CH402811A - Process for dyeing and printing polypropylene fibers with metal-containing monoazo dyes - Google Patents

Description

  

      Process for dyeing and printing polypropylene fibers with metal-containing monoazo dyes Despite numerous efforts, it has not yet been possible to dye or print modified and unmodified polypropylene materials with a fibrous structure in a manner that fully satisfies practical requirements. The previously proposed dyes for dyeing unmodified polypropylene materials are not satisfactory.

   In order to improve the dyeability of polypropylene fiber materials with dyes, a move has been made to modify the fiber in a suitable manner (cf. A. J. Hall, Skinner's Silk and Rayon Record, September 1962, pages 799-800).



  For dyeing polypropylene fibers that have been modified by metals or metal compounds, dyes have recently been proposed which should have improved fastness properties compared to the dyes previously known for dyeing polypropylene (cf. Chemical Week, November 24, 1962, page 65 , as well as the Belgian patent specification No. 614 566). These dyes, too, generally do not yet sufficiently meet the requirements of practice.



  The present invention now relates to a process for dyeing and printing polypropylene fibers, which is characterized in that nickel or copper complexes of sulfonic acid group-free monoazo dyes of the formula
EMI0001.0029
    except for the dye defined in claim of Patent No. 370,390.



  In the above formula, R denotes an aromatic radical, in particular one of the benzene or naphthalene series, or a heterocyclic radical of aromatic character, in particular one of the thiazole, benzthiazole, thiadiazole, triazole, benzimidazole, quinoline or pyrazole series, R1 the remainder of a coupling component, where the substituents X and Y in R and R1 are adjacent to the azo group;

   one of the two substituents stands for a metal complex-forming group and the other for hydrogen or a metal complex-forming group. Particularly suitable complex-forming groups are hydroxyl, alkoxy, carboxy, carbomethoxy, amino and substituted amino groups.

   The dyes can, with the exception of sulfonic acid groups, have other customary substituents, such as nitro, cyano, alkyl, alkoxy, optionally substituted amino, acylamino, hydroxy, rhodanic, carboxylic acid, halogen , Trifluoroalkyl, sulfonic,

      optionally substituted sulfonamide and carbonamide and carboxylic acid ester groups.



  The process can be carried out in detail in such a way that the finely dispersed color substances (1) on the polypropylene fibers z. B. can be in the form of tissues, from neutral, acidic or. Alkaline aqueous suspensions using dispersants from a dye bath or a pad, preferably at temperatures of 50-130 C, applies.

   When coloring blocks, it is advisable to dry at 70-90 C and then briefly heat to 130 C. At temperatures of up to 100 ° C., it is generally advantageous to add common carrier substances, such as trichlorobenzene, diphenyl, diphenyl ether or esters of aromatic carboxylic acids, to the dye bath.



  As dispersants, which are added to the dyes before geous, the commercially available products, such as sulfite cellulose degradation products, condensation products of higher alcohols and ethylene oxide, soaps, polyglycol ethers of fatty acid amides, formaldehyde condensation products of aromatic sulfonic acids or mixtures of such compounds.



  The dyes, which are sparingly soluble or insoluble in water, can also be applied to polypropylene fabric by printing. The printing paste can be thickened with a conventional thickener such as methyl cellulose, locust bean gum, industrial gum or sodium alginate, and can also contain the usual additives for printing pastes, such as urea, thiourea or thiodiglycol, or other additives which are used to apply water-insoluble dyes such as methylated alcohols,

       Sodium m-nitrobenzenesulfate or aqueous emulsions of sulfonated oils. The printing paste is expediently applied to the fabric by printing with a printing block, spray device, template, screen or roller, whereupon the printed material is dried and, if desired, steamed, at atmospheric pressure or in a closed vessel at overpressure, if one Temperature above 100 C, e.g. B. between 110 and 130 C, is required.



  Following the dyeing or printing of the polypropylene fibers, the colored materia lien can be post-treated in the usual way, for. B. by treating with a hot aqueous soap solution and / or a solution of a synthetic cleaning agent.



  Some of the dyes of the formula (I) are known. They can be built up according to customary preparative methols by, for example, diazo compounds of amines of the formula
EMI0002.0040
      combined in a preferably neutral to alkaline range with coupling components in the vicinity of X.

   Suitable compounds of aromatic character from the heterocyclic series are u. a .: 2-aminothiazole-1,3, 2-amino-benzothiazole-1,3, 2-amino-5-methoxy-benzothiazole-1,3, 2-amino-6-methylsulfonyl-benzthiazole-1,3, 2 -Amino-6-carboxy-benzothiazole-1,3, 2-amino-6-methyl-benzthiazole-1,3, 2-amino-6-carboethoxy-benzothiazole-1, 3,

         2-Amino-4- or -5-nitro- or -cyan- or -methyl- or -phenyl- or -carboxy- or carbo- ethoxy- or -hydroxy-thiazole-1,3, 2-amino-4-methyl -5-nitrothiazole-1,3, 5-amino-3-phenyl-thiadiazole-1,2,4, 5-amino-3-ethylsulfonyl-thiazole-1,2,4, 8-aminoquinoline, 2,5-diaminotriazole -1,3,4 and 2,5-diamino-4-phenyltriazole-1,3,4 and the like.

    From the aromatic series, to name just a few examples, the following are suitable: anthranilic acid, 5-chloro-2-aminobenzene-1-carboxylic acid, methyl 2- and 4-amino-benzoate, 2-aminoanisole, 1-amino-2-chloro 5-methylbenzene, 2-hydroxy-4- or -5-nitroaniline, 2-hydroxy-5-chloroaniline, 1-amino-2-hydroxybenzene-5-ethylsulfone, 1-amino-2-hydroxybenzene-4- or 5-sulfomethyl - or -dimethylamide,

            4-nitroaniline and 2-chloro-4-nitroaniline. Suitable coupling components for the synthesis of the dyes (I) are, in particular, oxybenzene and its ring-substituted products, oxynaphthalenes, 5-pyrazolones, acylacetic acid arylamides, hydroxythionaphthenes and others.

   The following are excerpts from the large number of components that can be used: 2-hydroxynaphthalene, 2-hydroxy-8-methylsulfonylaminonaphthalene, 2-hydroxy-8- (2,4-dichlorobenzoylamino) naphthalene, 2-hydroxy-8-acetylaminonaphthalene , 1-hydroxynaphthalene-3-sulfonmethylene ether-4 of the formula
EMI0002.0092
         1-N-methyl-4-hydroxy-carbostyril of the formula
EMI0002.0094
         3-hydroxy-5,6,7-trichlorothionaphthene, 2,4-dihydroxyquinoline, 1-hydroxynaphthalene,

                4-methyl-1-hydroxybenzene, 4-tert-butylphenol, 3-hydroxy-IN, N-diethylaminobenzene, 1-acetylamino-4-hydroxybenzene, 1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-5 -pyrazolone-3-carboxylic acid methyl or ethyl ester, 1- (3'-chlorophenyl) -3-methyl-5-pyrazolone, 1- (2 ', 5'-dichlorophenyl) -3-methyl-5-pyrazolone and Acetoacetic anilide, 2-aminonaphthalene, 2- (N-ethylamino) naphthalene,

            2- (N-Benzoylhydrazino) naphthalene, 1-phenyl-3-methyl-5-aminopyrazole, 3-ethoxydimethylaniline, 2,5-dimethoxyaniline and 3-chloro-dimethylaniline. In addition to these, a large number of other substitution products of the coupling components can of course be used, although sulfonic acid groups should not occur as substituents.



  The transfer of the metal-free monoazo dyes to the composition
EMI0003.0029
    in the corresponding metal-containing dyes he follows by known methods by z. B. the alcoholic dye solution in the presence of Am moniak or soda together with an aqueous metal salt solution, for. B. with a nickel-II and copper-II acetate solution, heated.



  The metal complex azo dyes used according to the invention are very quickly absorbed by the polypropylene fibers. The dyeings and prints available are characterized by very good fastness properties. In addition to very good dry cleaning resistance, the excellent rub, wash and light fastness properties are particularly noteworthy.



  Particularly favorable dyeing results are obtained when the dyes to be used according to the invention are used for dyeing and printing polypropylene fibers modified with metals or metal compounds, in particular with nickel or nickel compounds.



  <I> Example 1 </I> 0.2 g of the nickel complex of the dye of the composition
EMI0003.0045
    are in 400 ml of water containing 0.2 g of a conventional dispersant (z. B. a naphthalenesulfonic acid-formaldehyde condensation product) and 0.2 ml of 30% formic acid, dispersed and dyed on 10 g of polypropylene fiber yarn for one hour at boiling temperature.

   After a subsequent weakly alkaline aftertreatment at 50 ° C. with the addition of 0.5 ml of a commercially available detergent, a greenish dark blue dyeing with very good wet, rub, solvent and light fastness properties is obtained.



  If the nickel complexes of such azo dyes are used in this example, which are prepared from diazotized 2-aminobenzothiazole and the azo components given in the table below, dyes are obtained which also give very valuable colorations on polypropylene materials in the shades given.

    
EMI0003.0061
  
    Azo component <SEP> hue <SEP> of the <SEP> color <SEP>
<tb> polypropylene fiber
<tb> 2-Hydroxy-8-methylsulfonamino) naphthalene <SEP> red-violet brown
<tb> 2-Hydroxy-8- (2,4-dichlorobenzoylamino) naphthalene <SEP> Bordo
<tb> 2-Hydroxy-8- (acetylamino) naphthalene <SEP> red-violet brown
<tb> 1-Hydroxynaphthalene-3-sulfonmethylene ether-4 <SEP> brick red
<tb> 1-methyl-4-hydroxy-carbostyril <SEP> red
<tb> 3-Hydroxy-1-N, N-diethylaminobenzene <SEP> violet
<tb> 1-Phenyl-3-methylpyrazolon-5 <SEP> yellow
<tb> 1- (3'-Chlorophenyl) -3-methylpyrazolone-5 <SEP> yellow
<tb> 1- (2 ', 5'-dichlorophenyl) -3-methylpyrazolon-5 <SEP> yellow <I> Example 2 </I> 100 g of polypropylene fiber material in the form of a sliver are mixed in 2 l of water,

   which is adjusted to a pH of 4-5 with dilute sulfuric acid and still contains 0.4 g of an alkylaryl polyglycol ether, with 1 g of the nickel complex of the finely dispersed dye of the composition
EMI0004.0001
    stained at 100 ° C. for one hour. The somewhat reddish yellow dyeing obtainable in this way is distinguished by very good fastness properties.



  If the azo component in the nickel complex dye of this example is replaced by the azo components in the table below, nickel complex dyes are obtained which likewise provide valuable colorations on modified polypropylene materials in the specified hues.

    
EMI0004.0009
  
     <I> Example 3 </I> 10 g of polypropylene yarn are endless in a bath of 400 ml of water, 0.2 g of a naphthalenesulfonic acid-formaldehyde condensation product and 0.2 g of the copper complex of the dye of the composition
EMI0004.0013
    contains in finely dispersed form, treated at 90 C for 30 Minu th. After the aftertreatment described in Example 1, a red, stuffy yellow with excellent fastness properties is obtained.

      Also very valuable dyeings on polypropylene materials are obtained if the azo components of the following table are present in the dye used instead of the 3-hydroxy-1-N, N-diethylaminobenzene.

    
EMI0004.0020
  
     If, instead of the diazo component from Example 3, anthranilic acid methyl ester, 2-hydroxy-5-nitroaniline or 4-nitroaniline are used, then the azo components of the above table also give monoazo dyes, the copper complex compounds of which give valuable yellow to red colorations on modified polypropylene materials.

 

Claims (1)

PATENT CLAIM I Process for dyeing and printing polypropylene fibers, characterized in that nickel or copper complexes of sulfonic acid group-free monoazo dyes of the formula EMI0004.0036 where R is an aromatic radical or a heterocyclic radical of aromatic character, R1 is the radical of a coupling component, where X and Y are in R and R, in the vicinity of the azo group, and each represents a metal complex-forming group or X represents a metal complex-forming group and Y represents hydrogen or vice versa, with the exception of the dyestuff defined in the patent claim of patent No. 370,390. SUBClaims 1. The method according to claim I, characterized in that the dyes are applied to the polypropylene fiber in the presence of dispersants from a dye bath or a padding liquor, preferably at temperatures of 50-130 C. 2. Method according to claim 1, characterized in that polypropylene fibers modified with metals or metal compounds are dyed or printed. PATENT CLAIM II Polypropylene fibers dyed or printed according to the method according to claim <B> 1 </B>.