DE2335512A1 - STABLE, HIGHLY CONCENTRATED DYE SOLUTIONS MIXABLE WITH WATER IN ANY PROTECTION - Google Patents

Description

9335512

DR.BERG DIPL.-ING. STAPF " ⁰ ^ ^

DIPL.-1NG. SCHWABE DR. DR. SANDMAIR

PATENT LAWYERS t MÖNCHEN 80 · MAU ERKIRCHERSTR. 45 1-8295 / 8820 *

Attorney's file: 24 116 July 12, 1973

Stable, highly concentrated, with water in every ratio

miscible F arbstofflb'sungen

The present invention relates to stable, highly concentrated dye solutions which are miscible in all proportions with water of sulfonic acid group-containing azo and nitro dyes and of anthraquinone dyes, a process for Production of these dye solutions, as well as the use of these dye solutions for the preparation of dye baths for the dyeing or printing of textile material, in particular made of nitrogen-containing organic fibers.

Many dyes are usually sold as dried and finely ground powders that are used for dyeing in the dyebath must be dissolved or dispersed. However, this form of application has considerable disadvantages. Apart from the uncomfortable by weighing, transferring or filling in the intensely colored dye powder and the risk of dust formation Caking of the finely ground dye powder as a result improper storage due to the effects of moisture or Heat, the dissolving or dispersing of the powder in the dyebath cause serious difficulties, as the dyes are mostly only insufficiently soluble in water, especially if high dye concentrations are required, as e.g. are required in continuous dyeing or printing. If it is not possible to remove the undissolved dye

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proportions of a padding liquor or a printing paste into a sufficient one Bringing fine distribution, you get restless and flaky dyeings or prints.

It has therefore already been proposed to use dyes in the form of concentrated solutions. This allows certain Disadvantages, such as generation of dust and problem solving, Avoid that when using dye powders appear. Among other things, concentrated, heat and frost-resistant stock solutions of 2: 1 metal complexes from Azo dyes and anthraquinone dyes.

Furthermore, in DOS 1,794,132 solutions of specific acidic anthraquinone dyes described in an organic solvent or solvent mixture.

It has now been found that sulfonic acid groups are also advantageously high concentration of monosulfonsäuregruppenhaltigen, azo dyes and anthraquinone dyes and nitro, miscible in any ratio can be obtained between -20 ⁰ C and +50 ⁰ C storage-stable solutions. According to the invention, mixtures of an aprotic solvent or a mixture thereof, a glycol or glycol ether and optionally water are used as the solvent medium. Above all, this solvent mixture has a pronounced synergetic effect both for the solubility of the dyes and for the stability of the dye solution.

In the DOS 1,794,132 mentioned at the outset, such a synergetic effect with regard to the stability and the Increases in concentration are not observed; such an effect is nowhere described.

According to the invention, mixtures of an aprotic solvent which bring about this synergism are used as the solution medium or a mixture thereof, as well as a glycol or glycol ether and optionally water are used.

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The dye solutions according to the invention contain the dyes according to the definition preferably in amounts of 10 to 60% _3, in particular of 30 to 50%. The solvent mixture that can be used is advantageously composed of 5 to 60, especially 15 to 50 percent by weight of an aprotic solvent or its mixture, 15 to 50 percent by weight of a glycol or glycol ether and 0 to 50 percent by weight of water.

With the individual components of the solvent mixture mentioned In general, highly concentrated solutions of these dyes cannot be produced or have the same poor storage stability. on. Surprisingly, the solvent combination according to the invention, especially in the stated proportions, in particular for these commercially available dyes pronounced synergetic solubility effects and thus only enables the production of the stable, highly concentrated, Dye solutions miscible with water in any ratio.

The azo and nitro dyes containing sulfonic acid groups can in the form of their free sulfonic acids, but advantageously in the form of their metal salts, 2.B. Sodium, potassium or magnesium salts can be used according to the invention.

As azo dyes containing sulfonic acid groups, there are disazo dyes, but above all monoazo dyes are considered, e.g. the benzene-azo-benzene, benzene-azp-naphthalene, naphthalene * - azo-naphthalene, benzene-azo-pyrazolone, benzene-azo-aminopyrazole, Benzene-azo-acetacetic acid amide, benzene-azobenzene-azobenzene, Benzene-azo-naphthalene-azo-benzene or benzene-azo-benzene-azonaphthalene series belong, and also substituents, preferably alkyl or alkoxy groups with 1 to 6 carbon atoms, Halogen atoms, such as chlorine, bromine or fluorine, or nitro groups.

Nitro dyes containing sulfonic acid groups are proposed especially nitrodiphenylamine compounds which may contain further substituents, e.g. amino groups. The mentioned Dyes can also be present in mixtures with one another,

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The anthraquinone dyes can coloristically the belong to different classes. In particular, these are acidic dyes. Chemically, they are special interesting the 1-amino-4-arylamino-anthraquinones, which in 2-position can also have a sulfonic acid group.

Aprotic solvents which can be used according to the invention are, for example, the following water-soluble compounds which are liquid at ordinary temperature or mixtures thereof: nitrogen-containing compounds such as N, N, N ¹ , N'-tetramethylurea, N-methylpyrrolidone and 1,5-dimethylpyrrolidone; Sulfur-containing compounds, such as sulfolane (tetramethylene sulfone) and sulfolene (2,3- or 2,5-dihydrothiophene-S-dioxide) and their derivatives, substituted in the α- and / or β-position, in particular by alkyl or hydroxyalkyl groups, and dimethyl sulfoxide; as well as phosphorus-containing compounds such as hexamethylphosphoric acid triamide and bis (dimethylamido) methane phosphate "

The aprotic solvents mentioned include dimethyl sulfoxide, N-methylpyrrolidone and tetramethylurea or mixtures of these solvents are preferably used.

Glycols or glycol ethers which can be used according to the invention are for example: ethylene glycol, 1,2-propylene glycol, diethylene glycol, Triethylene glycol and tetraethylene glycol, 2-methylpentanediol-3,4, Ethylene glycol monomethyl, ethyl or n-butyl ether, diethylene glycol monomethyl, ethyl or butyl ether, Diethylene glycol morioethyl ether acetate, triethylene glycol monobutyl ether, Dipropylene glycol, glycerine, glycerine 1,3-diethyl ether or thiodiglycol.

Of the glycols or glycol ethers mentioned, ethylene glycol, Diethylene glycol, triethylene glycol, tetraethylene glycol, Ae thy lenglykolmonome thy lather, Ae thy 1 eng Ij'kolmonoä thy lather, Diethylene glycol monomethyl ether, diethylene glycol inonoethyl ether and diethylene glycol mono-n-butyl ether or mixtures thereof Glycols and glycol ethers are preferably used.

Mixtures that produce the synergetic effect in particular these solvents are N-methylpyrrolidone / diethylene glycol monomethyl ether; Tetramethylurea / diethylene glycol monomethyl ether; N-methylpyrrolidone / tetraethylene glycol and tetramethylurea f / diethylene glycol monobutyl ether.

Dye solutions according to the invention can also be used soluble additives such as urea, pentaerythritol, antifoam agents, Dispersants, etc. are added.

This gives the novel dye solutions, preferably by dissolving the dyes according to definition, in a dried powder form in said solvent mixture, optionally at elevated temperature, for example at 20 to 100 ⁰ C. The solution temperature and time depend on the dye used and the solvent mixture. Both data can easily be determined by preliminary tests.

If necessary, after filtering off the insoluble components, such as inorganic salts, impurities, etc., a storage-stable, highly concentrated and homogeneous dye solution is obtained which shows no crystallization or decomposition ^{even after three months of storage at a temperature of up to 50 ° C.}

The presence of solutions increases the risk of flocculation and sedimentation that is often present with dispersions avoided.

In continuous dyeing, the use of highly concentrated dye solutions facilitates the preparation of padding liquors extraordinary. This is particularly advantageous when, for example, floor coverings made of polyamide fiber material, such as Tufted carpets or needle felt carpets that are continuously dyed in large quantities and several per batch Cubic meters of block liquor are required.

The dye solutions according to the invention are without precipitation of the dye can be mixed with water in any ratio and can be easily dosed volumetrically, regardless of

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whether you dilute them with water or pour them into water. The introduction of the dye solutions according to the invention into the liquor can even at room temperature without the risk of clumping take place. In the case of dye preparations in powder form, on the other hand, it is often necessary Before adding the dye to the dyebath, a stock solution must be prepared in water at an elevated temperature so that it can be used completely dissolve or distribute the dyes in the dyebath.

The dye solutions according to the invention can also be used automatically metering, e.g. in metering pumps and are therefore valuable for automatic dyeing.

They are also particularly suitable for the production of ■ dyeing solutions for dyeing or printing, in particular natural ones or synthetic nitrogen-containing organic fibers, especially from polyamide carpets, are also available for others Can be used for purposes such as the production of inks or printing inks for display instruments, stamp pads, typewriter ribbons etc.

In the following examples, which illustrate the invention but do not limit it, the mean Unless otherwise stated, parts, parts by weight and temperatures are given in degrees Celsius.

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example 1

41 parts of the dry dye of the formula

\ 2

are at room temperature in a mixture of 25 parts of tetramethylurea, 18 parts of dimethyl sulfoxide and 16 parts of diethylene glycol monomethyl ether entered the mixture stirred for one hour at room temperature and then filtered off from the remaining residue. From the solution thus obtained the dye does not crystallize out even after a storage time of 3 months and at temperatures of -20 °, 25 ° and 50 °.

If the dye solution is poured into water, it takes place instantly a homogeneous distribution.

The good storage stability \\ drd only achieved when im mentioned solvent mixture the proportion of tetramethylurea at least 25% and that of Dirnethyjsulfoxyd smaller than 20%.

Example 2

46 parts of the dry dye powder of the formula

Cl

= N-CH-C-CH

I It

KN = .C N

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are composed in a solvent mixture at room temperature from 23.5 parts of water, 23.5 parts of ethylene glycol monoethyl ether and 7 parts of dimethyl sulfoxide, registered, the mixture stirred for one hour, the dye going into solution and the solution then filtered. Remains in the filtration practically no residue on the filter. The solution obtained is thin, stable in storage, with water in any proportion mixable and is characterized by particularly good stability.

Example 3

. A very storage-stable solution is obtained by introducing 31 parts of the dry dye of the at room temperature formula

in a mixture of 20 parts of N-methylpyrrolidone and 49 parts of diethylene glycol monomethyl ether. After completing the registration of the dye, the mixture is stirred for 2 hours at room temperature and the undissolved salt is removed by filtration freed, with practically no residue remaining on the filter.

It is possible to prepare a highly concentrated solution with diethylene glycol monomethyl ether alone, but that is not shelf-stable. An addition of 20% N-methylpyrrolidone is necessary to ensure stability and instant dilution to ensure with water.

Example 4

A very stable solution is obtained by entering 34 parts of the dye of the formula

in a mixture of 32 parts of dimethyl sulfoxide and 34 parts Ethylene glycol monomethyl ether.

If the rest of the procedure is as described in Example 1, so you get a highly concentrated. Storage stable for months Dye Ib * solution.

The stability of the solution is only achieved if the dimethyl sulfoxide content is above 30%. Besides, it is impossible to produce such a highly concentrated dye solution in one of the solvents mentioned alone.

Example 5

A stable solution is obtained if, as in Example 1 procedure described, but 44 parts of the dye of the formula

N - N

and a mixture of 16 parts of dimethyl sulfoxide and 41 parts of ethylene glycol monomethyl ether is used.

Here, too, the addition of at least 15% dimethyl sulfoxide is necessary in order to obtain a stable solution.

Example 6

28 parts of the dry dye of the formula

, ^H 3 ^C \ / -SO ₂ O- ^ J) -N =

, o-fV

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are at room temperature in a solvent mixture consisting of 50 parts of N-methylpyrrolidone and 22 parts of diethylene glycol monomethyl ether, entered, the mixture stirred for one hour, the dye goes into solution, and the resulting solution is filtered. Virtually no residue remains on the filter during filtration. The solution obtained is thin, shelf-stable and miscible with water in any proportion.

It is not possible to produce such a highly concentrated dye solution in just one of the solvents mentioned.

Example 7

29 parts of the dry dye of the formula

CH.

are at room temperature in a mixture of 25 parts N-methylpyrrolidone and 46 parts of diethylene glycol monomethyla'ther entered, the mixture for one hour at room temperature stirred and then filtered off from the remaining residue. From the solution thus obtained crystallizes even after one Storage time of 6 months and at temperatures of -20 °, 25 ° and 50 ° the dye does not expire.

If this dye solution is poured into water, it takes place instantly a homogeneous distribution.

A dye solution with similarly good properties is obtained, if in the above example the N-methylpyrrolidone is replaced by appropriate amounts of tetramethylurea and im the rest of the procedure is the same as described in the example. If, instead of the aforementioned mixture of solvents, the

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If the same alone, one does not get such a high solubility of the dye as well as no stability improvement Dye solution.

Example 8

A very storage-stable solution is obtained by introducing 24.5 parts of the dry dye at room temperature the formula

/ CH

0 HN - CH ^ό

in a mixture of 30 parts of N-methylpyrrolidone and 45.5 parts of tetraethylene glycol. After the dye has been added wird.das mixture stirred for one hour at 60 to 70 ° and freed from the undissolved salt by filtration, wherein practically no residue remains on the filter.

Although it is possible to prepare a highly concentrated solution with tetraethylene glycol alone, it is not storage-stable is. An addition of 30% N-methylpyrrolidone is necessary to ensure stability and instant dilutability with water to ensure 1 egg. st en.

Example 9

23 parts of the dry dye powder of the formula

0 InIH ₉

II. SO ₃ Il

0 HN- /

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are at 50 to 60 ° in a solvent mixture consisting of 25 parts of N-methylpyrrolidone and 52 parts of tetraethylene glycol, entered, the mixture stirred for one hour, the dye goes into solution, and then the solution filtered. Virtually no residue remains on the filter during filtration. The solution obtained is stable in storage and with Water miscible in any ratio.

Example 10

A very stable solution is obtained by adding 29 parts of the dye powder of the formula

CIL
\

0 HN {'? -

CH

CH,

QI ₂ NHOC

in a mixture of 10 parts of tetramethylurea and 61 parts of diethylene glycol monobutyl ether.

If the procedure is otherwise as described in Example 7, a highly concentrated product is obtained which is stable in storage for months Dye solution.

The solution obtained is thin, stable in storage and miscible with water in any proportion.

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Claims (10)

Claims 1. Stable, highly concentrated dye solutions which can be mixed with water in any ratio, characterized in that they at least one sulfonic acid group-containing azo or nitro, dye or an anthraquinone dye, dissolved in one with Water in any proportion miscible solvent mixture, consisting of an aprotic solvent or a Mixture of the same, a glycol or glycol ether and optionally water contain. 2. Dye solutions according to claim 1, characterized in that that they have at least one azo containing monosulfonic acid groups or contain nitro dye. 3. Dye solutions according to claim 1, characterized in that that the anthraquinone dye is a t-amino-4-arylaminoanthraquinone dye contain. 4. Dye solutions according to claim 1, characterized in that they ^{contain nitrogen-containing compounds, such as N, N, N 1} , N ¹ -tetramethylurea, N-methylpyrrolidone and 1,5-dimethylpyrrolidone, as aprotic solvent; Sulfur-containing compounds such as suIfolan (tetramethylene sulfone) and suIfölen (2,3- or 2,5-dihydrothiophene-S-dioxide) and their derivatives substituted in the α- and / or β-position, in particular by alkyl or hydroxyalkyl groups, and dimethyl sulfoxide; as well as phosphorus-containing compounds such as hexamethylphosphoric triamide and bis (dimethylamido) methane phosphate. 5. dye solutions according to claim 4, characterized in that that they use dimethyl sulfoxide, N-methylpyrrolidone, tetramethylurea or mixtures of these as aprotic solvents Contain solvents. 309Ö84 / UÖS 6. dye solutions according to claims 1 to 3, characterized characterized that they are ethylene glycol, diethylene glycol as glycols , Triethylene glycol or tetraethylene glycol, or as glycol ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol mono-n-butyl ether or mixtures these contain glycols or glycol ethers. 7. dye solutions according to claim 1, characterized in that that the solvent mixture consists of N-methylpyrrolidone / Diethylene glycol monomethyl ether or tetramethyl urea / diethylene glycol monomethyl ether, or N-methylpyrrolidone / tetraethylene glycol, or tetramethythurea / diethylene glycol monobutyl ether. 8. dye solutions according to claims 1 to 7, characterized characterized in that they contain 10 to 60, in particular 30 to 50, percent by weight of at least one sulfonic acid group Azo or nitro dye or an anthraquinone dye, 5 to 60, in particular 15 to 50 percent by weight of an aprotic solvent or its mixture, 15 to 50 Contain percent by weight of a glycol or glycol ether and 0 to 50 percent by weight of water. 9. Process for the preparation of stable, highly concentrated dye solutions according to claim 1, characterized in that that one said dyes in a solvent mixture consisting of an aprotic solvent, a glycol or Glycol ether and possibly water, dissolves. 10. Use of the dye solutions according to claims 1 to 8 for the preparation of dye baths for das_Färben or printing of textile material, in particular made of nitrogen-containing organic fibers, especially polyamide carpets. 30988A / U05