DEB0027138MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: August 22, 1953. Advertised on March 22, 1956

GERMAN PATENT OFFICE

It has been found that valuable lacquer pigment dyes are obtained when diazotized i-aminobenzene-2-sulfonic acids in the benzene nucleus carry at least ι halogen atom, with .solchen 2, J-Oxynaphthoesäureaniliden, which in the Anilido group contain an o-position substituent, and the obtained isulfonic acid group-containing Azo dyes by methods known per se with salts of manganese and / or ίο the calcium laked.

Suitable o-aminobenzenesulfonic acids are, for. B. the ι-amino-4-chlorobenzene-2-isulfo ⁱ acid tert. that ι - amino - 4, 5 - dichlorobenzene - 2 - sulf oic acid, 1-amino-4-chloro-5 - methylbenzene - 2 - sulf oic acid or the i-amino ^ -methyl-S-chlorobenzene ^ -sulfonic acid. Mixtures of these amino and sulfonic acids can also be used.

Examples of azo components are 2-methylanilide, 21-methoxy-anilide, the 2,4-di.methoxy-5-chloroanilide and also those Chloranilides of 2, 3-oxynaphthoic acid, in which a chlorine atom in o-position to NH group stands. Mixtures of such arylamides can also be used.

509 698/457

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The diazotization of the aminosulfonic acids, the coupling and the laking take place after known methods.

The lacquer pigment dyes obtainable in this way are completely in the usual organic solvents insoluble and extremely lightfast. You own That is why it is ideal for the production of overmouldable, lightfast paints.

Compared to that from Example 6 of the German

ίο Patent 584 578 known barium lacquer des Azo dye obtained by coupling diazotized 2-aminonaphthalene-i-isiulfonic acid with i- (2 ', 3'-oxynaphthoyl) - Amino - 3 - nitrobenizole is available, which stand out according to the present process available lacquer pigment dyes through better

• Lightfastness off. '

The parts mentioned in the examples are parts by weight.

example 1

A solution of 44.5 parts of i-amino-4-methyl-5-chlorobenzene-2-sulfonic acid in 600 parts of hot water is stirred without further heating until it has cooled to about 30 ^0, then with 100 parts i8 '° Hydrochloric acid is added and, after the required amount of ice has been added, it is diazotized at 0 ° with a solution of 13.8 parts of sodium nitrite in about 80 parts of water. In the meantime, 60 parts of i- (2 ', 3'-oxynaphthoyl) -amino-2-methoxybenzene are dissolved in a boiling mixture of 2000 parts of water and 70 parts of 45% sodium hydroxide solution, and after dissolution, the mixture is cooled to 5 to 10 ° then lets the diazo solution gradually flow in with stirring. After iostündigem stirring at ordinary temperature and at a _pH value 7 to 8 yon the mixture is heated to about 65 °. The precipitated dye, which becomes a little lighter in the process, can then be well suctioned off and washed out. The dyestuff paste, which has been squeezed out well, is stirred with 5000 parts of water, and at about 80 ° with 50 parts of manganese (II) chloride. lacquered. After boiling, suctioning off, washing out and drying, 112 parts of a yellow-red lacquer pigment dye of excellent lightfastness and overspray fastness are obtained. '

A yellow-red lacquer pigment of similarly good fastness is obtained if the i-amino-4,5-dichlorobenzene-2-sulfonic acid is used as the diazo component used.

Example 2

Dissolve 72 parts of i- (2 ', 3'-oxynaphthoyl) amino-2, 4-dimethoxy-s-chlorobenzene in a boiling mixture of 2Ό00 parts of water, 54Teilen45 ^o / cent sodium hydroxide solution and 2 parts of an oxyethylated fatty alcohol. The solution, filtered if necessary, is cooled to 5 to 10 ° and the diazo solution described in Example 1 is gradually added to it. The whole is stirred for about 10 to 15 hours at normal temperature, then heated to about 60 ° and finally, as in Example 1, laked with manganese (II) chloride. 124 parts of a red lacquer pigment dye are obtained from. very good fastness to light and overspray.

Calcium chloride can also be used in place of manganese (II) chloride with similarly good success for veiiackuing or use a mixture of both.

Example 3

22.15 parts of i-amino-4-chloro-5-methyrbenzene-2-sulfonic acid are in 250 parts of hot water with the addition of 8 parts of 45% sodium hydroxide solution solved. The cooled and filtered solution is mixed with 34 parts of a 23% strength sodium nitrite solution and then leaves it in a mixture of 200 parts of ice and 35 parts of concentrated hydrochloric acid pour in over the course of 1 hour. After 1 hour The diazotization is complete.

The coupling solution is prepared as follows: 29 parts ι- (2 ', 3'-Oxynaphthoyl-) amino-2-methyl-benzene is dissolved at 90 ⁰ in a mixture of 250 parts of water and 15 parts of 45 ° / cent sodium hydroxide solution and filled with water to 500 parts. After the addition of 27.3 parts of 33% formaldehyde solution is made up to 3000 parts, is at 30 ^0, and leaves the Diazosalzlösumg in about 30 minutes accrue. After the coupling, the very proceeds rapidly, is adjusted with acetic acid to p _H 7 and continued for several hours. Finally, it is heated to 90 ^0, where the hue of the dye is slightly brighter. After cooling to 70 ⁰ is suctioned off and stirred in the dye paste in 3000 parts of water to, mixed with 1 part oxäthyliertem sperm oil and laked at 25 ⁰ with 40 parts Mangamsulfat. After boiling for many hours, the product is filtered off with suction while hot and washed with 1000 parts of water. The _pH value of the filtrate is 6.6. After drying at 70 ⁰ 54 parts remain behind a red lake pigment with excellent overspray-v and Liehtechtheit. If the packaging is carried out with calcium chloride, a red lacquer pigment with similar properties is also obtained in a yield of 48 parts.

B e i s ρ i e 1 4

20.75 parts of i-amine-4-chlorobenzene-2-sulfonic acid are dissolved hot in a ^{solution 'prepared' from 8 parts of anhydrous 11Q} sodium carbonate and 200 parts of water. The filtered solution, cooled to 25 °, is mixed with 6.9 parts of pure sodium nitrate and added dropwise to a mixture of 50 parts of dilute hydrochloric acid, ^{X1 5,200} parts of water and 200 parts of ice over the course of 1 hour. After the end of the dropping in, the mixture is stirred for a further 2 hours and then added to a coupling solution which has been prepared according to the instructions in Example 3. After the usual work-up, a dye paste is obtained which is mixed with 3000 parts of water and laked by adding 20 parts of calcium chloride at 25 °. The brcarbonate-alkaline dye pulp is heated to the boil, filtered off with suction while hot and washed with about 2000 parts of water. After leaving

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suction and drying gives 50 parts of a lacquer pigment that has very good oil and lightfastness owns.

Be

ispi

el

60 parts of i- (2 ', 3'-oxynaphthoyl) -amino-2-methoxybenzene are dissolved in a hot mixture of 2000 parts of water and 70 parts of 45% sodium hydroxide solution and the resulting solution is cooled to 5' to 10 °. To this solution can be one of 44.5 parts of i-amino-4-cJilor-5-metrjiylbeaizol-2-sulfonsäuire incorporated as in Example 3 prepared diazo solution, followed immediately by adjusting with acetic acid to the _pH value 7 to 8 and then continue stirring for about 10 hours. Before the resulting dye is suctioned off, the mixture is heated to 60 °, the dye becoming somewhat more yellowish. The pressed dye paste is mixed with 6000 parts of water, mixed with 80 parts of solid manganese sulfate and gradually heated to 100 °. At around 80 °, the color of the initially red paint changes to yellow-red. It is vacuumed hot, washed with hot water and dried. 108 parts of a yellow-red lacquer pigment of excellent light and oversprimitness are obtained.

At sp i e1 6

The diazo solution prepared from 41.5 parts of i-amino-4-chlorobenzene-2-sulfonic acid as in Example 4 is left in one according to the example. 1 from 60 parts of ι - (2! ', 3' - oxynaphthoyl) - amino - 2 - methoxybenzene produced coupling solution run in. The dye, wife stated in Example 1, is lacquered with 50 parts of manganese (II) chloride and 106 parts of a yellow-red lacquer pigment of excellent light and overspray resistance are obtained.

Claims (1)

Claim: Process for the production of lacquer pigment dyes by coupling diazotized aromatic i-aminobenzene-2-sulfonic acids with 2, 3-oxynaphthoic acid arylamides and leaching of the suilfoneäuxegruppenhalitigen obtained Azo dyes with salts of polyvalent metals, characterized in that the diazo components diazotized i-aminoibenzene-2-sulfonic acids, which carry at least one halogen atom in the benzene nucleus, and such 2,3-oxynaphith'OeS'acid: -aniliide used as azo component, which contain an O-substituent in the anilido group, and that the lacquer with salts of manganese and / or calcium. Referred publications:
German patent specification No. 584 578.