CH450585A - Process for the preparation of reactive metal-containing azo dyes - Google Patents

Description

  

      Additional patent to main patent no. 397 909 Process for the production of reactive metal-containing azo dyes The present invention relates to a process for the production of reactive metal-containing azo dyes, which at least one on a benzene,

          Naphthalene- or pyrazolone-bonded group of the formula -X-arylene + CH # -NH-OCR-Hal) n (I), in which X is the direct bond, -0-, -NH- or -SO, - NH-, pure divalent saturated or unsaturated aliphatic,

          optionally halogen-substituted radicals with 1 to 3 carbon atoms, n one of the numbers 1 or 2, Hal chlorine or bromine and arylene an arylene radical of the benzene or naphtha series,

          which can contain lower alkyl or alkoxy groups and also halogen atoms.



  The process according to the invention is characterized in that azo dyes containing at least one group of the formula -X-arylene- (H) bonded to a benzene, naphthalene or pyrazolone nucleus are used. (1I) wear, in any order with a compound of the formula Y-CH, NH-OC-R-Hal (I11)

         where Y is a halogen atom, a hydroxy group or a group O-CH, NH-OC-R-Hal, and reacts with a metal donor.



       As residues -Arylen-H come z. B. contemplated: phenyl; 2-, 3- and 4-methylphenyl; 2-, 3- and 4-methoxy- or ethoxyphenyl; 2,4- and 2,5- and 2,6-dimethylphenyl; 2,4,6-trimethylphenyl; 2,4- and 2,5-dimethoxy- or diethoxyphenyl; 2-chloro-4- or -6-methylphenyl;

          2-methoxy-5-methylphenyl; 2 ethoxy-5-methylphenyl; 2-methoxy-4-methylphenyl; 2-methyl-4- or -5-methoxy- or ethoxyphenyl; 4-chloro-2,5-dimethoxyphenyl or diethoxyphenyl;

          4-chloro-2-methoxy-5-methylphenyl, naphthyl (1), naphthyl (2), 2- and 4-methoxynaphthyl- (1), 2-chloro-4,6-dimethyl phenyl.



  The compounds of the formula (III) are prepared from formaldehyde or formaldehyde, cleaving compounds and amides of lower aliphatic, saturated or unsaturated haloarboxylic acids and are the N-halogens:

  nmethyl and N-hydroxymethyl derivatives and the symmetrical ethers corresponding to the N-hydroxymethyl derivatives (if Y in formula (11I) stands for -O-CH.-NH-OC-R-Hal).



  The following compounds may be mentioned as formaldehyde-releasing compounds: Paraformaldehyde and the symmetrical dichloro and dibro # md # ime # ethyl ethers.



       As n_e @ dere aliphatic saturated or unsaturated halocarboxylic acids are z.

   B. to be mentioned: chloroacetic acid, bromoacetic acid, α-bromo- or α-chloropropionic acid, β-bromo- or β-chloropropionic acid, α-bromo- or β-bromobutyric acid, α-chloro- or β-chlorobutyric acid, α, f3-dibromopropionic acid , a, ss-dichloro-propionic acid, a-chloro- or a-bromoacrylic acid, etc.

    



  The metallizable azo dyes which carry at least one group of the formula (1I) bonded to a benzene, naphthalene or pyrazolone nucleus, can either be mixed first with a compound of the formula (III)

      and then reacted with a metal donor or vice versa first with a metal donor and then with a compound of formula (III). The reaction with a compound of the formula (11I) is carried out in concentrated sulfuric acid, preferably from 85-100 O / a,

      or carried out in concentrated phosphoric acid at temperatures between 0 and 30.degree. C., where the reaction time can vary widely depending on the reactants and can be up to 50 hours. The compounds resulting from the reaction can easily be carried out from the sulfuric or phosphoric acid solution

  Precipitation with water and optionally salting out can be isolated.



  The conversion of the metallizable azo dyes into iron, copper or nickel complex dyes is advantageously carried out in aqueous solution, in weakly acidic (e.g.

   B. acetic acid) to weakly alkaline Shem medium at temperatures of 20-70 C and the presence of an aqueous solution of an alkali metal salt of a low molecular weight aliphatic monocarboxylic acid. For one molecule of dye, the amount of an iron,

            copper or nickel releasing agent used.



  The conversion of the metalusable azo dyes into their chromium and cobalt complex compounds is advantageously carried out in an aqueous solution or in an organic medium, for example in formamide,

          or in the concentrated aqueous solution of an alkali metal salt of a low molecular weight aliphatic monocarboxylic acid. It is advantageous to leave one less than two molecules per two molecules of monoazo dye

          but at least one atom of metal-containing amount of a metal donating agent act.



  Suitable compounds of chromium are e.g. B. chromium fluoride, chromium sulfate, chromiformate, chromium acetate, potassium chromium sulfate or ammonium chromium sulfate. The chromium rate, e.g. B.

   Sodium or potassium chromate or bend chromate are particularly suitable for the mefiallization of monoazo dyes. It is advantageous to work here in a strongly alkaline medium, and reducing substances can be added if necessary.



  As cobalt compounds z. B. cobalt formate, coba: itoacetate and cobaltosulfate. If the metallization in the concentrated aqueous solution of one;

  If the alkali metal salt of a low molecular weight aliphatic monocarboxylic acid is made, water-insoluble metal compounds can also be used, for example cobalt hydroxide or cobalt carbonate.



       It is particularly advantageous to carry out the metallization in a wäs serigem or alkaline medium, the metal compounds being supplied in the presence of compounds which keep the metals dissolved in an alkaline medium in complex bonds, such as. B.

         Tartaric acid, citric acid and lactic acid.



  The chromium- and cobalt-containing azo dyes obtained are uniform metal complex compounds; in which essentially one atom of metal is bound to two molecules of the monoazo compound. The metal complex compounds are so-called 1:

  2 complexes in which one molecule of monoazo compound is linked to about 0.3-0.7 atoms of metal.



  The metallization conditions (temperature, pH value) should be selected so that the reactive group is not damaged. The metal complex compounds obtained are, if necessary, after pouring the organic metallization solutions into brine, separated from an aqueous medium by adding salt,

            then filtered off, optionally washed and then dried.



       The dyes obtained are used for dyeing, padding or printing wool, saide, synthetic polyamide fibers and leather as well as fibers made from natural and regenerated cellulose such as cotton, linen, hemp, viscose, rayon rayon,

   orange and red tones. The dyeings and prints on wool and synthetic polyamide fibers, which are optionally subjected to a heat treatment in the presence of acid-binding agents, have excellent light and wet fastness properties (water, washing, perspiration,

          Walk, rub and dry cleaning fastness). The dyeings or prints on cellulose fibers that are subjected to an alkaline treatment and, if necessary, a heat treatment during dyeing or after padding or printing are very fast to light, wash, water, sweat, solo, boil and rub.



  In the following examples, the parts are parts by weight, the percentages are percentages by weight and the temperatures are degrees Celsius. <I> Example 1 </I> 43.3 parts of the red dye are dissolved, which is obtained by acidic coupling of diazotized 2-amino-1-hydroxy-benzene-4-sulfonic acid with 2- (4'-methyl)

  -phenylamino- naphthalene is available, with stirring at 15-20 in 300 parts of 96% sulfuric acid. Subsequently, 25 parts of chloroacetic acid N-hydroxymethylamide are introduced in portions at <B> 0-5 '</B>,

       lets the temperature rise to 25 and stirs the mixture for 10 hours at this temperature.

   The mixture is then poured onto 1200 parts of ice, stirred until the temperature has risen to 10 and the dyestuff which has precipitated out is filtered off.

   The color paste, washed well with water, is mixed in 600 parts of water and, after addition of 15 parts of cobalt sulfate, heated to 40.

       The suspension is kept at pH 5-6 by carefully adding dropwise an aqueous solution of sodium carbonate until the red starting dye has converted into the blue metal complex compound. They are filtered

   wash them with 5% saline and dry them in vacuo at 30-4.0. A dye is obtained which gives dull blue dyeings on wool and nylon,

      which are lightfast and have better wet fastness properties than the cobalt-coated dye that has not been treated with chloroacetic acid @ -N = hydroxymethylamide.



  <I> Dyeing instructions </I> 2 parts of the above dye are dissolved in 4M0 parts of cold water and heated to 40%. It gives 2 parts of acetic acid and 3 parts of a Gemi cal of a polyoxyethylated fatty amine and an alkyl polyglycol ether and then goes with 100 parts of a woolen fabric.

   It is brought to the boil within 15-20 minutes and kept at boiling temperature for 45-60 minutes. About 5 parts of 50% ammonia or 3 parts of hexamethylene terorane are then added at 85-90 and the mixture is treated at 90 for 20 minutes.

         Then rinse thoroughly by adding a little acetic acid to the rinsing water in one passage, and then drying. A wash-, sweat-, and squeeze-fast as well as good lightfast, level blue dyeing is obtained.

      <I> Example 2 </I> 46.2 parts of the blue dye are dissolved, which is obtained by acidic coupling of 2-amino-1-hydroxybenzene-4-sulfonic acid with 2- (4'-methyl) -phenyl -aminonaphthalene and subsequent cobalt treatment is available,

       with stirring at 10-20 in 300 parts of 96% sulfuric acid. Subsequently, 25 parts of chloroacetic acid-N-hydroxymethylamide are introduced in portions at 0-5 and the mixture is stirred for several hours at this temperature,

      until the implementation is complete. The mixture is then poured onto 1200 parts of ice, stirred until the temperature has reached 10 and the dyestuff which has precipitated out is filtered off.

   The color paste is again stirred in 1500 parts of water and filtered. Then they are carefully dried at 4.0 in a vacuum.

   A dye is obtained which dyes wool and nylon in dull blue tones, which are very lightfast and have better wet fastness properties than the cobalt complex that has not been treated with chloroacetic acid @ N-hydroxymethylamide.



       The following table contains further reactive metal-containing azo dyes which can be obtained according to the information in Examples 1 and 2 and:

          are identified by the diazo and coupling components, the metal used, the reactive components and the shade of the wool dye in columns (I) to (V).

    
EMI0003.0060
  
    Example <SEP> No. <SEP> Diazo component <SEP> Coupling component <SEP> Metal <SEP> Reactive component <SEP> Nuance <SEP> der
<tb> (I) <SEP> (II) <SEP> (III) <SEP> (IV) <SEP> wool dye
<tb> (V)
<tb> 3 <SEP> 2-Amina-1 <SEP> hydroxy <SEP> 2 - @ (2 ', 4', 6'-trimethyl) - <SEP> Co <SEP> aJ-chloroacrylic acid- <SEP> blue
<tb> benzene-4-mlfonsäure- <SEP> phenyl <SEP> aminonaphthalene <SEP> N <SEP> chloromethylamide
<tb> (2'-carboxy) phenylamide
<tb> 4 <SEP> 2-amino-l-hydroxy-4- <SEP> 2- (2 ', 4'-dimethyl) - <SEP> Co <SEP> di- (ss-chloropropionyl- <SEP> blue
<tb> chlorobenzene-6-sulfone- <SEP> phonylammonaphthane <SEP> aminomethyl) -ether
<tb> acid
<tb> 5 <SEP> 2 <SEP> Ämino-l-hydroxy-4- <SEP> 1- (4'-methyl) <SEP> phenyl- <SEP> Cr <SEP> 2,

  3 <SEP> dichloropropionic acid <SEP> brown
<tb> nitrobenzene-6-sulfone- <SEP> 3-methyl-5-pyrazolone <SEP> N-chloromethyiamide
<tb> acid
<tb> 6 <SEP> 2-amino-1-methoxy- <SEP> 1-hydroxy-7- (2 ', 4', 6'- <SEP> Ctl. <SEP> bromoacetic acid-N-hydr- <SEP > <B> hoij </B>
<tb> benzene.4-sulfonic acid amide <SEP> tr'unethyzl) -phenylamino- <SEP> oxymethylamide
<tb> (acidic <SEP> coupling) <SEP> naphthalmic-3-sulfonic acid
<tb> 7 <SEP> 2-aminobenzoll-earbon <SEP> id. <SEP> CU <SEP> chloroacetic acid- <SEP> red
<tb> acid <SEP> N-chlarmethylamide
<tb> (alkaline <SEP> coupling)
<tb> 8 <SEP> 2 <SEP> Amino-l-hydroxy-4- <SEP> id. <SEP> Co <SEP> chloroacetic acid- <SEP> blue
<tb> chlor-6-nntrobenzoi <SEP> N-hydroxymethylamide
<tb> (alkaline <SEP> coupling)
<tb> 9 <SEP> id. <SEP> id. <SEP> he <SEP> id. <SEP> blue
<tb> 10 <SEP> id. <SEP> id. <SEP> Ni <SEP> id. <SEP> purple-brown
<tb> 11 <SEP> id. <SEP> id.

   <SEP> Fe <SEP> id. <SEP> brown
<tb> 12 <SEP> 2-amino-1-hydroxy-4- <SEP> 1-acetoacetylamino- <SEP> Co <SEP> id. <SEP> yellow
<tb> nitrobenzene6-sulfonic acid <SEP> (4-phenoxy) -benzene
<tb> 13 <SEP> 2. Amino-4-chloro-5-nitro- <SEP> 2, aminonaphthalene- <SEP> Co <SEP> chloroacetic acid- <SEP> blue-green
<tb> 1-hydroxybenzene <SEP> 6-asulfonic acid- (2 ', 4', 6'- <SEP> N <SEP> hydroxylethylamide
<tb> trimethyl) phenylamide
<tb> 14 <SEP> 2-Amino-3,4,6-trichloro- <SEP> 1-Hydroxy <SEP> 6- (4 '<SEP> meth- <SEP> Co <SEP> id. <SEP> violet
<tb> 1-hydroxybenzene <SEP> oxy) -phenyl <SEP> amino naphthalene, 3-sulfonic acid

 

Claims (1)

PATENT CLAIM A process for the preparation of reactive metal-containing azo dyes which contain at least one group of the formula -X-arylene- (CH2 NH-CO-R-Hal) "(I), where X is the direct bond, bonded to a benzene, naphthalene or pyrazolone nucleus , -0-, NH or -S02 NH-, R is a divalent, saturated or unsaturated .aliphatic, optionally halogen-substituted radical with 1 to 3 carbon atoms, n one of the numbers 1 or 2, Hall chlorine or bromine and arylene mean an arylene radical of the benzene or naphthalene series, which can contain lower alkyl or alkoxy groups and also halogen atoms, characterized in that azo dyes, which carry at least one group of the formula -X-arylene- (H) a (II) bonded to a benzene, naphthalene or pyrazolone nucleus., in any order with a compound of the formula Y-CHi- NH-OC-R-Hal ( III) wherein Y is a halogen atom, a hydroxy group or a group O-CH, NH-OC-R-Hal, and reacts with a metal donor. <I> Note from the </I> Federal <I> Office for Intellectual Property: </I> If parts of the description are inconsistent with the definition of the invention given in the claim, it should be remembered that according to Art. 51 of the Patent Act, the claim is decisive for the material scope of the patent.