140 to 145 ° for a further 2 hours and filtered off while hot. The filter residue is first with hot

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-19- 164411 ?.

Nitrobenzene and then washed with methanol and at 40 to 50 dried. The product can also be cleaned as follows are: '5 parts of pigment andΛ00 parts of nitrobenzene Maintained boiling for 2 hours and as described above worked up.

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Claims (7)

V- --.--. - ·. .-- Patent claims » " ■■, 1 »procedure to? Production of Disaz © pigments, (äadppcii gekeiTOzeiehnefe that one can get the acidic solution of a Diazonium saltsmi; fc of an aqueous-alkaline solution _______ a bis-i2 ~ hydr _t oxyn.aphtho ^ is continuously mixed with a strong vortex and the resulting pigment suspension is continuously drawn off. 2. The method according to claim 1, characterized in that that the combination of the liquids takes place in a mixing nozzle. . J>. Process according to Claims 1 and 2, characterized in that the bis (2-hydroxynaphthoyl- (3) 3-arylenediamine is brought into solution with the aid of a solubilizer. 4. The method according to claim 3, characterized in that that a water-miscible organic solvent is used as a solubilizer. 009844 / U45 5. The process of certain requests 1 to 4, thereby characterized in that a disperser is used, 6. The method according to ^^^ the ^ claims 1 to 5 ,, characterized in that inan the dyes obtained nachbehandejt with an organic solvent ^; 7. The according to the tosprltelienM; to 6 received Dyes. '. ■ ", - ■■■ ■"'■■;..;■;·' - ■■ -. - '. _. ^:; '' - ';^:;'■■".' ■ -, ORKaINAL INSPECTED