DE889042C - Process for the production of water-insoluble colored bodies - Google Patents

Description

Process for the production of water-insoluble color bodies Production of water-insoluble color bodies, e.g. B. azo pigments, lacquer dyes, if surface-active compounds and / or protective colloids have already been used, to recover the insoluble dye in a finely divided state. the The dye powders obtained in this way, however, have an extraordinary effect in many cases hard grain, and special grinding systems are often required for their processing.

It has now been found that water-insoluble azo dyes of soft grain can be obtained if, during the coupling, small amounts of oils which do not significantly exceed 5% of the dry dye are added in the form of an aqueous emulsion or an emulsifier-01 mixture.

The usual emulsifiers are used to produce the emulsions. For example, anion-active products such as higher molecular weight alkyl sulfonates, alkyl aryl sulfonates, alcohol sulfur acid esters, condensation products of fatty acids and amino or oxyalkyl sulfonic or carboxylic acids, fatty acids, sulfonated fatty acids or fatty acid derivatives or resin acids, nonionic products such as adducts of alcohols of ethylene oxide with higher molecular weight or alkylphenols with various oxyalkylation stages, or else cationic products, which can optionally also be alkoxylated. You can use emulsifiers; which are soluble in water or in oil or in both media. Oil- and water-soluble emulsifiers include, in particular, the condensation products of higher molecular weight alkyl sulfamides with halocarboxylic acids, which can be prepared as follows: Fractions of higher molecular weight aliphatic hydrocarbons from the boiling range from about 50 to 35 ° are converted at the same time with sulfur dioxide and chlorine using conventional methods. It is expedient to work in such a way that only about half of the hydrocarbons are sulfochlorinated. The Sulfochlorierungsgemzsch is set with 'ammonia, -bzw. primary amines and continue to condense with halocarboxylic acids. This gives higher molecular weight alkylsulfamidoacetic acids, which contain a larger proportion of unchanged hydrocarbons and proportions of sulfamides and all #: ylsulfonic acid salts. The aqueous emulsion of an oil can be produced from an emulsifier-oil mixture, which is expediently clarified beforehand if the oil-emulsifier mixture is not clear from the outset. To clarify this, solubilizers, for example water, high molecular weight fatty acids such as olein, alcohols such as butanol, or low molecular weight, liquid, aliphatic carboxylic acids such as acetic acid, can also be used. An emulsifier-oil mixture can be added immediately or after dilution with water during coupling. However, the emulsions can also be produced by the so-called paste method by initially placing an aqueous emulsifier solution and slowly stirring in oil, the further oil being added only when the previously added oil has set. To achieve this better, you can add a little water from time to time. The paste obtained in this way can then be adjusted to the desired concentration as desired. The amount of oil can be within very wide limits, e.g. B. i to 95 %, vary. With a small amount of oil added, extremely finely divided, colloidal emulsions are obtained that have the appearance of real solutions.

One can perhaps assume that during the coupling there is a gradual Destruction of the emulsions occurs, with the oil particles precipitating in fine distribution and affect the formation of the dye particles. In some cases it can It may be useful to add electrolytes (salts or acids).

The following oils can be used, for example: Fatty oils, such as peanut oil, linseed oil, Corn kernel oil and others, also mineral oils or synthetic oils; z. B. from the Fischer-Tropsch synthesis.

The water-insoluble ones obtainable by the claimed process Azo dyes have an extremely soft grain and are therefore generally necessary no special grinding, but can be done by manual or simple mechanical Distribution can be converted into a powder that is free from hard particles. The high degree of softness of the powder and the fine distribution of the dyes are essential a good processing option, e.g. in drying oils, varnishes, printing thickeners, Offset printing inks, thermoplastic masses. Thereby are remarkable coloristic Achieved benefits such. B. higher color strength, livelier hue, better fastness properties, For example, oil and solvent fastness and others, as well as freedom from specks. As a result The dye powder or colored dough can be easily and evenly distributed with advantage in aqueous or oily media, for example in the production of Use wallpaper and colored paper or for pigmentation on textiles. Further they can be used in anhydrous media, e.g. B. for the production of colored lacquers dry way by grinding on the pan mill, for grinding with oils for graphic purposes. Purposes, for pigmentation of nitrocellulose lacquer, for coloring artificial and natural ones thermoplastic masses, inter alia. to serve.

From -the patents 697 o65 and 709 - 979 it is already bekdnnt, highly concentrated, to produce water-dye compositions containing the fact that in the preparation of the dyes or to the aqueous suspension in the water difficult or insoluble liquid compounds of the aliphatic or isocyclic series in added in such an amount that is insufficient to break the aqueous suspension. The liquid compounds of the aliphatic or isocyclic series can werden.- added in emulsified form as far as one has added the liquid compounds in the coupling reaction (see. Example .4 Patent o65 697), one has neither with nor emulsions with oils, such as used according to the invention worked. In addition, the liquid compounds have been used in very large quantities. As far as one has worked with fatty oils (. See Examples 7 and 8 of patent specification 697 o65); no emulsions were used and no addition was made to the coupling. In addition, large amounts of oil were used in this process. Insofar as small amounts of liquid additives have been used in emulsion form (cf. example sb of patent 7o2 27g), neither oils have been used nor the additives have been added during the coupling.

Following the procedure of the patents mentioned, no dyes are produced obtained from soft grain. The particular method according to the invention comes in not expressed in the publications. Example i For a coupling solution Zoo parts by weight of i-phenyl-3-carbethoxy-5-pyrazolone, which still contains chalk 4 parts by weight of a mixture of 6o parts by weight by half sulfochlorination recovered sodium alkylsulfamidoacetate, 40 parts by weight of spindle oil and 15 Parts by weight of water. A tetrazo solution of = 0.2 parts by weight is then left at 50 ° 3, 3'-dichloro-4, 4'-diaminodiphenyl run in. You can use the specified amount of Allow the concentrate to run in even during the coupling.

The clutch fluid becomes Congo acidic after the clutch has ended Asked, and there are another 4 parts by weight of. emulsifier-oil mixture given above added. It is then boiled for 1 hour, filtered, washed hot and dried.

For example, about 6 parts by weight can also be used for the coupling add the concentrate, the further addition can be omitted during the boiling; or you can only use the concentrate when boiling it. Instead of Above concentrate you can in all cases also a corresponding amount of a aqueous emulsion, for example of 20%, use.

Sodium alkylsulfamidoacetate is obtained as follows: One from the Fischer-Tropsch synthesis derived hydrocarbon fraction with boiling limits 22o up to 32o ° is used simultaneously with sulfur dioxide and chlorine according to the usual methods treats up to about half of the hydrocarbons present in sulfochlorides has been convicted. -The sulfochlorination mixture is treated with ammonia. The sulfamide mixture formed is further condensed with chloroacetic acid. To Neutralization gives a product which, in addition to sodium alkylsulfamidoacetate still considerable proportions of unchanged hydrocarbons and smaller proportions of alkylsulfamide and sodium alkylsulfonate.

The above procedure gives extremely soft powders, even without Mahlurig, just by manually pulverizing and sieving, after Incorporation in rubber with the necessary aggregates on the roller after Vulcanization of the mixture delivers strong, pure red tones in rubber. The inclination for dusting is greatly reduced in the dye powder according to the invention.

Instead of the above mixture of 60 parts by weight obtained by semi-sulfochlorination Alkylsilfamidoacetic acid and 40 parts by weight of spindle oil can also be a product to which no additional oil content is added. It was already on it pointed out that the alkylsulfamidoacetic acid prepared in the manner indicated above has a significant content of hydrocarbon oils.

One can color bodies based on the above azo dye with the same Also produce the result if you use 12 parts by weight of a mixture for the coupling also used, the 25 parts by weight of a condensation product of dodecylphenol with 8 moles of ethylene oxide and 75 parts by weight of mineral oil (with water and olein clear provided).

With equal success you can use the above dye in the form of a very soft powder obtained if you add 4 parts by weight of a copper component with water, olein and butanol made clear mixture of 2.6 parts by weight of oleic acid methyl tauride and adding 75 parts by weight of mineral oil. After the coupling is completed, the coupling fluid becomes made Congo acidic, and a further 8 parts by weight of the above mixture are added. It is then boiled for 1 hour, filtered, washed hot and dried.

You can do the above: Mixture also in the form of an emulsion, for example of io ° / o, apply. Example 2 A dye is prepared Diazotization of 77.5 parts by weight of i-amino-2-methoxybenzene-5-sulfonic acid diethylamide and coupling with 113 parts by weight of 2-oxynaphthalene-3-carboxylic acid-2 ', 4'-dimethoxy-5'-chloroanilide at pn 3.8 to 4; 6 at 2o to 25 °.

Before coupling, 9 parts by weight are added to the weakly Congo-acidic diazo solution of the above-mentioned, oil-containing sodium alkylsulfamidoacetate without further Oil addition too. After the coupling has ended, the mixture is heated to 40 to 50 °, filtered, good washed and dried. In this way you get a very loose, soft Powder that is extremely useful in oil grinding for surface coloring when diluted pure and strongly colored pink tones result and in the uri-cut spread a beautiful one Has opacity that, depending on the heating temperature, weaker if desired or can be set stronger. Also in the coloring of thermoplastics the purity of the shade is striking.

By increasing the amount of the alkylsulfamidoacetic acid given above Sodium, for example, 18 parts by weight, the powders are even softer and the hue brighter.

Instead of the alkylsulfamidoacetic acid obtained by semi-sulfochlorination Sodium without added oil can also be 9 parts by weight of a mixture of 60 parts by weight of the sodium salt mentioned and 40 parts by weight of mineral oil. Further one can start from a clearly stated concentrate, for example from 15 -Parts by weight of a 30 to 40% oleic acid methyl tauride and about 85 parts by weight Mineral oil.

A clear mixture of emulsifier and oil can be equally successful are used, which are made from 25 parts by weight of isooctylphenyl polyglycol ether (6.5 mol Ethylene oxide) and 75 parts by weight of mineral oil. Example 3 You put one Dye produced by diazotizing 48.4 parts by weight of i-amino-2-methoxybenzene-5-carboxylic acid anilide and coupling with 70.8 parts by weight of 2-oxynaphthalene-3-carboxylic acid-3'-nitranilide at pH 3.8 to 4.5 and i5 °.

Before coupling, the coupling component is added to the alkaline solution before the precipitation or the acidic precipitation bath before or after the addition of the acid 10 parts by weight a mixture consisting of 80 parts by weight of the above-mentioned alkylsulfamidoacetic acid Sodium, 20 parts by weight of mineral oil, 12 parts by weight of water in the form of a 20% strength aqueous emulsion too. After the coupling has ended, it is filtered, washed well and dried. You only get an extremely soft dye powder, which is ground manually rubbed, very strong and pure Bordo tones in connection with the paint with drying oil there. After working in rubber with the necessary After vulcanization, aggregates are obtained with extremely strong rubber colors very floral shade.

Instead of the sodium salt of alkylsulfamidoacetic acid, salts of other inorganic or organic bases can also be used, e.g. B. the potassium, ammonium, triethanolamine or cyclohexylamine salts. Furthermore, the amount of mineral oil can be reduced or increased. Example 4 A dye is prepared by diazotizing 30.3 parts by weight of i-amino-2-methyl-5-nitrobenzene and coupling with 62.5 parts by weight of 2-oxynaphthalene-3-carboxylic acid 4'-chloroanilide in a caustic medium at 40 ° . When the 2-oxynaphthalene-3-carboxylic acid-4'-chloranilide is dissolved, 5 parts by weight of the sodium alkylsulfamidoacetate specified above are added. After the coupling has ended, the mixture is made weakly acidic to Congo with hydrochloric acid, heated to g5 °, held for 1 hour, filtered, washed and dried.

Quite apart from the fact that the above addition reduces the solubility of 2-oxynaphthalene-3-carboxylic acid-4'-chloranilide greatly favored, one obtains extremely loose dye powder in this way very soft grain that even does not dry the press cake at higher temperatures in the spread with drying oil to be covered, strongly colored surface colorations with lead good ole ness.

Even softer powders are obtained with better fastness properties, such as oilyness, Solvent fastness, overspray fastness, and more vivid hue when you get the Coupling instead of in a caustic alkaline medium at pH values between 4.3 and 6.5 and 4o up to 50 °. One gives, for example, to the alkaline naphthol solution before Coupling and before the precipitation of the naphthol with an organic or inorganic one Acid a mixture of 2.3 parts by weight of dibutylnaphthalenesulfonic acid emulsified in water Sodium and 0.4 parts by weight of sodium alkylsulfamidoacetate, which is still unchanged Contains hydrocarbon oil. Example 5 A dye is prepared by diazotization of 40.5 parts by weight of i-amino-2, 5-dichlorobenzene and domes with 70 parts by weight 2,3-Oxynaphthoylaminobenzene at a pH of 3.8 to 6.5.

One sets to the alkaline naphthol solution before the coupling and before the precipitation of the naphthol with an organic or inorganic acid 6 parts by weight a clarified mixture of 8 parts by weight of 3o to 40% oleic acid methyl tauride and 75 parts by weight of mineral oil. The oil-emulsifier mixture is added to the It is advisable to first carefully mix the naphthol solution with a little water; Then it will be by further addition of water an approximately 5 to 10% emulsion is produced, which the Naphthol solution is added shortly before the precipitation.

With the help of this additive, an extremely loose, very soft one is obtained Dye powder # with very good oiliness and excellent solvent fastness. Without this addition, the coupling of the dye does not go up to at all Execute end. Another advantage is the better 1J overmolding fastness as well to highlight the much purer color in the oil rub.

With the same success you can, for example, in place of the above mixture Use a 10% emulsion made from 6 parts by weight of a clarified mixture from 8 parts by weight of isooctylphenyl polyglycol ether (5 moles of ethylene oxide) and 9o parts by weight Peanut oil is produced '. One can also start from a clarified mixture, for example 85 parts by weight of a higher molecular weight alkylarylsulfonate and Contains 15 parts by weight of mineral oil. The percentage of mineral oil can also be higher or higher be chosen lower. Instead of the sodium salt of alkylarylsulfonic acid, you can salts of inorganic or organic bases can also be used.

Furthermore, 4 parts by weight of a mixture of 2o parts by weight can also be used a higher molecular weight quaternary ammonium compound, for example a product, that by oxethylation of octodecylamine and. subsequent reaction with dimethyl sulfate is obtained, and 80 parts by weight of mineral oil, which by adding small amounts of olein, Ammonia and water are clarified, can be used. Example 6 You put one Dye by diazotizing 81 parts by weight of i-amino-2,5-dichlorobenzene and coupling with 160 parts by weight of 2,3-oxynaphthoyl-2'-anisidide at pH between 3.8 and 5.5 at about 3o °. The alkaline naphthol solution is used the coupling and before the precipitation of the naphthol with an organic or inorganic one Acid an aqueous emulsion of 15 parts by weight of sodium alkylsulfamidoacetate, as described in example i, too.

Instead of this mixture, a clear mixture can also be used 85 parts by weight of alkylphenylsulfonic acid triethanolamine and 15 parts by weight of mineral oil be used.

In this way you get a very soft, fluffy powder that can be processed very easily. Example 7 A dye is prepared Diazotization of 48.7 parts by weight of i-amino-3-methyl-4-chlorobenzene-6-sulfonic acid and coupling at pH values between 8.5 and 12 with 32.6 parts by weight of β-naphthol at 2o °.

For example, it is added to the alkaline naphthol solution shortly before the inlet of the diazo compound 4 parts by weight of a mixture of 6o parts by weight of methyl acid methyl tauride as about 30 to 40% paste and 40 parts by weight of mineral oil in the form of an aqueous one Emulsion is obtained after coupling the dye, pasting the press cake with 1.4 l of water and let it run into a solution within 20 minutes at about 80 ° 2io g of table salt in 1.8 l of water is a soft powder, while powder without this The addition has a very hard grain.

Instead of the above mixture, 1.3 parts by weight of alkylsulfamidoacetic acid can also be used Sodium, as described in Example i, was added as, for example, an emulsion of 10% will.

Claims (1)

Claim: Process for the preparation of water-insoluble azo dyes of soft grain, characterized in that small amounts of oils in the form of an aqueous emulsion or an emulsifier-oil mixture, which do not significantly exceed 5 % of the dry dye, are added during the coupling.