CH475309A - Process for the production of azo dyes that are sparingly soluble in water - Google Patents

Description

  

      Method of production in e water difficult. more soluble. Azo dyes The subject of the invention is. , a process for the production of new, sparingly water-soluble azo dyes of the formula
EMI0001.0012
    wherein R1, hydrogen; chlorine, or bromine ,.



       Rz, a given company suhstitut. low molecular alkyl radical and R3. "and R4, Köllenwasserstoffreste mean ..



  The most hydrocarbon. R3 and R.4 are preferably identical or different alkyl radicals with 1 to 4 carbon atoms. They can be saturated or unsaturated and branched or unbranched and together with <B> -N <- </B> form a ring which may contain further heteroatoms. This process is characterized in that

   that one is an amine, of the formula
EMI0001.0040
         diazotized and with a compound of the formula
EMI0001.0043
    clutch. In general, the coupling is carried out in an acidic, optionally buffered, medium with cooling, for example at temperatures between −0 and −51 ° C. It is particularly advantageous to use the new dyes obtained in this way. in front of her.

   Use, in a known manner, to be converted into ear material preparations. -To be. it shreds until the average particle size is about 0.01 to 1-0 microns. and in particular about 0.1: to 5 microns. The crushing can take place in the presence of dispersants or fillers.

   For example, will. the dried dye with a dispersant, optionally in the presence of fillers, ground or kneaded in paste form with a dispersant and then dried in a vacuum or by atomization.

   With the. Preparations obtained in this way can be; after adding more. less water, dye ,. pad or print - when dyeing. in: long fleet turns. man in. generally mean up to about 20 g: dye in the liter, when pumping: up to. about 150-g> im;

   Liter, preferably: 0.1 to 100 g per liter, and when printing up to. to: about 15O.g@im; KilogrammiDrurckpaste .. The liquor ratio can be selected within wide limits, e.g. between. about -1,:. 3: and.1-: 200, preferably between 1: 3 and. 1 @: 80 ..



  The dyes are drawn from an aqueous suspension onto moldings made from fully synthetic or semi-synthetic high-molecular substances. They are particularly suitable for dyeing, padding or printing fibers, threads or fleeces, woven or knitted fabrics made from linear, aromatic polyesters, as well as from cellulose 21/2 acetate or cellulose triacetate. Synthetic polyamides, polyolefins, acrylonitrile polymerization products and polyvinyl compounds can also be colored with them.

       Special & valuable colorations are on. linear, - aromatic. Polyesters = preserved. These are generally polycondensation products from terephthalic acid and @ .Glycals, sometimes ethylene glycol, and. z-.B.-. under: the. protected, designation KTery- leny @:

        .Diols, or. D.acron =: in the trade. It is colored according to methods known per se. Polyester fibers can be dyed in the presence of carriers at temperatures between about 80 and 125 C or in the absence of carriers under pressure at about 100 to 140 C by the exhaust process. They can also be padded with the aqueous dispersions of the new dyes, padded or printed and the impregnation obtained fixed at about 140 to 230 C, for. B. with the help of steam or air.

   In the particularly favorable temperature range between 180 and 220 C, the dyes quickly diffuse into the polyester fiber and do not sublime again, even if these high temperatures are left to act for a longer period of time. This avoids annoying soiling of the dyeing equipment. Cellulose-21 / e-acetate is preferably dyed between about 65 and 80 C and cellulose triacetate at temperatures up to about 115 C. The most favorable pH range is between 2 and 9 and especially between 4 and B.



  Usually the usual dispersants are added, which are preferably anionic or nonionic and can also be used as a mixture with one another. About 0.5 g of dispensing agent per liter of dye preparation are often sufficient, but larger amounts, e.g. B. up to about 3 g per liter can be used. Amounts exceeding 5 g usually result in no further benefit.

   Known anionic dispersants which are suitable for the process are, for example, condensation products of naphthalenesulfonic acids and formaldehyde, especially dinaphthylmethane disulfonates, esters of sulfonated succinic acid, Turkish red oil and alkali salts of sulfuric acid esters of fatty alcohols, e.g.

   B. sodium lauryl sulfate or sodium cetyl sulfate, sulfite cellulose liquor or their alkali salts, soaps or alkali sulfates of monoglycerides of fatty acids.

   Examples of known and particularly suitable nonionic dispersants are adducts of about 3-40 mol of ethylene oxide with alkylphenols, fatty alcohols or fatty amines and their neutral sulfuric acid esters.



  When padding and printing you will use the usual thickeners, such. B. modified or unmodified natural products, such as alginates, British gum, gum arabic, crystal gum, locust bean gum, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products such as polyacrylamides or polyvinyl alcohols.



  The colorations obtained are extremely genuine, e.g. B. excellent thermofixing, subliming, pleating, smoke gas, dyeing, dry cleaning, chlorine and wet fast, z.

   B. water, wash and perspiration resistant. Caustic
EMI0002.0061
  
    <I> table </I>
<tb> Example <SEP> No. <SEP> Ri <SEP> R2 <SEP> R3 <SEP> R4 <SEP> Y <SEP> Nuance <SEP> on <SEP> polyester
<tb> 3 <SEP> Cl <SEP> -CH3 <SEP> -CH3 <SEP> -CH3 <SEP> -C00- <SEP> blue
<tb> 4 <SEP> Cl <SEP> -C2H5 <SEP> -CH3 <SEP> -CH3 <SEP> -C00-- <SEP> blue
<tb> 5 <SEP> Cl <SEP> -C2H4Br <SEP> -C2H5 <SEP> -C2H5 <SEP> -C00- <SEP> blue
<tb> 6 <SEP> H <SEP> -C2H5 <SEP> -C3H7 <SEP> -C3H7 <SEP> -C00- <SEP> violet
<tb> 7 <SEP> H <SEP> -C2H4C1 <SEP> -C2H5 <SEP> -C2H5 <SEP> -C00- <SEP> violet <I> Dyeing instructions </I> 7 parts of the dye obtained according to Example 1 are used with 4 parts dinaphthylmethandisulfonsaurem availability and reserves of wool and cotton are good.

   The lightfastness is excellent, even in light tones, so that the new dyes are also very suitable as mixing components for the production of pastel-colored fashion tones. The dyes are resistant to boiling and reduction at temperatures up to at least 220 C and especially at 80 to 140 C. This resistance is not affected unfavorably by either the liquor ratio or the presence of dye accelerators.



  In the following examples, parts are to be understood as parts by weight. The temperatures are given in degrees Celsius.



  <I> Example 1 </I> 6.9 parts of sodium nitrite are slowly added to 120 parts of concentrated sulfuric acid at 60-70 with vigorous stirring. The mixture is stirred for 10 minutes at 60, then cooled to 10 and 16.3 parts of 2-amino-5-nitrobenzonitrile are added at this temperature. The diazotization is complete after 3 hours.

   Man. the sulfuric acid diazonium salt solution is poured into a mixture of 23.6 parts of 3-diethylamino-1-carbethoxyamino-benzene, 80 parts of glacial acetic acid, 150 parts of ice and 10 parts of aminosulfonic acid. The coupling is completed at 0 in a buffered medium. The dye is filtered off with suction, washed free of acid, dried and recrystallized from acetone. It melts at 156. It dyes synthetic fibers in brilliant reddish purple shades with good fastness properties.



  <I> Example 2 </I> To 120 parts of concentrated sulfuric acid are slowly added at 60-70 with stirring. 6.9 parts of sodium nitrite are added .. The mixture is stirred for a further 10 minutes at 60, then cooled to 10 and 100 parts of glacial acetic acid and then 19.7 parts of 2-amino-3-chloro-5-nitrobenzonitrile are added at 10-20 and 100 parts of glacial acetic acid. The mixture is stirred for 2 hours, the diazonium salt solution is mixed with 10 parts of urea and after 10 minutes it is poured into a cold mixture of 23.6 parts of 3-diethylamino-1-carbethoxyaminobenzene, 20 parts of concentrated hydrochloric acid and 100 parts of ice. The coupling reaction is completed at 0 in an acid medium.

   The dye obtained is filtered off, washed free of acid and dried. It can be recrystallized from monochlorobenzene. The pure dye melts at 210. It dyes synthetic fibers in purple tones with good fastness properties. The absorption maximum is 578 mg (solvent: dimethylformamide).



  The dyes of the formula (I) mentioned in the table below are prepared by the process of Example 1. Sodium, 4 parts of sodium cetyl sulfate and 5 parts of water-free sodium sulfate were ground in a ball mill for 48 hours to a fine powder. With the dye preparation obtained in this way, a polyester fiber fabric (Dacron, registered trademark), e.g. B. with the addition of lauryl sulfonate and the emulsion of a chlorinated benzene in water at 80-100 or in the absence of a dye accelerator under pressure at 110-140.

 

Claims (1)

PATENT CLAIM Process for the production of azo dyes of the formula that are sparingly soluble in water EMI0003.0007 where R, hydrogen, chlorine or bromine, Rg- is an optionally substituted, low-molecular-weight alkyl radical and R3 and R4 are hydrocarbon radicals, characterized in that an amine of the formula EMI0003.0015 diazotized and with a compound of the formula EMI0003.0017 clutch. <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 patent claim is authoritative for the material scope of the patent.