DE2856225A1 - PROCESS FOR THE PRODUCTION OF SOLUTIONS OF SALT OF HYDRO-SOLUBLE CARBONIC ACIDS OF CATIONIC COLORS OR. OPTICAL BRIGHTENER - Google Patents

Abstract

A process for producing solutions of salts of water-soluble carboxylic acids of cationic dyes or optical brighteners, the solutions of cationic dye salts or brightener salts which are obtained by this process and which are miscible with water in any proportion, and the use of these solutions for preparing dye liquors and printing pastes for dyeing, optical brightening and printing of, in particular, synthetic textile materials, which process comprises reacting a dye salt of the formula I D<(+)>An<(-)> (I> in which D<(+)> is the radical of a cationic dye or cationic brightener, and An<(-)> is a complex anion of which the donor atom is a soft atom, in an aqueous or anhydrous medium, with at least one water-soluble carboxylic acid in the presence of an epoxide compound.

Description

DR. BERG D-PL.-ING SIAPF DIPL.-ING. SCHWABH DR. DR. SANDMATR 2856225

PATENTANWÄLTE PO Box 860245 8000 Munich 86

Attorney's file: 29 639 December 27, 1978

CIBA-GEIGY AG Basel / SWITZERLAND

Process for the preparation of solutions of salts of water-soluble carboxylic acids of cationic dyes or optical brighteners

Case 1-11511 *

8Θ9827 / 0954

9 (089) 988272 Telegrams: Bank accounts: Hypo-Bank Munich 4410122850

988273 BERGSTAPFPATENT Munich fBLZ 70020011) Swift Code: HYPO DE MM

988274 TEtEX: Bayer Vereinsbank Munich 453100 (BLZ 70020270) 983310 0524560BERGd Postscheck Munich 65343-808 (BLZ 70010080)

CBA-GEIGY

CLBA-GEIGY AG. CH-4002 Basel

1-11511 * Germany

Process for the preparation of solutions of salts of water-soluble carboxylic acids of cationic dyes or optical dyes

Brightener

The invention relates to a process for the preparation of solutions of salts of water-soluble carboxylic acids cationic dyes or optical brighteners, the solutions obtained by means of this process of cationic dye or. Lightening salts, which are miscible with water in any ratio and their use for the production of Dye liquors and printing pastes for dyeing, optical brightening and printing, in particular synthetic textile materials.

The handling and use of cationic dyes or optical brighteners are known to be in the form of powders is associated with an unpleasant dust development, not only for the personnel handling these powders is perceived as annoying and unhygienic, but also leads to constant contamination of the premises and workplaces and equipment, which requires the use of appropriate protective devices. Furthermore, it is often difficult powdery, cationic dyes or optical brighteners Dissolve in water, as they are difficult to wet and sometimes form lumps. The preparation of dye or This makes brightener liquors more difficult. Therefore, there was a need to remedy these drawbacks.

809827/0954

Various proposals have already been made for this purpose. So it was recommended to use cationic dyes and Bringing optical brighteners in the form of aqueous or organic, especially concentrated solutions on the market.

However, the requirements that are placed on concentrated liquid forms of commerce are numerous. So they have to Be unrestrictedly miscible with water and without decomposition after storage for different lengths of time, often at elevated temperatures Temperatures, withstand. In many cases, real solutions in a very narrow pH range are also required. The possibly for Any solvents used should not be volatile and should be as little toxic as possible.

The manufacture of liquid commercial forms of cationic dyes and optical brighteners has been around for a long time Been the subject of many inventions.

The kafionic dyes or brighteners are included in synthesis often as salts "of strong acids (especially sulfates, chlorides, methosulfates). As such, they are mostly Slightly soluble in water or organic media. In order to remedy this disadvantage, it has therefore already been recommended to use salts strong acids of cationic dyes or optical brighteners first the corresponding free dye or brightener bases and then convert them to salts of water-soluble carboxylic acids (e.g. acetic acid). These carboxylic acid salts (e.g. acetates) are in a solvent which is miscible with water in every ratio, such as polyhydric alcohols and their Ethers or esters, polyethers, amides, lactones, nitriles, Dimethyl sulfoxide, tetrahydrofuran or dioxane dissolved to one side the desired liquid form and, on the other hand, the desired solubility of the cationic dyes or brighteners obtain.

But there are cationic dyes and optical brighteners, where it is not possible to use the acetates on the

called type from the corresponding salts of strong acids, because the coloring or brightening bases are not stable are or cannot be deposited.

It has also already been proposed. Salts of carboxylic acids by anion exchange or by reaction of the sparingly soluble carbonates or bicarbonates of cationic dyes with carboxylic acids.

While ion exchange is technically very often uneconomical, the method using bicarbonate fails mostly because it is two-stage and the bicarbonates often crystallize with difficulty and therefore not on an industrial scale can be deposited.

In French Patent No. 2.290.479, a Process described in which the halides, especially the chlorides, cationic dyes in salts of lower aliphatic Carboxylic acids are converted by placing them in an aqueous or anhydrous medium with lower aliphatic carboxylic acids and with an epoxy compound with a maximum of 12 carbon atoms at room temperature.

However, this known method is limited to the use of halide salts of cationic dyes. Many However, cationic dyes or optical brighteners cannot be isolated as halide, since they are either too soluble are or do not crystallize out, and must therefore be used as sparingly soluble salts of a complex ion, such as the zinc double salt or rhodanide can be precipitated and isolated.

It has now surprisingly been found that one can now also the sparingly soluble complex salts, especially the sparingly soluble zinc tetrahalides, or the cyanides and rhodanides can convert cationic dyes in a simple manner into salts of water-soluble carboxylic acids.

"Hardly soluble" in this sense means that the dye salt is not sufficiently soluble to produce a desired concentrated solution sufficient for a dye preparation to get the same.

9B9827 / 0954

The complex anions of poorly soluble cationic dyes and brighteners are those whose donor atom is a so-called soft atom, ie '.'soft bases ", as described by Ralph G. Pearson in" Survey of Progress in Chemistry " 5_, 1-52 (1969) are defined, which have low electronegativity and are highly polarizable and easily oxidizable. Complex anions, the donor atom of which has a log K value greater than 5. Particularly suitable complex anions are cyanide, rhodanide, and above all Metal halide anions, such as zinc tetrahalide, in particular zinc tetrachloride.

Since the zinc halide bond is more stable than, for example, the zinc acetate bond (see e.g. Chemical Society Special Publication No. 17, Stability Constants of Metal-Ion Complexes, London 1964, cited in A.F. Trotman-Dickenson et al., Comprehensive Inorganic Chemistry, Volume 3, Pergamon Press 1973, pages 209-214 and 235) it is unexpected that one according to the present invention practically a complete conversion of all halogen atoms from zinc halides by carboxylic acid groups, e.g. through acetate groups, what the production of concentrated, stable solutions can achieve cationic dyes based on the sparingly soluble complex salts allowed in a simple manner.

It is also surprising and unexpected that among the metal halide anions other than those discussed, which also form poorly soluble complex salts of cationic dyes, specific ones such as the rhodanide and cyanide anions, can also be converted into the corresponding carboxylic acid salts according to the process of the present invention, however, especially oxygen-containing complex anions are not. The definition of the anion also prevents the latter includes.

999827/0914

The present invention thus relates to a process for the preparation of solutions of salts of water-soluble carboxylic acids cationic dyes or cationic optical brighteners, which is characterized in that one Dye salt of the formula I

D © An © (I)

where D ^ is the remainder of a cationic dye or brightener and an its complex anion whose donor atom is a soft atom is, mean in aqueous or anhydrous medium with at least one water-soluble carboxylic acid in Reacts the presence of an epoxy compound.

Processes according to the invention are used as dye salts for dag Salts of cationic dyes or brighteners with complex anions, such as those obtained during manufacture, are in question, which are mostly sparingly soluble in water and solvents and therefore not for the production of concentrated and storage-stable Solutions according to known methods can be used.

The sparingly soluble complex salts which can be used according to the invention Cationic dyes and brighteners are known and can be prepared by known methods. It deals are chemically dyes, which are a colored cation and, as a colorless anion, an anion according to the definition, whose Donor atom is a soft anion. The dyes can belong to the most varied of chemical classes; for example it is azo dyes, such as monoazo, disazo and polyazo dyes, anthraquinone dyes, phthalocyanine dyes, Diphenylmethane and triarylmethane dyes, naphtholactam, methine, polymethine and azomethine dyes, Enamine, hydrazone, thiazole, ketonimine, acridine, cyanine, Nitro, quinoline, benzimidazole, xanthene, azine and thiazine dyes. Preferred cationic dyes are azacyanine and oxazine dyes.

889827 / 09S4

Suitable optical brighteners are, for example, quaternization products of pyrazolines, naphthalimides, imidazoles (e.g. Derivatives of benzimidazol- (2) -yl-2-benzofuran, of 5-phenyl-2-benzimidazol- (2) -yl-furans or derivatives of Coumarins with imidazole residues in the 3- and / or 7-position) or Triazoles (such as derivatives of coumarins with triazole residues in the 3- and / or 7-position) with quaternizable tertiary Nitrogen atoms, as well as oxacyanine derivatives.

Suitable water-soluble ones which can be used according to the invention Carboxylic acids are above all water-soluble aliphatic, in particular lower aliphatic (C 1 -C 4) carboxylic acids, such as e.g. water-soluble saturated and unsaturated aliphatic mono- and polycarboxylic acids, which may be substituted can. The main substituents are halogen, such as chlorine, Bromine and fluorine, alkoxy, preferably hydroxy, and optionally substituted phenyl are possible. Among polycarboxylic acids one understands above all di- and tri-carboxylic acids. Mixtures of these water-soluble carboxylic acids can also be used.

. The saturated water-soluble aliphatic monocarboxylic acids are, for example, saturated unsubstituted ones Monocarboxylic acids, such as formic acid, acetic acid, propionic, η-valeric and caproic acid, as well as substituted lower ones Monocarboxylic acids such as glycolic acid and lactic acid, halogen-substituted lower aliphatic monocarboxylic acids such as fluoroacetic acid, Chloroacetic acid, bromoacetic acid, iodoacetic acid, dichloro and trichloroacetic acid, α-chloropropionic and β-chloropropionic acid as well as methoxyacetic acid, cyanoacetic acid, glyoxalic acid and phenylacetic acid.

Examples of optionally substituted dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Tartaric acid and malic acid. Citric acid is an example of a tricarboxylic acid.

689827 / 09Sl

'<Τ ΑΧ.

Acrylic and methacrylic acid and vinyl acetic acid may be mentioned as examples of unsaturated monocarboxylic acids. Examples of unsaturated dicarboxylic acids include maleic and fumaric acids.

Substituted and unsubstituted lower aliphatic carboxylic acids are advantageously used, in particular ants or Acetic acid.

These carboxylic acids can be used in the form of aqueous (e.g. 20 to 99.5%) solutions. The Carboxylic acid in an excess, in particular from 30 to 2000%, especially from 110 to 500%, preferably from 110 to 300%, based on the anions to be converted, used to ensure a quantitative course of the reaction. Using Liquid carboxylic acids can also be worked anhydrous.

A wide variety of epoxy compounds can be used according to the invention be used. They are, for example, monoepoxide compounds such as alkylene oxides, cyclic alkylene oxides and Reaction products of epichlorohydrin with saturated and unsaturated aliphatic, aromatic or araliphatic alcohols and phenols to diepoxide compounds such as dialkylene dioxides and reaction products of epichlorohydrin with dialcohols, polyalkylene glycols or heterocyclic compounds, as well as around Triepoxide compounds.

The epoxy compound is also used with advantage in excess. The excess is between 10 and 300%, preferably between 10 and 200%, of the theoretical amount, based on the anions to be converted.

Suitable monoepoxides are, for example, alkylene oxides such as ethylene, propylene and butylene oxide. They can also be substituted be e.g. with chlorine or phenyl such as epichlorohydrin or styrene oxide. They are preferably lower alkylene oxides, especially unsubstituted alkylene oxides having 2 to 5 carbon atoms, preferably propylene oxide.

8Θ9827 / 09Ι4

Suitable cyclic alkylene oxides are, for example, the compounds
formulas

Ott

location '

wherein χ is a number from 3 to 10, for example cyclohexene oxide
(when X = 4).

In the case of saturated and unsaturated reaction products of Alcohols and phenols with epichlorohydrin are, for example, compounds of the formula

RO _{- CH 2} - CH - CH ₂

where R is an aliphatic, aromatic or araliphatic radical, such as allyl glycidyl ether.

Suitable diepoxides are, for example, dialkylene dioxides, such as
Compounds of the general formula

CH ₂ - CH - (CH ₂ ) - CH - CH ₂

where y is 0 or a number from 1 to 6, such as butadiene diepoxide (y = 0) or diepoxioctane (y = 4).

Reaction products of epichlorohydrin with dialcohols
are, for example, compounds of the general formula

CH ₂ - CH - CH ₂ - 0 - (CH ₂ ) _m - 0 - CH ₂ - CH -

where m is a number from 1 to 6, e.g., butanediol diglycidyl ether (m - 4).

Reaction products of epichlorohydrin with polyalkylene glycols are, for example, compounds of the general formula

CH ₂ - CH - CH ₂ - 0 - (CH-CH ₂ O) _n - CH ₂ - CH -

where η is a number from 1 to 10 and RH or CHo, for example the compound in which RH and η is λ / 6 to 7.

§69827 / 0914

Reaction products of epichlorohydrin with heterocyclic compounds are, for example, the diepoxide compounds of the general formula

CH ₂ - CH - CH ₂ - X - CH ₂ - CH - CH ₂

in which X is a divalent heterocyclic radical, such as the compounds of the formulas

₂ -CH- CH ₂

N-CH ₀ -

CH ₀ -CH-CH ₀ N N CH ₀ - CH - CH ₀

ί. Δ.

^ ^ »Τ» ^ vr ^ »τ ^ T ^^ w ^ 4W ^^ ^ * w ^ tTT ^^^^ TT

CH ₀ - CH - CH ₀ - NN - CH ₀ - CH - O - CH ₀ - CH

Suitable triepoxides are, for example, the triepoxide compounds

of the formulas

CHo

37 \ 3 ^C ~ 7 ~ \ / ⁰ V

CHCHN N-CH ₀ -CH-CH ₀ -NN - CH ₀ - CH - CH

^H 3 ^C ~ 7 ~ \

r ν; · ..τ

CH ₀ - CH - CH ₀

and ■ - ^ Ό \

CH ₀ - CH - CHo

CH ₂ -CH- CH ₂ - Ν ^^ Ν - CH ₂ - CH - CH ₂

The inventive method is preferably on carried out in the following way:

The sparingly soluble complex salt of the cationic dye or brightener is first placed in the water

27/0914

soluble carboxylic acid or a carboxylic acid mixture, optionally in the form of an aqueous solution, added and stirred well using mixing devices customary in the art, such as stirrers or turbo mixers, for h to 1 hour. The epoxy compound is then slowly added dropwise, advantageously in excess, or introduced in gaseous form below level. The temperature can rise slightly. The reaction mixture is stirred for about 30 minutes to 1 hour. Then, if appropriate, the reaction mixture can be ^{heated to 100 °} C., advantageously to 30 to 70 ^° C. and in particular to about 35 to 60 ^° C., and kept at this temperature for about 1 to 2 hours. The excess of epoxy compound can, if appropriate, be removed by adding the amount of hydrohalic acid, in particular hydrochloric acid, which is just necessary for this. In many cases it is advantageous to clarify the resulting solution of any inorganic residues present by filtration. If necessary, the solution can then be diluted with water or an organic solvent in order to achieve the desired color strength or concentration.

The solutions of cationic dye salts or brightener salts of water-soluble carboxylic acids obtainable according to the present invention can be used directly as ready-to-use coloring or brightener preparations without further work-up. They are storage-stable, temperature-stable concentrated over 3 to 12 months of -10 ⁰ C to +40 ⁰ C and in that they contain from about 10 to 50% of the salt of a water-soluble carboxylic acid, in particular an acetate, of the cationic dye or brightener solutions are miscible with water in any ratio without precipitation of the dyes and can therefore be easily dosed volumetrically, regardless of whether they are diluted with water or poured into water.

109827/0864

Any desired concentration can be obtained by concentrating the resulting solutions.

The main advantage of the method according to the invention lies in that concentrated solutions that are directly usable are obtained during the manufacturing process.

Another advantage of the process according to the invention is that the amount of excess acid used can choose so that the pH of the reaction solution a reached a certain value (e.g. 4 to 5). This allows you to use the solution afterwards by simply adding it dilute water or organic solvent to the desired strength, and thus the annoying handling in the company avoid with acid.

One can obtain those obtainable according to the present invention Mix the solutions with any other identical dye or brightener preparations without the anions interfering with each other, i.e. without impairing the storage stability. That is why they are ideally suited for the production of so-called premixes.

After diluting the solutions obtainable according to the invention with water or an organic solvent, they can be used directly as Liquor for dyeing, optical brightening or printing of organic materials such as leather, wool, silk, cellulose acetate, Tanned cotton, paper, and especially textile material made from acid-modified hydrophobic synthetic fibers, such as acid modified polyamide, polyurethane, polypropylene and polyester, but especially of fiber material made of acid modified polyacrylonitrile can be used.

By adding suitable thickeners, thickened solutions are also obtained, which are ideal for use suitable in continuous dyeing and printing processes.

The following examples serve to illustrate the invention without restricting it thereto. In it the parts mean Parts by weight, percentages percentages by weight and the temperatures are given in degrees Celsius.

§098 2 7/0954

example 1

10 parts of the dye of the formula ^CH 3

CH

(ZnCl.)

are suspended in 12 parts of glacial acetic acid and 4 parts of water. 6.4 parts of propylene oxide are added dropwise at room temperature. After stirring for one hour, the mixture is heated to 50 to 55 ° and stirred for one hour at this temperature. To dilution with 15.6 parts of water gives 48 parts of a dye acetate solution, which leaves no residue when filtered clear leaves behind.

Ionic residual chlorine found: 0.17 "L Calculated before the reaction: 3.7% Calculated conversion -: 95 ° L.

In this way, a concentrated, ready-to-use dye solution is obtained which is stable to storage and temperature.

If "equimolar amounts" are used instead of propylene oxide of ethylene oxide, butylene oxide, epichlorohydrin or allyl glycidyl ether, or the corresponding half amount of butanediol glycidyl ether or a diepoxide of the formula

CH ₂ - CH - CH ₂ - 0 - (CH ₂ -CH ₂ O) _6-7 - CH ₂ -CH- or CH _{3 Q}

CH ₂ - CH - CH ₂ - N N _{- CH 2} - CH - CH ₂

or one third of the corresponding amount of an epoxide of the formula

2 7/0914

9 ^H 3 O f ^H 3 O

^H 3 ^C -tK H - CHo - CH - CH

CH ₀ - CH - CH ₀ - NN - CH ₀ - CH - CH ₀ - N N- CH ₀ - CH - CH ₀ 2 2 v> - 2/2 N _n ^ 2

CH ₂ -CH- CH ₂

so one also obtains with the rest of the same working method concentrated storage-stable dye acetate solutions.

999827/0914

Example 2

10 parts of the dye of the formula

^^ 1

are suspended in 6.4 parts of glacial acetic acid, 1.3 parts of oxalic acid hydrate and 6.4 parts of water. Be at room temperature 5 parts of propylene oxide were added dropwise. After stirring for one hour, the mixture is warmed to 50 to 55 ° and stirred for one hour After the addition of 6.9 parts of water and clarification filtration, it is obtained one 31.7 parts of a chloride ion-free dye solution.

Ionic residual chlorine found: <0.0l % Calculated before conversion: 5.3%

Turnover: 100%

In this way you get a concentrated, direct Ready-to-use dye solution that is storage and temperature stable is.

Use equimolar amounts instead of acetic acid Formic acid, propionic acid, butyric acid or lactic acid are also obtained with otherwise the same procedure stable dye solutions which contain the cationic dye as salts of the corresponding carboxylic acid.

999827/09

Example 3

10 parts of the dye given in Example 1 are dissolved in 20 parts of water and 10.3 parts of citric acid suspended. 4.6 parts of propylene oxide are added dropwise. After stirring for one hour, the mixture is heated to 50 to 55 ° and stirred for an hour. After adding 4 parts of water, the mixture is clarified by filtration. 42 parts of a dye solution are obtained in this way which contains the dye as citrate.

Ionic residual chlorine found: 0.17% Calculated before the conversion: 3.6%

Calculated conversion: 95%.

The dye solution obtained is stable in storage and ready for immediate use.

If part of the citric acid used is replaced by corresponding amounts of formic acid, acetic acid, Propionic acid, lactic acid, acrylic acid, hydroxyacetic acid, chloroacetic acid, oxalic acid, malonic acid, succinic acid, Tartaric acid or malic acid, then you also get dye solutions in which the dye is a mixture of salts corresponding carboxylic acids is present.

Example 4

10 parts of the optical brightener of the formula

are suspended in 7.7 parts of glacial acetic acid, 2.7 parts of oxalic acid and 5 parts of water. 2.3 parts of ethylene oxide will be initiated below level. After stirring for 30 minutes, the mixture is warmed to 35 ° and stirred for a further two hours. To the addition of 39 parts of water is clarified by filtration. Man in this way, a solution is obtained which contains the optical brightener in the form of acetate.

Ionogenas residual chlorine found: 0.09% Calculated before conversion: 2.2% Calculated conversion: 96%.

The solution obtained is immediately ready for use and has a storage and temperature stability of several months.

Used in the above examples instead of the zinc chloride salts the corresponding zinc bromides and zinc iodides, the corresponding optical brightener carboxylic acid salt is likewise obtained .

909827 / 09S4

Example 5

10 parts of the dye of the formula

(C ₂ H ₅ )

SCN

are suspended in 16.8 parts of glacial acetic acid. 4.4 parts of propylene oxide are added at room temperature and the mixture is stirred for 30 minutes. The mixture is then stirred for 2 hours at 60 ° and clarified by filtration. This gives 31 parts of a dye solution which contains the dye acetate. Ionic rhodanide found: 0.03 % Calculated before the reaction: 2.2% Calculated conversion: 98.5 %.

The resulting solution is ready to use and can be diluted to the desired concentration with 31 parts of water be asked.

In the above example, instead of 16.8 parts of glacial acetic acid, a mixture of 16.8 parts of acetic acid and up to is used 50% water, dye acetate solutions with equally good properties are obtained.

Dyeing prescription

3 parts of a dye solution obtained according to Example 1 are 40% strength in 2000 parts of water with the addition of 4 parts Acetic acid, 1 part of crystallized sodium acetate and 10 parts of anhydrous sodium sulfate dissolved. In this dye bath if 100 parts of dried polyacrylonitrile staple fiber yarn are added at 60 °, the temperature is increased within half an hour to 100 ° and colors for an hour at boiling temperature. Then the dye is rinsed well and dried

A level red dyeing with excellent fastness properties is obtained.

Claims (29)

Location. BC = RG Din.-INO. STAPF Λο ^ DiFL.-üiC ·. rc: Mv.v · r; ·. ■■ ':.' '.. · ί .ι «Attorney's file: 29 639-VT- ... Λν-: · ΐ ..' .: ■ .. ■ .. ·. ■ -.- i 6 PONC Ή Ci N 60 · f; I., iJ £ iiKIRCM.EpSTR. "Patent Claims' 2856225 1. Process for the preparation of solutions of salts water-soluble carboxylic acids of cationic dyes or Cationic optical brightener, characterized in that a dye salt of the formula I An Θ (I) wherein D ^ the remainder of a cationic dye or brightener and an its complex anion whose donor atom is a soft atom is, mean, in an aqueous or anhydrous medium with at least one water-soluble carboxylic acid in Reacts the presence of an epoxy compound. 2. The method according to claim 1, characterized in that a dye salt of the formula I is used, in which Ansein complex anion, the donor atom of which is a log K value larger than 5. 3. The method according to claims 1 and 2, characterized in that that a dye salt of the formula I is used in which the complex anion is cyanide, rhodanide or a metal halide anion is. 4. The method according to claim 3, characterized in that a dye salt of the formula I is used in which the metal halide anion is a zinc tetrahalide. 5. The method according to claims 3 and 4, characterized in that that a dye salt of the formula I is used in which the metal halide anion is zinc tetrachloride. 9098? 7/0954 6. The method according to claims 1 to 5, characterized in that that at least one water-soluble aliphatic carboxylic acid is used. 7. The method according to claim 6, characterized in that a substituted or substituted carboxylic acid is used as the water-soluble carboxylic acid unsubstituted lower aliphatic carboxylic acid used. 8. The method according to claims 6 and 7, characterized in that that a monocarboxylic acid is used as the water-soluble carboxylic acid. 9. The method according to claims 6 and 7, characterized in that that a dicarboxylic acid is used as the water-soluble carboxylic acid. 10. The method according to claim 6, characterized in that a tricarboxylic acid is used as the water-soluble carboxylic acid, 11. The method according to claim 1, characterized in that the reaction is carried out in aqueous carboxylic acid. 12. The method according to claim 1, characterized in that the reaction is carried out in anhydrous liquid carboxylic acid. 13. The method according to claim 1, characterized in that there is a 30 to 2000% excess of water-soluble Carboxylic acid used. 14. The method according to claims 11 to 13, characterized in that that the water-soluble aliphatic carboxylic acid used is formic acid or acetic acid. Ö09827 / 09S4 15. The method according to claim 1, characterized in that a mixture of water-soluble carboxylic acids is used. 16. The method according to claim 1, characterized in that there is an excess of 10 to 300% of epoxy compound used. 17. The method according to claims 1 to 16, characterized in that that lower alkylene oxides are used as epoxy compounds. 18. The method according to claim 17, characterized in that the epoxy compounds are unsubstituted alkylene oxides with 2 up to 5 carbon atoms used. 19. The method according to claim 18, characterized in that the epoxy compound used is propylene oxide. 20. The method according to claims 1 to 16, characterized in that that the epoxy compounds are reaction products of epichlorohydrin with aliphatic alcohols or phenols used. 21. The method according to claims 1 to 16, characterized in that that reaction products of epichlorohydrin with dialcohols are used as epoxy compounds. 22. The method according to claims 1 to 16, characterized in that that reaction products with polyalkylene glycols are used as epoxy compounds. 23. The method according to claims 1 to 16, characterized in that that reaction products of epichlorohydrin with heterocyclic compounds are used as epoxy compounds. 909827 / 09S4 24. The method according to claims 1 to 23, characterized in that that the resulting solution is then diluted with water. 25. The method according to claims 1 to 23, characterized in that that the resulting solution is then diluted with an organic solvent. 26. Liquid dye or brightener preparation obtained according to the method of claim 1. 27. A liquid dye or brightener preparation according to claim 26, characterized in that it contains 10 to 50% of at least one Contains salt of a water-soluble carboxylic acid of a cationic dye or optical brightener. 28. Use of the dyeing or dyeing obtained according to the process of claims 1 to. Brightener preparations or the liquid Preparation according to claims 26 and 27 for the production of coloring or brightening liquors and printing pastes on aqueous Based or based on an organic solvent. 29. Use of the liquors and printing pastes prepared according to claim 28 for dyeing, optical brightening or printing of synthetic textile materials, especially polyacrylonitrile. B09827 / 0954