DE1544597A1 - Process for the production of dyes - Google Patents

Description

PATENT LAWYERS

DR.-ING. H. F (NCKE DIPL-ING. H ΒΟΗ * DIPL.-ING. S. STAEGER

15U597

MONKS 5

MOLLERSTR. 31

March 10, 196S

17238 - Dr, F / br Case i). 13040

Description based on patent application by CHÄtCAL INDOSIRlJBö LlHlIJiD, London *. \ I concerning:

"Process for the production of dyes"

Retired from patent ... (file number: I 15 178 IVe / 22a)

August 7, 1957 and July 11, 1958 Great Britain

The invention relates to new dyes and their use and in particular bolts containing s-l'riazine rings, and the dyeing process that is used to apply them to cellulosic © To apply textiles.

009819/0663

BATH ORIGINAL

It has already been proposed to use dyes, e.g. the A20- and Antbrachiwon series, which have one or more s-iriaain kernels contain, to produce, and these dyes, among other things, as simple to apply direct dyes for dyeing cellulose.

It is also known that the class of direct dyes are not very fast to vigorous washing treatments compared to W KAipen dyes and other temporarily solubilized dyes.

The present invention is based on the observation that certain new water-soluble s-triazine compounds which have valuable properties that they can be used for dyeing Cellulose-containing textiles can be used to color shades that are extremely authentic compared to vigorous washing treatments and almost reach the VJasfastness of vat dyes or in most cases equivalent to the latter, provided that the dyeing process is in conjunction with a treatment with an alkaline substance is carried out.

The new s-5riazine compounds that are the subject of this Invention form, bind those that, on the one hand, have two groups

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of the class consisting of eulfonated arylthio groups and on the other hand contain the remainder of a colored compound or the remainder of a colorless compound, which at least contains a group known to be colorless with it Connections in situ on a textile material in a colored compound can be converted, the remainder being bonded to the triazine nucleus via a nitrogen atom.

Ks, although this cannot be fully proven, is believed to be stains with such high resistance compared to washing treatments using the new coloring substances can only be obtained because of this can, veil the new coloring substances when they are in In combination with an alkaline agent, react chemically with the textile material. Obviously, the sulfonated arylthio groups are split off in the process and a triazinyl ester of cellulose is formed.

According to the invention, new water-soluble coloring bubatan-2s suggested the formula:

X-C

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BATH ORIGINAL

correspond, in which X is a group in which the remainder a colored compound or the remainder of a colorless compound contains the groups known to be with their help, colorless compounds in situ on one lerfcilmaterial can be converted into a colored compound can, is bonded to a nitrogen atom that is still on the carbon atom of the triazine nucleus and Y is a sulfonated arylthio group.

The Löaiich-making groups, a »13. bulfonsäure or _a C-rbon Bäuregruppen, in the new coloring substances of the groups may be contained in jjeder, which are shown in the above formula by X and Y.

The nitrogen atom in X attached to a carbon atom of the Triazine ring, can have one or two bonds with the remainder of the dye or pigment intermediate molecule be linked «If it is linked by two bonds, it can, for example, form part of a saturated heterocyclic ring, e.g. a piperazine ring. VJenn it is bound via only one bond, the third substituent on the nitrogen atom can be a hydrogen atom, a Be an alkyl, aralkyl or cycloalkyl group.

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The new coloring substances can be produced according to the invention be by adding a Q! riazin to the three to the Carbon atoms of the same containing bonded halogen atoms, with 2 KoI of a sulfonated mereaptoaryl compound and 1 Hol converts a compound which is once characterized in that it has one or more amino or monosubs ^ ituted Contains amino groups, and secondly is characterized in that it is colored, or if it is colorless, also contains groups of which it is known that with their help a colorless substance is converted into a colored substance can be"

As examples of suitable iCriazines, according to the invention can be used, cyanuric chloride and cyanuric bromide may be mentioned.

Examples of sulfonated mercaptoary compounds »which are used are: Thiophenol-5-Bulfonic acid, Thiophenol-4-sulfonic acid, 2-thionaphthol-6,8-disulfonic acid, S-thionaphthol-B-sulfonic acid "

Examples of monosubstituted amino groups in the compounds used in the process according to the invention

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may be present include, for example, alkylamino ^ ethylamino, • Athylamino, propylamino, butylamino, .beta.-hydroxyethylamino, .beta.-Sulfoäthylamino, ß-sulfatoethylamino, ß-Chloräthylamino, ^ chloro-beta and beta-hydroxypropylainino Carboxyäthylamino, aralkylamino, z " B, benzylaaino, and cycloalkyl amino groups such as cyclohexylamines.

The compounds used in the process according to the invention are further characterized in that they are colored or, neon they are colorless, contain groups of which it is known that a colorless substance can be converted into a colored substance with their help.

Suitable compounds are a.B. Dyes of the various series that contain amino groups, such as nitro dyes, aaofarbfctoffe, including thiazole dyes, azoxystilbene-L dyes and pyrasoloa or hydrazone dyes, di- and Triarylmethane dyes, aöridine, qxyazine, ihiazine and Azine dyes, indigoids, aminoanthraquinones, aminoanthraquinone dyes, Phthalocyanine dyes, aromatic diamines, aminophenols, aminonaphthols and N- and O-acidyl or alkyl, Aralkyl ~, or aryl derivatives of these compounds »

009819/0663

The method according to the invention is expediently carried out in carried out in a liquid medium and preferably in an aqueous medium, i.e. in water or in a mixture of water and a water-miscible organic liquid ι such as acetone, dioxane or dimethylformamide. If that Process is carried out in an aqueous medium, the sulfonated hercaptoaryl compound is preferably in the form their alkali salt implemented. If necessary, you can use an acid-binding gown, preferably a carbonate or bicarbonate, add to the reaction medium.

It has often been found useful, in particular, when the process is carried out in an aqueous medium, a slight excess of cyanuric halide over to apply the theoretical amounts specified in the preceding Paragraphs were specified. X) you can wear anything with it Decomposition of the cyanuric halide, e.g. hydrolysis to cyanuric acid under the conditions of transfer and you can from the coloring component, which is usually more expensive than the other starting materials, a higher relative yield achieve. Usually an excess of up to 30 wt. sufficient cyanuric halide and often one can stay far below this value.

. ; - β - 0 09819/0663 BAD ORlGlMAL

The new coloring substances containing an azo group can also be prepared by adding a diazonium compound reacts with a coupling component, either the diazonium compound or the coupling component or both compounds have at least one s-triazinylamino group contained in the two carbon atoms of the iriazine nucleus are substituted by a sulfonated arylthio group.

In this modified process, it is appropriate to use the Diazotization and coupling at the lowest possible temperature and preferably below 10 ° and the coupling process to be carried out at the lowest possible pH in order to avoid, as far as possible, sulfonated arytofchio groups through Hydroxylrestβ can be replaced, which is easily converted into strongly alkaline f-iedien

The new coloring substances are for coloring cellulosic Textiles are suitable ', especially if the weeding is carried out in conjunction with an alkaline agent will",

The treatment of the cellulosic textile material with the Alkaline agents can be used before or during treatment

009819/0663 _ß -

bath

perform with the coloring substance, however, generally will preferred, the textile material only after treatment with the new coloring substance with the alkaline agent to treat·

Suitable alkaline agents in the paint process according to the invention can be used, and for example sodium hydroxide, Potassium hydroxide, sodium carbonate, sodium bicarbonate and irisodium phosphate.

When the entire surface of the iPextile material are dyed you can apply the new coloring substance by immersing the textile material in an aqueous solution that contains the containing coloring substance, and topical treatment with the coloring substance can be achieved by printing the textile material with a printing paste that has the coloring Substance contains

If the alkaline coat is used at the same time as the new dyeing Substance is to be applied, it is expedient dissolved in the aqueous solution or printing paste containing the coloring substance

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009819/0663 -

BATH ORIGINAL

The aqueous solution of the coloring substance according to the invention Regardless of whether or not it contains alkaline agents, it can be the conventionally used additives for aqueous ones Baths for applying dyes, e.g. sodium chloride, sodium sulfate, sodium alginate, urea and water soluble Contain alkyl ethers of cellulose.

The printing paste can also be used regardless of whether it is alkaline Contains agents that are commonly used additives, e.g. urea and thickeners such as methyl cellulose, Starch and carob seed thickening, however, alginates, e.g. Sodium alginate.

When the textile material both with the new coloring substance as well as having been treated with the alkaline agent, it can be washed, e.g. "by rinsing in" barrels, in order to remove it to remove loosely bound staining substance. In general it is useful if in the washing stage with a hot, dilute aqueous solution of soap or a Cleaning agent because the coloring substance that is not removed by such treatment, is very authentic to subsequent washing treatments

β 009 119/0663

In numerous cases it is found that the amount of coloring Substance, d: Le removed in such a purification step is reduced if the dyed textile material, after being treated with both the coloring substance and the alkaline agent, a short time, e.g. up to 5 minutes, is treated with ifasserdarapf.

If the applied in the inventive color process the new coloring substance is colorless, the coloring process naturally includes further treatments that are required, to convert the colorless compound into a colored compound. Such treatments can also be used if necessary then be included in the color process when the new one coloring substance used in the coloring process itself colored is, äedoeh contains groups, with the help of which by post-treatment according to the usual general methods in known Way the shade or the fastness properties of dyed Connections can be modified.

When the new coloring substance is substituted by suitable groups it can be applied to the fiber, e.g. a diazotization stage and then a treatment with a coupling component, a treatment with a di-

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azonium compound or a metallizing treatment subject.

When the new coloring substance is in situ on the fiber is to modify the color shade or the authenticity properties, this treatment is preferably carried out first carried out when the textile material has been treated and washed with the alkaline gown and with steam is·

The invention is illustrated in more detail in the following examples, in which parts mean parts by weight.

example 1

18.6 parts of cyanuric chloride are dissolved in 120 parts of acetone and the solution is added to a stirred mixture of 400 parts of water and 400 parts of ice below 0 °. The thus obtained Suspension is within 30 minutes between 0 and 4 ° with a solution of 42.4 parts of thiophenol-4-sulforic acid and 16 parts of sodium hydroxide in 200 parts of water are added and the reaction mixture was stirred for a further 30 minutes.

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37ι4 parts of the disodium salt used in Example 1 Aminoazo compound are dissolved in 600 parts of V / water and this solution to the above mixture within 30 minutes. The mixture is 16 hours below 10 stirred, then by adding 10 5 »sodium ~ carbonate solution neutralized against LaoJanus, warmed to 20 ° and stirred, with - as required - further Uatriuracarbonatlösung is added to keep the mixture neutral, until all of the aminoazo compound has reacted.

Then 180 parts of sodium chloride are added and the precipitated Dye filtered off and dried at room temperature.

The dye obtained contains the analysis after 6 sulfur atoms ie azo group and consists essentially of the 2,4-di- (4'-sulfophenylthio) -s-triazinylderivat the Aminoaapverbindung used as Ausgangsrnaterial.

BAD OPJGlNAL 009819/0663

Example 2

15 ropes of copper phthalocyanine ^ -K-CJ'-ajaino ^ '- sulfophenyl) -sulfonamide-4-3ulfonic acid

are dissolved in 700 parts of water and with as much aqueous 2n sodium carbonate solution is added so that the pH of the solution is 7 The solution is stirred and cooled to 5 °, and a solution of 4 parts of cyanuric chloride in 70 parts of acetone is added. The pH of the mixture is adjusted to 7 again by adding 2N aqueous sodium carbonate solution. Make more complete Reaction becomes a solution of 7.3 parts of sodium thiophenol-3-sulfonate and 1.4 parts of Hatriuiji hydroxide in 200 Parts of water given. The mixture is heated for 2.5 hours, then 300 parts of potassium chloride are added and the precipitated dye is filtered off, washed with saturated potassium chloride solution and dried.

The product obtained in this way, when applied to cellulose-containing materials by the method described above, dyes these greenish-blue, very washfast colors »

009819/0663

^4t -

Similar products are obtained if, instead of the im previous example used Hatriumthiophenoi-3-sulfonats 9.1 parts Hatriui & -2-thionaphthol-6-sulfonate or 12.6 Parts of Dinatrim-2-thionaphthol-6,8-disul £ onat are used.

009819/0663 sad

Claims (2)

-ie- 154 * 597 PATENT CLAIMS: 1. Process for the preparation of water-soluble coloring agents Substances, characterized in that a triazine, the contains three halogen atoms bonded to its carbon atoms, with 2 moles of a sulfonated carcaptoaryl compound and converting 1 mole of a compound which is once characterized in that it is one or more amino or monosubstituted Contains amino groups, and boo other characterized is that it is colored or, if it is colorless, still contains groups of which it is known that with their help a colorless substance can be converted into a colored substance. 2. Process for the preparation of water-soluble coloring agents Substances of the A ^ o series according to claim 1, characterized in that that one is an oiazonium compound with a coupling component coupling, being either the diazonium compound or the or both connections m at least one contained in the white carbon atoms iüriazinlcems äiaarefe & i.ne s «lfonierte ÄryltMo ^ ri ^ pe spb» «A1IMTANWIK.TE