CH473874A - Process for the production of metal complex compounds of reactive dyes - Google Patents

Description

  

  Process for the production of metal complex compounds of reactive dyes The invention relates to a process for the production of metal complex compounds of reactive dyes, which in the metal-free state of the formula
EMI0001.0006
    correspond, where A1 is an optionally further substituted radical from the benzene, naphthalene or heterocyclic series,

   A- is an optionally further substituted radical of the hydroxynaphthalene or pyrazolone series coupled ortho to a phenolic or enolic hydroxyl group, R is a radical that enables chemical bonding with the substrate, n and m are one of the numbers 1, 2 or 3 mean.



  The process is characterized in that the copper complex compounds of reactive dyes which correspond to formula (I) in the metal-free state are decuppered and converted into a metal complex compound different from the copper complex compound.



  The copper complex compounds of reactive dyes, which correspond to formula (1) in the metal-free state, can be produced by the process of Swiss patent specification No. 415 904 or Swiss patent specification No. 460 209.



  The copper removal can be carried out, for example, by treating the copper complex compound in a mineral acid medium at temperatures of 20 to 100 ° C., whereby it must be ensured that the reactive residue present remains unchanged. After the O, O'-dihydroxyazo dye has been separated out in an acidic medium, the copper salts present in dissolved form are separated off by filtration.



  The conversion of the O, O'-dihydroxy-disazo dyes into their nickel complex compounds takes place advantageously in an aqueous solution. An amount of a metal donor containing one atom of nickel is allowed to act on one molecule of disazo dye. It is preferable to work in slightly acidic (e.g.

    acetic acid) to slightly alkaline medium at temperatures of 20-70 C and with the addition of an aqueous solution of an alkali metal hydroxide, an alkali metal carbonate or an alkali metal salt of a low molecular weight aliphatic monocarboxylic acid.



  As nickel compounds, for. B. nickel formate, nickel acetate and nickel sulfate.



  The nickel complex compounds obtained, containing at least one reactive group, can be separated from their aqueous solutions by adding salt, then filtered off, optionally washed and then dried.



  The nickel-containing azo dyes obtained are uniform nickel complex compounds in which essentially one atom of nickel is bonded to one molecule of disazo compound.



  The conversion of the O, O'-dihydroxy disazo dyes into their chromium or cobalt complex compounds is advantageous in aqueous solution or in an organic medium, for example in formamide, or in the concentrated aqueous solution of an alkali metal salt. a low molecular weight aliphatic monocarboxylic acid.

   It is advantageous to allow an amount of a metal-releasing agent containing less than two but at least one atom of metal to act on two molecules of disazo dye.



  Suitable compounds of chromium are, for. B. Chromiflüorid, Chromisulfat, Chromiformiat, Chromi- acetate, potassium chromisulfate or ammoniumchromisulfat. The chromates, e.g. B. sodium or potassium chromate or -biehromat, are ideally suited for the metallization of disazo dyes.



  It is advantageous to work here in a strongly alkaline medium, it being possible to add reducing substances if necessary. As cobalt compounds z. B. cobalt formate, cobalt acetate and cobalt sulfate. If the metallization is carried out in the concentrated aqueous solution of an alkali metal salt of a low molecular weight aliphatic monocarboxylic acid,

   so water-insoluble metal compounds can also be used, for example cobalt hydroxide or cobalt carbonate.



  The metallization is particularly advantageously carried out in an aqueous, alkaline medium, the metal compounds being added in the presence of compounds which keep the metals dissolved in a complex bond in a caustic alkaline medium, e.g. B. tartaric acid, citric acid and lactic acid.



  The obtained azo dyes containing at least one reactive group and containing chromium or cobalt are uniform metal complex compounds in which essentially one atom of metal is bonded to two molecules of the disazo compound. These metal complex compounds are so-called 1: 2 complexes, in which one mole of disazo compound is linked to about 0.3-0.7 atoms of metal.



  The metal complex compounds obtained can, if appropriate after pouring the organic metallization solutions into brine, separated out from an aqueous medium by adding salt, then filtered off, if appropriate washed and then dried.



  The new nickel-containing reactive dyes which contain three or more water-soluble groups, e.g. B. Carboxylic acid or preferably sulfonic acid groups, and the chromium or cobalt-containing reactive dyes, which carry two or more water-solubilizing groups per molecule of the metal-free dye, have good solubility in water,

   good stability in the printing pastes and padding solutions, good compatibility with salts and hard water, good reactivity with vegetable fibers, animal and synthetic polyamide fibers;

      they are insensitive to heavy metal ions such as copper, iron and chromium ions and reserve acetate, triacetate, polyester, polyacrylonitrile, polyvinyl chloride, polyvinyl acetate and polyalkylene fibers. Thanks to their only moderate substantivity, the unfixed dye part is from the.

       Prints or dyeings on cellulose fibers can be easily washed out.



  The nickel-containing reactive dyes, which carry 2 to 3 water-solubilizing groups, are particularly suitable for the so-called exhaust process for cellulose fibers, while the chromium or cobalt-containing reactive dyes, which carry 1 to 2 water-solubilizing groups per molecule of the metal-free dye, are mainly acidic Dyeing wool,

   Silk and synthetic polyamide fibers are used.



  The new metalliferous. Reactive dyes are suitable for dyeing, padding and printing fibers of animal origin, e.g. B. wool, silk, synthetic polyamide fibers, e.g. B. nylon, leather, cellulose fibers, z. B. cotton, linen, and regenerated cellulose fibers, e.g. B. viscose rayon, copper rayon, rayon, and mixtures and / or structures made of these fibers.

   The optimal application conditions vary depending on the type of fiber and the dyes used. Animal fibers and synthetic polyamide fibers can preferably be dyed and printed or fixed in an acidic, neutral or weakly alkaline medium, e.g. B. in the presence of acetic acid, formic acid, sulfuric acid, ammonium sulfate, sodium metaphosphate, etc. You can also in the presence of leveling agents such.

   B. polyoxäthylier- th fatty amines, or mixtures of the same with alkyl polyglycol ethers, color acetic acid to neutral and at the end of the coloration the bath by adding small amounts of an alkaline agent such. B. ammonia, sodium bicarbonate or carbonate, etc., or compounds which react alkaline in the heat ren, z. B. hexamethylenetetramine, urea, to a neutral or slightly alkaline reaction from blunt.

   This is followed by thorough rinsing and, if necessary, acidified with a little acetic acid.



  The dyeings and prints obtained have good fastness properties to light, washing, perspiration, fulling, water, sea water, potting, acid, alkali, rubbing, flue gas, chlorine, bleach (peroxide) and dry cleaning fastness (organic solvents).



  The dyeing, padding and printing or fixing of the dyes on cellulose fibers is advantageously carried out in an alkaline medium, e.g. B. in the presence of sodium bicarbonate, sodium carbonate, caustic soda, potassium hydroxide, sodium metasilicate, sodium borate, trisodium phosphate, ammonia, etc.

   To avoid reduction phenomena, mild oxidizing agents such as sodium 1-nitrobenzene-3-sulfonic acid are often advantageously added when dyeing, padding or printing the fibers. In the case of cellulose fibers, too, the dyes are usually fixed in the heat. Some of the dyes can, depending on the reactivity of the re active groups, even at low temperatures, e.g. B. 20 to 40 C, colored or fixed.



  The addition of certain quaternizable amines, such as trimethylamine or triethylenediamine, or asymmetric dimethylhydrazine, preferably in stoichiometric amounts, accelerates the fixing of the dye on the fiber, so that the fixing temperature can be lowered and / or the fixing time can be shortened.

   The dyeings and prints on cellulose fibers are particularly notable for their excellent wet fastness properties. These are based on the formation of a stable chemical bond between the dye molecule and the cellulose molecule. Often not all of the dye takes part in the chemical reaction with the fiber. The proportion of the unreacted dye is removed from the fiber in these cases by suitable Ope rations, such as rinsing and / or soaps, optionally using higher temperatures, synthetic detergents such.

   B. alkylarylsulfonates, sodium lauryl sulfate, sodium lauryl polyglycol ether sulfate and mono- and dialkyl phenyl polyglycol ethers, find use. Blue, green, olive, gray and black dyeings and prints are obtained, which are good light, washing, water, sea water, sweat, rubbing, alkali, acid, vulcanizing, chlorine, bleaching (Peroxide), flue gas and dry cleaning properties (organic solvents).

    They are also resistant to anti-crease finishes and acidic and alkaline hydrolytic influences.



  In the examples below, the parts are parts by weight, the percentages are percentages by weight, and the temperatures are given in degrees Celsius. <I> Example 1 </I> 10.35 parts of disazo dye of the formula
EMI0003.0002
    are dissolved in the form of the sodium salt at 40 in 100 parts of water and treated with 30 parts of 30% hydrochloric acid. The mixture is stirred for 2 hours at 30-40, the precipitated demetallized dye is filtered off and it is washed with 100 parts of 10% sodium chloride solution. The residue is taken up in 100 parts of water.

   The dye is dissolved at 60 ° with the addition of the amount of sodium carbonate necessary for neutralization and then mixed with enough concentrated, aqueous nickel sulfate solution until excess nickel ions can be detected in the solution. When the metallization is complete, the dye is separated off with the aid of sodium chloride, filtered off and dried. After grinding it is a dark powder that dissolves in water with a dark blue color and dyes cellulose fibers in dark blue tones.

      <I> Example 2 </I> 10.85 parts of disazo dye of the formula
EMI0003.0017
    are demetallized in the manner described in Example 1 and stirred as a moist paste in 50 parts of water with the addition of sodium carbonate in a neutral reaction. 3.5 parts of crystallized sodium acetate and 1.6 parts of crystallized cobalt sulfate are added and the mixture is stirred at 90 until the metallization has ended.

   The dye is precipitated by adding sodium chloride and then filtered off and dried. He dyes cotton in dark blue tones.



  <I> Printing instructions: </I> Mercerized cotton sateen is printed with a pressure vaste of the following composition:
EMI0003.0031
  
    80 <SEP> parts <SEP> of the <SEP> according to <SEP> above <SEP> information <SEP> received <SEP> dye,
<tb> 100 <SEP> parts <SEP> urea,
<tb> 330 <SEP> parts <SEP> water,
<tb> 450 <SEP> parts <SEP> of a <SEP> 3 <SEP>% <SEP> sodium alginate thickener,
<tb> 15 <SEP> parts <SEP> 1-nitrobenzene-3-sulfonic acid <SEP> sodium,
<tb> <U> 25 <SEP> parts </U> <SEP> sodium carbonate
<tb> 1000 <SEP> parts The dried textile material is steamed for 10-15 minutes at 102-104 and then rinsed cold and warm.

   After the boiling soap, followed by renewed rinsing and drying, a dark blue print with good wet and lightfastness is obtained.



  <I> Example 3 </I> 9.2 parts of decoppered disazo dye from Example 2 are stirred in 40 parts of water and the reaction is neutralized by adding sodium carbonate. 3 parts of crystallized chromium potassium sulfate are added and the mixture is held for 24 hours. at 90. At the same time, a pH value of 5-6 is maintained by gradually adding sodium carbonate solution.

   After the metallization has ended, the dissolved dye is deposited using sodium chloride and then filtered off, dried and ground. A dark powder is obtained which dissolves in water with a blue-gray color.

 

Claims (1)

PATENT CLAIM Process for the production of metal complex compounds of reactive dyes, which in the metal-free state of the formula EMI0003.0046 correspond, in which A, an optionally further substituted radical of the benzene, naphthalene or heterocyclic series, A2 is an ortho-coupled to a phenolic or enolic hydroxyl group, optionally further substituted radical of the hydroxynaphthalene or pyrazolone series, R a radical which enables the chemical bond with the substrate, n and m mean one of the numbers 1, 2 or 3, characterized in that the copper complex compounds of reactive dyes which are in the metal correspond to the free state of formula (1), decoppered and converted into a metal complex compound different from the copper complex compound.