DE2044924A1 - Dyestuff modification with aziridines - to improve solubility in water and affinity to cellulose fibres - Google Patents

Abstract

Dyes are modified by process of DT 2018855, an -OH or -nh2 gp. in the dye being reacted with an aziridine (opt. substd. ethylene imine) and polymerised by opening of the aziridine ring and reaction with excess aziridine. An azo dye inter. may be first treated in this way and then coupled to form the dye. A wide range of azo and other dyes and inters. e.g. naphthol- and amino- naphthol-sulphonic acids contg. -OH or -NH2 gps., may be treated.

Description

Process for the preparation of water-soluble. Fasoraffin dyes Addendum to patent ........ (Application Az.s P 20 18 855.0) It is known (German Offenlegungssohrift 1 419 797), high molecular weight dye derivatives by reaction of polymers containing amino and / or imino groups with reactive dyes. In this process, suitable intermediates for dye formation can also be used are used after the reaction by condensation or by coupling or diazotization and coupling are converted into dyes. In the main patent (German Patent application P 18 15 133.2) is a process for the production of water-soluble Sulfur dyes have been proposed in which water-insoluble sulfur dyes be reacted with alkyleneimines, in particular ethyleneimine. One receives thereby water-soluble sulfur dyes that can be colored without reducing agents and have an excellent affinity for cellulosic materials. These Implementation is according to the additional patent ............... (German patent application Az .: P 20 18 855.0) when using aziridines general application for the production capable of water-soluble, cationic dyes. After the procedure of the additional patent ................. (German patent application Az .: P 20 18 855.0) the water-soluble dyes are produced by mixing aziridines with dyes or intermediate dye products that contain functional groups in the molecule, which react with aziridines, reacted and with opening of the aziridine ring polymerized and any intermediate products formed by coupling be converted into dyes.

It has now been found that water-soluble cationic dyes in easier and cheaper way can be prepared that aziridines with Dyes or dye intermediates with at least one NH2 and / or OH group implemented in the molecule and polymerized with opening of the aziridine ring and optionally intermediate products formed are converted into dyes by coupling. Dyes or intermediate dye products with at least one NH2 and / or OH group in the molecule are mostly easy to manufacture and are therefore cheap to obtain. Suitable starting compounds can be found, for example, in the following classes of substances: Monoazo, disazo, trisazo, tetrakisazo, anthraquinone, xanthine, thiazole, pyrazolone, Methine, stilbene, thiazine, oxazine, azine, dioxazine, nitro and triphenylmethane dyes.

Dye intermediates suitable as starting compounds are for example: Naphtholsulphonic acids, aminonaphtholsulphonic acids and aminonaphthalenesulfonic acids, such as the I-acids, the γ-acid, the H-acid, the Chicago acid, the G acid, the R acid and the chromotropic acid. Through implementation the intermediate dye products with an airidin and polymerization lit excess Aziridine with opening of the aziridine ring, dye intermediates are obtained, which can be converted into dyes by coupling with diazo compounds.

For example, it is also possible to use the dye intermediate obtained Apply cellulosic materials and then perform the coupling.

The reaction, i.e. the initial conversion of the dye or dye intermediate with the aziridine and the subsequent or simultaneous polymerization with excess aliridine, opening the aziridine ring, can be used in solvents or preferably carried out in water. Also mixtures of solvents and water can be used. The starting dyes or starting dye intermediates can be in suspension or can be dissolved or partially dissolved. In In some cases it may be appropriate to use an insoluble starting dye or an insoluble starting dye intermediate is added prior to reaction in solution bring. In most cases, however, the implementation according to the invention can also be used insoluble starting materials are carried out. The reaction takes place at temperatures from about 10 to 120.degree. C., preferably from 30 to 1100.degree.

As in the first additional patent (German patent application P 20 18 855.0), especially the aziridine itself (ethyleneimine) and substituted Aziridines, for example 2-methylaziridine (= 1,2-propyleneimine) understood.

Other suitable substituted aziridines are, for example, 1-acetyl-aziridine (= N-acetyl-ethyleneimine), 2-carbowamidoaziridine (= ß-ethyleneimino-propionamide), l-methyl-aziridine = N-methyl-ethyleneimine); 2,2-dimethyl-aziridine (= 2,2-dimethyl-ethyleneimine), 2,3-Dimethyl-aziridine (= 2,3-dimethylethyleneimine), 2-carbmethoxy-aziridine, ß-ethyleneimino-propionic acid methyl ester and 2-ethyl-aziridine (= 2-ethyl-ethylenimine).

The polymerization with opening of the aziridine ring is acidic Catalysts or alkylating agents favored.

Suitable catalysts are, for example, acids, especially hydrohalic acids, Carboxylic and sulfonic acids, aluminum chloride, fluoride, borofluorodietherate, dialkyl sulfate, Alkyl halides, especially ethylene chloride, epichlorohydrin, sulfur dioxide and Carbon dioxide. Conveniently, sulfur dioxide or carbon dioxide becomes gaseous introduced into the reaction mixture. The use of a catalyst mixture, e.g. epichlorohydrin and carbon dioxide, is useful in many cases.

A copolymerization can also be carried out instead of a polymerization will. This is done after the dye or dye intermediate has reacted with an aziridine, another aziridine or an aziridine mixture is added and the Copolymerization triggered by a catalyst already mentioned. Implementation too of Starting dye or starting dye intermediate can already with a Aztridine mixed.

In many cases the polymerization or copolymerization is after the reaction of the dye or intermediate dye made with the aziridine.

For this purpose, the reaction mixture, which between the end of the reaction the starting product and the aziridine usually has a temperature of 80 to 110 ° C, generally about cooled and at about 60 to 75 ° C by adding the catalyst the polymerization or copolymerization triggered, which is then normally at higher rates Temperature, preferably up to 110 ° C, is carried out to the end. Before adding the catalyst further aziridine or mixture of asiridine can be added.

In the dye or intermediate dye used as the starting material two or more NH2 and / or OH groups can also be present in the molecule, Other groups that react with the aliride may also be present, e.g. one or more SO3H groups. Such starting compounds can also be used in which the NR2 and / or OH group only arises during the implementation. For example, it is possible to use dyes with an ONa group, Even which according to the present invention using dyes or dye intermediates, which contain at least one NH2 and / or OH group in the molecule, can be produced Cationic dyes are characterized above all by a special brilliance and high affinity for cellulosic material ion. They are soluble in Water or acidified water and in the form of the dye pastes obtained directly for dyeing e.g. cotton, rayon, regenerated cellulose and paper, in Excellent for every processing stage. Because of the high affinity of the polymeric cationic dyes compared to cellulose, arise e.g. during dyeing significant advantages of paper. The dyes produced can be in the form of The paste obtained can be admixed with the paper pulp during the papermaking process. The dyes are completely absorbed by the paper fibers, so that no dyes contaminated wastewater is produced. The dyeings show excellent fastness properties and there is a risk of two-sided dyeing when using the dyes according to the invention practically impossible.

Example 1 10 g of diamine deep black EC (C.I. Direct Black 38, C.I. No.

30235) of the formula were suspended in 50 ml of water and 30 ml of ethyleneimine and then 0.1 ml of epichlorohydrin were added dropwise at room temperature. The mixture was then carefully heated to reflux, a brief exothermic reaction occurring. It was heated to reflux for 3 hours and then the resulting dark brown solution was cooled to 60-62 ° C. and a weak stream of carbon dioxide was passed into the mixture for 5 minutes. The reaction mixture was stirred at a bath temperature of 120 ° C. for a further two hours.

A brown viscous solution was obtained which dissolves well in water loosened and stained bleached sulfite pulp in a black-brown shade.

The dyes listed below can be prepared in an analogous manner react with aziridines, with sulfur dioxide in place of carbon dioxide in the mixture could be initiated. The final dyes obtained are colored bleached Sufite pulp in the following colors.

Color of the final dye obtained on paper a) Diamine Fast Red N (CI Direct Red 1, CI No. 22310) red b) diamine dark green N (CI Direct Green 1, CI No. 30280) green c) Cotonerol BC (CI Direct Black 22, CI No. 35435) black SO 3Na OH N112 H2N \ N = /% = ¼ff \ / = NN 2 Na0 5 03Na 3 Example 2 10 g of primulin (CI Direct Yellow 59, CI No. 49000), which consists of a mixture of two compounds of the following formulas was suspended in 90 ml of water and added dropwise 30 ml of ethyleneimine. This resulted in an exothermic reaction. The temperature rose to 86 ° C. and a clear solution was formed. The mixture was then heated in a bath at 100 ° C. for a further 2 hours.

A thick brown solution was obtained in this way. The product was completely soluble in water and stained cellulose a brilliant yellow.

The dehydrothiotoluidinesulfonic acid can be converted in an analogous manner will.

Example 3 20 g of Celliton Fast Pink BN (C.I. Dispersion Red 15, C.I.

No. 60710) of the formula were suspended in 50 ml of water, added dropwise 30 ml of ethyleneimine and heated to 83-93 ° C (internal temperature) for 2 hours. The mixture was then cooled to 650.degree. C., a further 10 ml of ethyleneimine and 0.1 ml of epichlorohydrin were added dropwise and carbon dioxide was passed in for 10 minutes. This was followed by post-condensation in a bath at 110 ° C. for 2 hours. The dye mass obtained was completely soluble in water and stained the sulfite pulp in a red-violet color.

The following dye could also be reacted with ethyleneimine in an analogous manner: Color of the final dye obtained on paper Cellitonech Orange Git (CI Disperse Orange 3, CI No. 11005) orange Example 4 8.08 kg diamond deep black RW (CI Direct Blaok 4, CINr.

30245) of the Constitution were dispersed in 32.4 l of water and heated to 62 ° C. in a 60 l kettle. 4.04 l of ethyleneimine were added in 8 equal portions over the course of 70 minutes. The temperature in the reaction mixture was kept at 62-84 ° C. by cooling. After the reaction had subsided, carbon dioxide was passed in for 15 minutes, then briefly evacuated and cooled to 30 ° C. A thin liquid product which can be diluted indefinitely in water was obtained. In order to achieve good storage stability, it was advantageous to adjust the product to a concentration of not much more than 15-20%.

The liquid dye obtained according to the invention colored paper in the mass, consisting of more or less ground, bleached or unbleached Sulphite or sulphate pulps immediately and completely turn black.

Unsized papers, e.g. neutrally reacting filter papers, as well as sized papers with the usual pH adjustment of the paper stock between 4,5 and 5 are colored. Because of the fast dyeability of the paper stock, in continuous dosing immediately in front of the headbox on the paper machine to be colored. Even with neutrally reacting papers, this was the case with the sheet formation The water running off the paper machine sieve is clear, i.e. without any tint or even Staining, ab.

Beieniel 9 10 g of 1-mercapto-2-amino-anthraquinone and 50 ml of ethyleneimine were refluxed for 5 hours. The resulting red-brown solution was on Chilled 700C, Naoh Addition of 0.5 ml of epichlorohydrin was during 15 minutes of carbon dioxide initiated. A strong exothermic reaction occurred and the temperature rose to 1150C. It was diluted with 25 ml of water and still heated in a bath of 120 0C for one hour. The dye solution obtained was perfect soluble in water and easily incorporated into a bleached paper stock suspension Enter sulphate pulp, 390 SR. Here too, the dye moved immediately and completely on the fibers that have been dyed brown.

The wastewater obtained remained uncolored.

Example 6 10 g of fuchsine (CI Basic Violet 14, CI Solvent Red 41, CI Pigment Violet 4, CI No. 42510) of the constitution were dissolved in 50 ml of water and, after the addition of 30 ml of ethyleneimine and 0.1 ml of epichlorohydrin, heated to 83-99 ° C (internal temperature) for 3 hours. The viscous solution is soluble in dilute acetic acid and turns red. The following dye could be reacted with ethyleneimine in an analogous manner: Chromoxane violet B (CI Merdant Violet 27, CI No. 43860) Example 7 10 g of eosin (CI Acid Red 87, Pigment Red 90, CI No.

45380) of the Constitution were dissolved in 50 ml of water, 30 ml of ethylene imine and heated for 3 hours in a bath at 1100C (internal temperature 89-92 ° C). The viscous solution was cooled to 6500, 0.1 ml of epichlorohydrin was added and carbon dioxide was passed in over 9 minutes. This was followed by post-condensation in a bath at 120 ° C. for 2 hours. A red, viscous solution was obtained which was soluble in water and stained pulp red.

Example 8 10 g of H-acid, a substance of the formula were suspended in 50 ml of water and heated to 650c. At this temperature, 17 ml of ethyleneimine were slowly added dropwise with stirring; the temperature of the reaction mixture rises to 82-85 ° C. during this process. After the heat of reaction has subsided, carbon dioxide is passed into the reaction mixture at 730 ° C. for 5 minutes and then stirred for a further 30 minutes at 70 ° C. The reaction product is a brownish colored clear solution.

50 mg of the obtained reaction product became an aqueous one Suspension of bleached sulfite pulp (15 g dry matter) added. To Intimate mixing was suction filtered and the residue dried. That on this Paper obtained in this way could be dripped on, sprayed, impregnated or Colorize printing with diazotized aromatic amines (real salts). So became e.g. with a 5% aqueous solution of real orange salt GR (Azoic Diazo Component 6, C.I. No. 37025) a bluish brown and with a 5% solution of real garnet salt GC (Azoic Diazo Component 27, C.I. No. 37215) obtained a blue.

Claims (1)

P a t e n t a n s p r u c h Process for the preparation of water-soluble dyes, in particular according to patent ......................... (Application As .: P 20 18 855.0), characterized in that an aliridine with a dye brw, dye intermediate with at least one NH2 and / or OH group converted in the molecule and polymerized with opening of the aziridine ring and any intermediate product formed by coupling into a dye is convicted.