DE1644253A1 - Process for the production of monoazo pigments - Google Patents

Description

-J.E. Geigy A.G. 1-2370 / 2572 *

Dr. F. Zumstein Sr. - Dr. E. Assmann Dr ILKoenigsberger Dipl.Phys. R. Hofzbauer

Dr. F. Zumstein jun.

Patent attorneys

S Munich 2, Bräuhausstraße 4 / III

New complete registration documents

Process for the production of monoazo pigments

The present invention relates to new monaazo pigments, a process for their production, their use for Pigmenting of high molecular weight organic material and, as an industrial product, the material pigmented with it.

The need for strong, pure, lightfast yellow pigments, especially for the production of printing inks for the graphic trade is well known. Among other things, pure, red-tinged yellows are searched for, for themselves or in Combination with orange pigments, gold, orange and brown tones allow to manufacture. It is required of the printing inks produced with such yellow pigments that they also with high pigment content have good flow properties and that the prints produced with it show gloss and transparency.

Mr. new monoazo pigments have now been found which these ÄnCoriurua ^ r; largely suffice. These pigments are conservation ^ir n _t w = iin is the Diamond umverbiridung an amine dor formula I

NO,

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wherein X is a lower alkoxy group or the halogens are fluorine

or means chlorine,
with a compound of the formula II

(II)

OCH,

H ₃ CO

where Y is chlorine or bromine,
couples to a monoazo pigment of the formula III,

CH,

(III)

OCH,

in the

X have the meaning given under formula I and Y under formula II.

As a lower alkoxy group in the position of X comes for example the methoxy and preferably the ethoxy group, chlorine as halogen.

The coupling is expediently carried out in aqueous or aqueous organic, preferably carried out weakly acidic, in particular acetic acid solution or suspension. To speed up

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the coupling or to influence the particle size and crystal form of the pigment formed can be added to the coupling mixture known auxiliaries. Mention may be made, for example, water-miscible organic solvents such as lower alkanols, for example methanol, ethanol, ethylene glycol mono-methyl or ethyl ether, cyclic aliphatic ether, for example dioxane, lower fatty acids, for example formic acid or acetic acid, lower fatty acid amides, such as ä Dimethylformamide; or certain tertiary nitrogen bases, e.g. triethanolamine or pyridine, also organic solvents which are immiscible with water, such as optionally halogenated or nitrated aromatic hydrocarbons, e.g. benzene, toluene, chlorobenzene, nitrobenzene or tetrahydronaphthalene, and also nonionic, anionic or cationic dispersants - as such are suitable in particular investment products of more than one equivalent of alkylene oxide, in particular ethylene oxide, with fatty alcohols or fatty acids, condensation products of naphthalenesulfonic acids with formaldehyde or, for example, lauryldimethylbenzylammonium chloride, also resins or resin soaps, for example based on rosin, protective colloids such as casein or solid methylcellulose, softeners, oils Substrates such as barium sulfate or alumina hydrates.

The new monoazo pigments fall out of the coupling mixture the end. They are isolated in the usual way by filtration and purified by washing. Depending on the intended use you can dry the raw pigment press cake

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and grind, process into watery doughs and pastes or flush in organic media. The pigments can also granular or powdery with auxiliaries such as carrier resins Process preparations.

To improve the color strength and / or to change the hue, the new pigments can also be mixed with one another or together with other pigments. For example, up to 30% of the diazo component can be used of the formula I or the coupling component of the formula II by another diazo component from the nitroaniline series or replace it with another coupling component from the acetoacetanilide series.

The monoazo pigments according to the invention are for pigmenting suitable for high-molecular organic materials,

binders primarily for printing inks / for the graphic industry, especially for paper printing, but also for pulp dyeing and, more generally, for paper coating. Possible areas of application are, for example, packaging or poster printing, printing or coating wallpaper and colored paper, or the production of paper laminates. The pigments can also be used, for example, in paints on an oily basis, such as linseed oil paints, or on an aqueous basis, such as emulsion paints, in paints of various types, such as nitro or alkyd resin paints, and also for pigmenting plastics such as polyethylene, polystyrene, polyvinyl chloride, especially hard -Polyvinyl chloride, as well as hardenable resins, cellulose esters, especially for diο

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Spin dyeing of viscose or acetate silk, as well as for pigment printing and padding of textiles can be used.

The new pigments color these materials in pure, reddish yellow, very strong and lightfast shades. The high color strength allows the production of good flowing, strongly colored printing inks and therefore relatively thin printing films, which is extremely valuable for the graphic arts industry. When using the new pigments for the graphic print Λ also the beautiful gloss and transparency of the prints and the good overcoating should be mentioned. Transparency is also very desirable in the spin dyeing of rayon. Furthermore, the oil and solvent fastness properties of the new yellow pigments are good.

Compared to the known, by coupling tetrazotized 3,3'-dichlorobenzidine with 2,5-dimethoxy-4-chloro- or -4-bromo-acetoacetanilifl according to the German patent no. 921,404 or Belgian patent no. 638,512 available important yellow pigments of the benzidine series, the new pigments have the advantage that they can be educated against the harmful, carcinogenic 3,3'-dichlorobenzidine '/ during their production. Compared to that in the American patent no. 3,032,546 described yellow pigment au ε ΛI azo ti η r ^f ; em 1 ~ Amlrio-2-methoxy-4-nitrobenzene and ': -WV [\'>'/. Y- ^ Ci (Mf, -i ^r - '. \ t-nii \.) i <\ woLf: fin the new pigments are not changed, have significantly more reddish shades and cannot be replaced by the familiar V \ i> mi <it . The new pigments also transfer the well-known yellow from diazo-

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tated l-atnino-4-nitrobenzene and 2,5-dimethoxy-4-chloroacetoacetanilide in terms of their reddish shade and their much better color strength, for example in Lacquers, paints and printing inks. This previously known monoazo pigment also has the disadvantage that it does not allow the production of flowing, strongly colored, reddish-tinged yellow printing inks permitted. The pigments which can be prepared according to the invention are also significantly more lightfast than those from the American one Patent No. 1,051,565 known pigment from diazotized l-amino-2-methoxy-4-nitrobenzene and 2-chloroacetoacetanilide.

Particularly surprising is the fact that the new pigments, in contrast to previously known, comparable dyes, all mentioned valuable properties at the same time unite in oneself.

That which can be obtained according to the invention is particularly valuable Pigment of the formula III, in which X is the ethoxy group and Y is a chlorine atom. It excels in printing inks an above-average brilliance and a particularly good color strength,

The following examples illustrate the invention. The temperatures are given in degrees Celsius.

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example 1

1.68 g of l-amino ^ -methoxy ^ -nitrobenzene are dissolved in 25 ml of glacial acetic acid, whereupon 15 ml of 2N hydrochloric acid are added to the solution. Shortly afterwards, add 10.5 ml of 1N sodium nitrite solution to this mixture at 10 ° with stirring, and stir the diazonium salt solution thus obtained for a further 30 minutes. Separately, 2.81 g of 2,5-dimethoxy-4- chloro-acetoacetanilide in 80 mL of methanol and 0.25 g ä are an adduct of 20 mols of ethylene oxide and 1 mole of stearyl alcohol, dissolved in 5 ml of water and 10.5 ml of 2 N sodium acetate solution added. to this is coupled by the filtered diazonium salt solution is allowed to flow over the course of 10 minutes with stirring into the solution of the coupling component at 20 ° C. The resulting pigment suspension is then heated to 40 ° for a further 5 minutes, filtered off on a suction filter, the residue is washed neutral with water and dried at 50 ° and pulverized.

The pigment produced in this way is a yellow powder. It is ideally suited for the production of printing inks for the graphic industry and produces very strong, pure, reddish tones yellow prints of good gloss, high transparency and very good lightfastness. In combination with red printing inks e.g. very pure orange tones are available.

If one uses an equimolecular menu of l-amino-2-chloro-4-nitrobenzene instead of the l-amino-2-methoxy-4-nitrobenzene, vn vv one holds at anr.oii :: i the same arbojtrwcirc wif in the example angogohori, a pigment with similar wf.rtvnl] cn Kigonnchai'tnn.

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Example 2 '■. . ■ "

8.40 g of finely powdered 1-amino-2-methoxy-4-nitrobenzene are carried while stirring in 146 ml of 2N hydrochloric acid and stirring is continued for 2 hours at 25 °. Then one transfers the mixture with 60 g of crushed ice and then diazotized the Ämin at 0 to 2 ° by dropping 10.35 g 33.3% sodium nitrite solution for about an hour, the - obtained diazonium salt solution is clarified and with 100 ml Ice water and 52.5 ml of 2N sodium acetate solution were added from 0 to 2 °. Immediately afterwards one leaves a 2 ° with stirring cold solution of 14.00 g of 2,5-dimethoxy-4-chloroacetoacetanilide

half in 108 ml of 2N sodium hydroxide solution and 525 ml of water within 30 minutes

add dropwise, the temperature keeps at 0 to 2 ° for another 30 minutes ; and finally increases it for another half Hour to 40 °. The pigment formed is filtered off, washed with water, dried at 60 ° and then pul · verized. ■

The pigment obtained in this way is a reddish yellow Powder. It produces similarly strong and pure in printing inks reddish-tinged yellow prints like the pigment produced according to example 1, paragraph 1.

Is used instead of 1-amino-2-methoxy-4-nitrobenzene 8.63 g of l-amino - ^ - chloro ^ -nitrobenzene and is otherwise the same as described in Example 2, one obtains a Yellow pigment .. has similar properties.

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Example 3 '

1.82 g of l-amino-2-ethoxy-4-nitrobenzene are dissolved in 25 ml Glacial acetic acid, 15 ml of 2N hydrochloric acid are added to this solution, the mixture is cooled to 10 ° and the amine is diazotized with stirring rapid flow in of 10.5 ml of 1N sodium nitrite solution.

In addition, 2 _} 81 g of 2,5-dimethoxy-4-chloroacetoacetanilide are dissolved in 100 ml of methanol with the addition of 0.15 g of an adduct of 20 moles of ethylene oxide with 1 mole of stearyl alcohol, dissolved in 3 ml of water, and 10 ml 2 n.-sodium acetate solution.

The filtered diazonium salt solution is then left within 7 minutes with stirring to the solution of the coupling component flow and then heats the resulting Pigment suspension to 40 ° over the course of half an hour. Afterward the pigment is filtered off, washed with water, dried at 60 ° and pulverized.

The product manufactured in this way is ideally suited for Manufacture of printing inks for the graphic industry and supplies reddish yellow prints of high color strength and color excellent lightfastness.

Heir: pi el 4 -.

1.68 g of l-amino-2-methoxy-4-nitrobenzene are -in 25 ml Eiinosnig dissolved, whereupon 15 ml of 2N hydrochloric acid are added to the solution added and the mixture cooled to 10 °. ' On that the amine is diazotized by rapidly pouring it in RUhreri of 10.5 ml 1N sodium nitrite solution,

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- ίο - '-.- ■■

On the other hand, 3.28 g of 2,5-dimethoxy-4-broiiiacetoacetanilide are dissolved in 100 ml of methanol ^ at 25 ° and adds 0.35 g of an addition product of 20 mol of ethylene oxide to 1.Mol Stearly alcohol dissolved in 7 ml of water and 10 ml of 2N sodium acetate solution added. The clarified diazonium salt solution is then left with stirring for 10 minutes to dissolve the coupling component and then heat the suspension up within 30 minutes 40 °. When the coupling is complete, the pigment formed is filtered off, washed with water, dried at 60 ° and pulverized.

The pigment obtained in this way is a very strong, reddish yellow. It is ideal for the production of printing inks for the graphic industry and delivers very strong, pure, reddish-tinged yellow prints of very good lightfastness, - "

Example 5

1.82 g of l-amino - ^ - ethoxy - ^ - nitrobehzole are dissolved in 25 ml Glacial acetic acid, add 15 ml of 2N hydrochloric acid, cool the solution to 10 ° and diazotise the amine with stirring rapid flow in of 10.5 ml of 1N sodium nitrite solution. '- "■■'"

In addition, 3.26 g of 2,5-dimethoxy ~ l-bromo-acetoaeetanilide are dissolved in 200 ml of methanol and 10 ml of 2N sodium acetate solution are added to the solution. Then leave the filtered Diazonium salt solution -auflie-ssen within 7 minutes with stirring to dissolve the coupling component and heated

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then the suspension formed within a half an hour at 4-0 °, when the coupling has ended, the pigment which has separated out is filtered off, washed with water, at 60 ° dried and powdered,

The pigment obtained in this way is a strongly colored, reddish yellow. It is suitable for the production of Printing inks for the graphic industry and supplies reddish-tinged yellow, very strong prints of very good lightfastness. - '

Example 6 . . . .

1.00-.g of that according to Example -3, Sections 1 to 3, prepared Pigments are mixed with 4.00 g of varnish of the composition

: 29.4 % linseed oil stand oil (300 poise), 67.2 % linseed oil stand oil (20 poise), 2.1 % Okta Soligen cobalt (8% Co) [Farbwerke Hoechst, Frankfurt a / M, Germany] and

1.3 % Octa Soligen Lead ($ 24 Pb) ■

Finely rubbed on an Engelsmann grinding machine and then on with the help of a cliché in the book printing process with 1 g

Printing color / m printed on art paper. You get one strong, pure, reddish shade of yellow with good transparency, good gloss and very good light fastness.

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

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Claims (1)

Paterite claims 1, process for the production of monoazo pigments. through this characterized in that one is the diazonium compound of an amine of formula I. NH, N-O, wherein X is a; lower alfcoxy group ,, means fluorine or chlorine, with a compound of formula II (II) OCH, CO CH ₉ .CO IH where Y is chlorine or bromine, coupling to a monoazo pigment of the formula III, CH- (III) - OCH. in which X is given under formula I and Y is given under formula II Have meaning. 009836/1609 2. Process according to claim I _3, characterized by the use of an amine of the formula I in which X represents the ethoxy group T represents ₃ and an acetoacetanilide of the formula II in which T represents chlorine. 3, monoazo pigments of formula III, Y
in which X is a lower alkoxy group, fluorine or chlorine and Y chlorine or bromine
mean. 4. Process for pigmenting high molecular weight organic Material characterized by the use of monoazo pigments according to claim 3. 5. The method according to claim 4, characterized in that the high molecular weight organic material is a printing ink binder for the graphic industry. 6, The material pigmented using monoazo pigments according to claim 3. 27.2.67 Jü / St / sh 009836/1609