FR2626903A1 - METHOD FOR DYING MIXED SUBSTRATES - Google Patents

Abstract

The present invention relates to a process for dyeing a mixed substrate capable of being dyed with a dispersion dye and with a direct dye and / or metalliferous reactive, characterized in that the following is applied to the substrate: a) in minus a dispersion dye; b) at least one direct and / or reactive dye containing copper; c) a complexing agent having a stability constant (K value) with the metal of the direct or reactive dye of between 6 and 17 inclusive; d) a ligninsulphonate as a dispersant; and e) an oxidizing agent capable of converting copper I to copper II at temperatures between 100 and 130 degree (s) C and at a pH of 5 to 7 in the process of dyeing the mixed substrate.

Description

The subject of the present invention is a method

  of a single bath dyeing of a mixed substrate capable of being dyed with a disperse dye

  and with a direct dye and / or reactive metalliferous ..

  One of the problems with dyeing

  mixtures of cellulosic fibers and poly-

  ester or polyamide with a disperse dye and a direct dye or reactive metalliferous, lies in the fact that free metal ions that are not

  complexed with the dye molecule and which accompanies

  Naturally the direct or reactive dye.

  interfere with the disperse dye. This results not only in causing an undesirable change in the shade of the dyes made with these dispersion dyes, but also in the reproducibility of the shades with these dyes.

disperse dyes.

  Complexing agents, such as acid

  in general, avoid these

  vantages. However, when dyes having an intensity higher than the standard intensity I11 are desired and when the dispersant used is a lignin sulphonate, this undesirable effect is observed again. the dispersion dye and this effect can not be fully offset by the addition of additional complexing agent, such as citric acid alone. The Applicant has now found a method which allows

to avoid these disadvantages.

  The invention relates to a dyeing process

  a substrate consisting of a mixture of fibers

  may be dyed with a dispersion dye and with a direct metalliferous dye and / or a metalliferous reactive dye, wherein the substrate (a) at least one disperse dye, (b) at least one direct dye and / or reagent containing copper, preferably in a sufficient amount

  to obtain a tincture of superior intensity

  is an intensity. standard -d: on the substrate, '

  c) a complexing agent having a stabilizing constant

  (K value) with the metal of the direct dye or

  reagent between 6 and 17 inclusive ,.

  d) a lignin sulfonate as a dispersant and e) an oxidizing agent capable of converting copper (1) to copper (II) at temperatures between 100 and 130 ° C and at a pH of 5 & 7 in the

  dyeing process of the mixed substrate.

  Preferably, the components a) to e) are

  applied at the same time on the substrate.

  The direct dyes used in the process according to the invention are preferably the complexes with a heavy metal, preferably azoXques, more preferably C.I. Direct Red 261 dyes,

  C.I. Direct Blue 90 and C., I Direct Brown 240.

  Dispersion dyes are commercially available in the form of a powder or filter cake generally containing a lignin sulphonate, such as a dispersant. The direct dyes mentioned above are dyes containing copper. In the absence of the complexing and oxidizing agents of the process according to the invention, the free copper which is associated with

  these dyes are such as to cause an adverse effect

  that can be observed on poly-colored dyes

  ester or polyamide made with the disperse dye, given the sensitivity of these dyes

  of copper ion dispersion in the dye bath.

  Preferred reactive dyes for the process of the invention are heavy metal complexes, preferably azo, more preferably copper-containing reactive dyes which have an effect.

  unfavorable on the dispersion dye used for.

  dyeing the polyester or polyamide fibers of the

mixed substrate.

  The preferred disperse dyes used

  in the process of the invention are those whose grade is likely to be modified by the metals according to the modified ISO0 Z02 standard (dyeing the polyester in the presence of a metal salt at 130 ° C. instead of

  980c). Dispersion dyes are more preferable

  those with lower values & 4-5 as determined. according to ISO Z02 modified,

especially from 1 to 4.

  The preferred dispersion dyes for use in the process of the invention are as follows: C.I. Disperse Blue 79, C.I. Disperse Blue 81, C.I. Disperse Blue 180, C.I. Disperse Blue 183, C.1. Disperse Blue 291, C.I. Disperse Violet 63, C.1. Disperse Violet 93i1, Dispersion Blue 56 and C.I.

C.I. Disperse Blue 73.

  The preferred complexing agents of the invention

  are selected from citric acid, biguanide,

  amino-trimythylenephosphonic acid, ethyl & nedi--

  amine, glycine and derivatives (such as salts) of

  each of the above complexing agents.

  The K values are described in the "Stability Constants of Metal Ion Complexes" manual: Section Z: Organic Ligands (LG Sillen) and Section II: Inorganic Ligands (AE Martell) published by the Chemeaia Society (London, 1964). The definition of K is shown on pages X-XVII of the above-mentioned manual and is incorporated in this application as a reference.When a metal and a complexing agent have several K values, the indicated K value

  in the present description is preferably delle

  corresponding to the metal and the complexing agent in a

  medium with a pH of between 4 and 5.5 (preferably

  at a temperature of 100 & 1400C).

  K is preferably between 10 and 17 inclusive. The oxidizing agent is preferably a strong oxidizing agent at pH 5 and 1300C and is essentially colorless. The oxidizing agent more preferably has an EM (Standard Electrode Potential) value of between 1.1 and 1.8, especially between 1.18 and 1.6. E0 values are described in "Fundamentals of Analytical

  Chemistry "(3rd Edition) - D.A. Skoog and D.M. West -

  published by Holt-Saunders International Editions. Pages 780 to 782 of this publication are incorporated herein by reference. The oxidizing agent is especially a chlorate, bromate or iodate of an alkali metal or alkaline earth metal, more preferably a chlorate or a bromate, especially

sodium bromate.

  The amount of lignin sulphonate dispersant is preferably such that it causes dispersion of the disperse dye in the bath (preferably a bath by exhaustion), more preferably

  amount between 0.02 and 10 g / l bath.used.

  The invention also relates to a composition

  comprising a) a complexing agent as defined above, preferably citric acid, and b) an oxidizing agent as defined above, preferably an alkali metal chlorate or bromate.

or alkaline earth metal.

  Such a composition is intended to be

  added to the dyebaths and preferably includes

ence

  a) from 50 to 70% by weight of a complexing agent such as

  as defined above, and b) from 50 to 30% by weight of an oxidizing agent such as

defined above.

  The dyeing of the polyester / cellulose fibers is usually carried out at a temperature of

  between 60 and 135C and the dyeing of poly-

  amide / cellulose is usually performed -

  -1250C. Some copper-containing direct dyes or reagents tend to dissociate at elevated temperatures, for example above 100 ° C., which causes the release of copper ions during the dyeing process. However, even when there is no copper release at elevated temperatures, the copper that normally accompanies the direct or reactive dye and is not complexed with the dye

  question, interferes however with the dye of -

  dispersion. In this description, we mean

  therefore by "free copper" any copper ion present which is not complexed with the direct or reactive dye, whether this copper ion is present from the beginning of the dyeing process or is produced by

  dissociation of the dye during dyeing.

  The amount of "free copper" accompanying a direct or reactive dye can be determined by visual comparison of the negative effect of the direct or reactive dye, for example a change of shade, with the negative effect of various concentrations of a solution of oxtail sulfate on a dye made with the same dispersion dye. When the effect is the same, the copper sulphate content is considered to be the "free copper content" of the direct or reactive dye. The free copper content of a direct or reactive dye can also be determined by atomic absorption spectroscopy (for example as described in "Flame Emission and Atomic

  Spectroscopy ", John R. Dean, Vol 1, Chapter 1, [ZIII ..

  a Perkin Elmer spectrometer is preferably used.

  The weight ratio of the complexing agent to the free copper present in the process of the invention is

  preferably between 20: 1 and 1000: 1.

  When the dyeing process according to

  The reaction is carried out at temperatures above C and the direct dye or copper reagent used is a dye which liberates the copper during the process, the weight ratio of the complexing agent to free copper is preferably between 500.degree. and 1000: 1. When copper is not released during the dyeing process, the weight ratio of the complexing agent to the free copper is from 20: 1 to 1. The amount of oxidizing agent present is preferably between 30 and 100% of the amount

of complexing agent present.

  The process of the invention is preferably carried out in an aqueous bath according to a process of exhaustion. The method is preferably carried out in

a unique bath.

  The temperature of the dyebath is preferably increased from 60 to 125-135c during dyeing. The dyeing with the dispersion dye is preferably carried out for 15 minutes at a temperature between 125 and 1350.degree.

  dyeing with the direct dye or reagent is carried out

  preferably killed for 15 to 45 minutes at a tempera-

between 60 and 800C.

  The process of the invention is carried out

  preferably using at least one disperse dye

  and at least one direct dye.

  The process is preferably carried out in a Jet dyeing apparatus, preferably completely filled with dyebath. As jet dyeing apparatus, there may be mentioned an autoclave for the dyeing of beams. The dyeing according to the process of the invention is carried out at a pH of preferably between 4 and

  6, more preferably between 4 and 5, 5.

  The process of the invention can be carried out in the presence of other usual additives such as slfate

  sodium and anionic dispersing agents.

  The preferred polyester / cellulose substrates are those made of polyester and cotton and those

  constituas-polyester and viscose.

  In the process of the invention, the polyester / cellulose or polyamide / cellulose substrates are preferably subjected to a post-treatment with a

or more of the following products-

  HAVE. the reaction product of a mono- or polyfunctional primary or secondary amine with cyanamide, dicyandiamide, guanidine or biguanide, up to 50 mol% of cyanamide, dicyandiamide, guanidine or biguanide

  may be replaced by a dicarboxylic acid

  or one of its mono-esters or di-esters, said product containing reactive hydrogen atoms bonded to nitrogen, or A). the above reaction product of AI with an N-methylol derivative of a urea, a melamine, a -guanamine, a triazinone, a urone, a carbamate or a amide, optionally in the presence of a catalyst for the crosslinking of

  N-methylylol compounds of the type mentioned

  above, or A3) the reaction product of AI above with epichlorohydrin. Products A 1 and A 2 are described in British Patent No. 2,070,006 and US Pat. No. 4,441,652, and A3 is described in British Patent Application No. 2,142,642 A and in US Pat. US Patent Nos. 4,439,203 and 4,559,058, the contents of which are incorporated in

  present application & title of reference.

  The amount of composition according to the invention intended to be added to the dyeing bath is preferably between 0.2 and 1.5 g / l of the aqueous bath. The following examples illustrate the present invention without in any way limiting its scope. In these examples, parts and percentages are by weight and temperatures are in degrees Celsius unless otherwise indicated. In these examples, the amount of lignin sulfonate dispersant

  is between 2 and 5 g / 1 dye bath.

EXAMPLE 1

  A dyebath having the composition shown in the following Table 1 is prepared and the pH is adjusted to 5 by the addition of formic acid. 5 g of a polyester / cotton substrate (50:50) are introduced into 75 ml bath at 600 (bath ratio = 1:15) and the temperature is increased from 60 to 1350 at a rate of 20 per minute. The bath is maintained at this temperature for 30 minutes and the bath is drained. We rinse

then the substrate & cold water.

  Subsequently, the substrate is subjected to

  treatment with the reaction product of rpiohlor-

  hydrine with the condensation product of diethyl-

  acetriamine with dicyandiamide.

TABLEAJU 1

  a) Recipe 1 having the following composition 2.3% of C.i. Disperse Blue 79 0.11% C ... Disperse Brown 19 0.018% C.I. Disperse Violet 33 0.53% C. *. Direct Blue 251 0.26% of C.1. Direct Green 69 and 0.26% of C. Direct Red 83: b) 9/1 sodium sulfate, 1 g / 1 ammonium sulfate and c) 0.5 g / 1 sodium citrate and

0.2 g / I sodium bromate.

  The procedure of Example 1 is repeated using 1.0 g / l of sodium citrate (instead of 0.5 g / l) and 0.5 g / l of sodium bromate (instead of

0.2 g / l).

  After dyeing, the substrate is thoroughly rinsed and treated with 1.5% (based on the weight of the substrate) of the reaction product of 103 parts of diethylenetriamine and 84 parts of dicyandiamide (prepared according to Example 1 of US Pat. 4,410,652) and 5 g / l of sodium sulfate with a bath ratio of 1:15. The temperature of the bath was raised from room temperature to 600, subjected to post-treatment for 20 minutes at 60 ° C. and

rinse with water.

EXEKPLE 2

  The procedure is as described in Example 1, replacing recipe 1 with recipe 2 below: 2.5% of a mixture of CI Disperse Blue 183, C.1.I Disperse Blue 81, CI Disperse Blue 180, CI Disperse Blue 79, CI Disperse Violet 63, CI Disperse Orange 25, and CI Disperse Orange 96i 0.6% CI Mixture Disperse Orange 30, CI Disperse Violet 93: 1, and CI Disperse Blue 79, Q. 3% of C. Disperse Yellow 235,

  3.0% of a mixture of C.I. Direct Yellow 162 ,.

  C.X. Direct Red 261, C.I. Direct Blue 90, and C.I. Direct Brown 240, and 0.2% of a mixture of C.1. Direct Yellow 162, C.Z. Direct Red 261, and

C.I. Direct Blue 90.

KXAMPLE 3

  The procedure is as described in Example 1, but replacing Recipe 1 with Recipe 3 below: 2.7% of a mixture of C.1. Disperse Orange 30, C.T. Disperse Blue 79, C.I. Disperse Violet 93: 1 and C.1. Disperse Red 64,

2Z626903

l1

  3.7% of a mixture of C.I. Direct Yellow 162 ,.

  C.Z. Direct Red 261, C.Zl Direct Blue 90, and

C.I. Direct-Brown 240.

EXTENSION 4

  the procedure is as described in Example 1, but

  by replacing recipe i with recipe 4 below.

  4.4% of a mixture of C.X. Direct Yellow 162, C. ^. Direct Red 261, C * I. Direct Blue 90, and C.1. Direct Brown 240, and 3.0% of a mixture of C.I. Disperse Red 54, C.I. Disperse Orange 30, and

C.!. Disperse Blue 79.

EXEUPLE 5

  The procedure is as described in Example 1, with maik replacing recipe 1 with recipe 5 below: 2.0% of a mixture of C.I. Direct Yellow 162, C.I. Direct Red 261, Cl. Direct Blue 90 and C.X. Direct Brown 240, 0.42% of a mixture of C.I. Direct Yellow 162, C.,. Direct Red 261, and C. Direct Blue 90, and 6% of a mixture of C.I. Disperse Brown 19, C.I. Disperse Violet 93: 1, and

C.I. Disperse Blue 291.

EXENPLB 6

  The procedure is as described in Example 1, but replacing Recipe 1 with Recipe 6 below: 1.0% of a mixture of CI Direct Yellow 162, CI Direct Red 261, CI Direct Blue 90, and CI Direct Brown 240, 0, S15% CI-. Disperse Orange 37, and 6.0% .de Serilene Black VX-RL containing

of C.I. Direct Blue 291 ..

EXAMPLE 7

  The procedure is as described in Example 1, but replacing Recipe 1 with Recipe 7 below: 0.22% CI Disperse Yellow 235, 2.0% of a mixture of CI Direct Yellow 162, CI Direct Red 261, - C.1. Direct Blue 90, and CI Direct Erown 240, - 0.8% CI Direct Yellow 162 Blend, CI Direct Red 261, CI Direct Blue 90, 2.0% CI Mix Disperse Orange 30, CI Disperse Blue 79, CI Disperse Violet 93: 1, and CI Disperse Red 54, and 0.9% CX Blend Disperse Orange 30, C.I. Disperse Violet 93: 1, and

C.1. Disperse Blue 79.

Claims (17)

  A process for dyeing a mixed substrate capable of being dyed with a dispersion dye and with a direct and / or reactive metalliferous dye, characterized in that at least one dye of dispersion, b) at least one direct dye and / or reagent containing copper,   c) a complexing agent having a de-stabilizing constant   (K value) with the metal of the direct or reactive dye between 6 and 17 inclusive, d) a lignin sulphonate as a dispersant and e) an oxidizing agent capable of converting copper (1) to copper (IX) at temperatures between 100 and 130 C and a pH of 5 S 7 in the   dyeing process of the mixed substrate.   2. A process according to claim 1, characterized in that the oxidizing agent is an agent strong oxidant at pH 5 and 130C.   3. A process according to claim 1 or 2, characterized in that the oxidizing agent has an EO value between 1.1 and 1.8.   4. A process according to any of the   1 to 3, characterized in that the agent   oxidant is a metal chlorate, bromate or iodate alkaline or alkaline earth.   5. A process according to claim 4.   characterized in that the oxidizing agent is sodium bromate. 6. A method according to any one of   claims I to 5, characterized in that the agent   complexant has a K value between 10 and 17 inclusive. 7. A method according to any one of   Claims 1 to 6, characterized in that the agent   complexing is. selected from citric acid, biguanide, amtno-trimethylenphosphonic acid, ethylenediamine, glycine and the excesses of each complexing agents above.   8. A procedure ... according to any of the   Claims 1 & 7, characterized in that the agent   complexing agent is sodium citrate.   9. A process according to any of the   Claims 1 to 8, characterized in that the substrate   is a polyester / cellulose or polyamide / cellulose substrate.   Iose. 10. A process according to any one of   Claims 1 to 9, characterized in that the dyeing   is carried out at a temperature between 60 and e. 11, A process4 according to any one of   Claims 1 to 10, characterized in that it is   carried out using at least one dispersing dye   sion and. at least one direct dye metalliferous.   12. A process according to any of   1 to 1, characterized in that the pH is between 4 and 6 inclusive.   13. A process according to any one of   Claims 1 to 12, characters. in that the report   from the complexing agent to the free metal associated with the colo-   direct or reactive metalliferous * 1 and 1000,: 1.   14. A method according to any one of   Claims 1 to 13, characterized in that   the complexing agent and the oxidizing agent squs form a composition comprising a) from 50 to 70% by weight of complexing agent, and   b) from 50 to 30% by weight of oxidizing agent.   15. A process according to any one of   Claims 1 to 14, characterized in that   The substrate is subjected to post-treatment with one or more of the following products: AI) the reaction product of a mono- or polyfunctional primary or secondary amine with cyanamide, dicyandiamide, guanidine or biguanide, up to 50 moles% of cyanamide, dicyandiamide, guanidine or biguanide   may be replaced by a dicarboxylic acid   that or one of its mono-esters or di-esters,   said product containing nitrogen-reactive hydrogen atoms, or A2) the reaction product of Ai above with an N-methylol derivative. a urea, a melamine, a guanamine, a triazinone, a urone, a carbamate or an amide, optionally in the presence of a catalyst for the crosslinking of   N-methylol compounds of the type mentioned   above, or A3> the reaction product of A above with epichlorohydrin. 16. A mixed fibrous substrate, characterized in that it has been dyed with at least one dispersion dye and at least one direct and / or reactive dye   mixed in the presence of a complexing agent having   a K value with the metal of the direct dye or   metal-bearing active matter between 6 and 17 inclusive and   presence of an oxidizing agent capable of transforming the.   copper (1) copper (II) at a temperature included   between 100 and 1300C and at a pH of 5 to 7 in the process. dyeing the mixed substrate.   17. A composition comprising a) from 50 to 70% by weight of a complexing agent such as   defined in any one of claims 1, 7 and 8, and -2626903   50- & 30% by weight of an oxidizing agent such as   defined in any one of claims 1 & S.