FR2663053A1 - PROCESS FOR DYING TEXTILE MATERIAL CONTAINING CELLULOSE - Google Patents

Abstract

The subject of the invention is a process for dyeing cellulosic substrates with reactive dyes, comprising a) the addition in an aqueous bath of one or more dyeing auxiliaries chosen from the condensation products of sulfonated diphenyl ethers, the condensation products sulfonated ditolyl ethers, the condensation products of polydiphenylsulfones with formaldehyde and the condensation products of polyditolylsulfones with formaldehyde, and their salts, b) the introduction of the substrate into the dye bath and the addition of one or more dyes reagents, and c) fixing the dye to the substrate, salt being added in step a) or b) of the process.

Description

The present invention relates to a process for dyeing materials

  textiles containing cellulose with reactive dyes, preferably by exhaustion, to obtain dyes having excellent unison. The exhaust dyeing of textile materials containing cellulose with reactive dyes is

  usually carried out in the presence of a certain quantity

  The salt promotes the rise of the reactive dye on the fiber (by adsorption) and the alkali promotes the fixation of the dye (eliminating the presence of salt). hydrochloric acid) The type of salt and alkali and how to introduce them into the bath have been

  a significant influence on the unison and the reproduction

  In most cases, the necessary amount of salt is added to the bath prior to the addition of the dye. However, in many cases this causes the dye to rise too fast on the fiber, leading to dyes with poor uniformity. An optimal distribution of the dye has

  was obtained by adding metered amounts of salt.

  The disadvantage, however, of such a process is that the addition of the necessary amount of salt as an aqueous solution causes, even when the

  solution is highly concentrated, the dilution of the bath.

  The addition of the salt in solid form is costly in time and personnel. The Applicant has now found a method which makes it possible to obtain a good distribution of the dye and stains that are solid and reproducible on

cellulosic substrates.

  The subject of the invention is therefore a process for dyeing cellulosic substrates with reactive dyes, characterized in that it comprises a) the addition in an aqueous bath of one or more dyeing auxiliaries chosen from the condensation products of the ethers sulphonated diphenyls, the condensation products of ditolyl ethers

  sulphonated, the condensation products of polydiphenyl-

  sulphones with formaldehyde and

  condensation of polyditolylsulfones with the

  maldehyde, and their salts, b) introducing the substrate into the dye bath and adding one or more reactive dyes, and c) fixing the dye to the substrate, salt being added in step a) or b) the dyeing process. Preferred dyeing aids for use in the process according to the invention are the condensation products of the sulphonated diphenyl ethers and the condensation products of sulphonated ditolyl ethers, in which the phenyl groups are unsubstituted.

  substituted or substituted by halogens.

  More particularly, the dyeing auxiliaries are chosen from the compounds of formula I

(HO S) O SO I O 502 H

(E 35 X 9 50 Z - (f 4 3 y

R R LR, R R R.

  in the form of free acids or in the form of salts, in which x and y independently signify 0 or 1, at least one of x and y must be 1, each R is independently hydrogen, halogen or methyl group, and

  n means O or an integer from 1 to 6 inclusive.

  In the process of the invention, the reactive dye

  may be added before or after the addition of the substrate.

  The amount of auxiliary dye added is

  preferably between 0.05 and 5 g / l, more particularly

between 0.2 and 2.5 g / l.

  In this application, the quantities are

  data in grams per liter of bath.

  The addition of the dyeing aid may have

  place before or after the addition of salt.

  The process according to the invention is preferably a

  dyeing process by exhaustion.

  The compounds of formula I are advantageously in the form of alkali metal salts, such as sodium or potassium, or, preferably, in the form of salts

of ammonium.

  R preferably means R ', R' meaning

hydrogen or a methyl group.

  Especially preferred dyeing aids

  are those described in Swiss Patent No. 660 828,

  in Example 1, the contents of which are incorporated in

  this application for reference.

  The polydiphenylsulfone is preferably the condensation product of dihydroxydiphenylsulfone,

  m-xylenesulfonic acid and formaldehyde.

  The salt used in step a) or b) of the process is preferably sodium chloride or sodium sulfate. The amount of salt added is preferably between 1 and 200 g / l, in particular 1-100 g / l

more particularly 5-80 g / l.

  Preferably, the fixing according to stage c) of the process is carried out by addition of alkali after a immersion time of the substrate in the bath of at least 2 minutes.

  at 1 hour, preferably 5 to 30 minutes.

  The amount of alkali added is preferably between 0.1 and 50 g / l, more preferably 0.2

at 20 g / l.

  The alkalis used in stage c) of the process are preferably sodium hydroxide, sodium carbonate, sodium silicate and sodium phosphate, more particularly sodium carbonate and

sodium hydroxide.

  According to a preferred embodiment of the process of the invention, an alkali metal tetraborate is added before step c) of the process. In this way, it is possible to compensate for the fixing irregularities due to the addition of the alkali, allowing to obtain dyes

united and reproducible.

  The amount of tetraborate added is preferably

  Preferably, the alkali metal tetraborates are sodium or potassium tetraborate and their hydrates, such as borax or kernite, are preferably from 0.01 to 5 g / l, in particular from 0.1 to 2 g / l. tetraborate can be added at the same time or after the addition of the dyeing aid and before or after the salt However, it must be added before fixing

with alkali.

  The bath used in the process of the invention may also contain other auxiliaries, such as dispersing agents, emulsifying agents and softeners. In the process according to the invention, the substrate to be dyed is preferably added before the reactive dye. The invention also relates to an aqueous composition comprising a) from 1 to 50% of a dyeing aid chosen from the condensation products of sulphonated diphenyl ethers, the condensation products of the sulphonated ditolyl ethers, the condensation products of

  polydiphenylsulfones with formaldehyde and

  condensation products of polyditolylsulfones with formaldehyde, b) from 1 to 50% of an alkali metal tetraborate, c) from 0 to 30% of a solubilising agent, for example a hydrotropic agent, and d) from 0 to 80% % water,

  the percentages given being percentages by weight.

  The preferred compositions for use in the process according to the invention are chosen from compositions I to III below: Composition I 17.6% of a condensation product of sulphonated ditolyl ether, 0% borax ( sodium tetraborate 10H20), 0% glycerine and 22.4% water Composition II 22.0% of a condensation product of sulfonated ditolyl ether 24.0% of potassium tetraborate tetrahydrate, 0% of glycerin 1.5% urea, and 42.5% water Composition III, 0% of a condensation product of sulfonated ditolyl ether 4.0% borax (sodium tetraborate 10H20) 2.8 % urea 7.8% ammonium sulfate 0.8% polyacrylic acid (molecular weight about 5000)

  0.8% of the sodium salt of diethylene

  triaminepenta (methylenephosphonic) and

43.8% water.

  The compositions are preferably added in an amount of between 0.1 and 10 g / l, in particular

0.1 to 5 g / l.

  Such a solution or composition according to the invention

  may contain a complexing agent In the composition

  sition III, the sodium salt of diethylene

  triaminepenta (methylenephosphonic) and polyacrylic acid are complexing agents They are added to prevent the precipitation of any insoluble compound that may be present, for example CaCO 3, on the substrate They also allow dyeing in hard water

  with dyes sensitive to hard water.

  The amount of solubilizing agent depends on the solubility of the tetraborate used Since borax for example is less soluble than potassium tetraborate, it is advisable to use more agent

  solubilizing when borax is used.

  As solubilizing agents or hydrotropic agents, mention may be made of carbonyl compounds, such as urea and thiourea, alcohols, glycol ethers, esters and heterocyclic compounds. The solubilizing agents are preferably methanol, ethanol, butanol, glycerin, ethylene glycol, diethylene glycol, sorbitol, glycerol acetate, glycol monoethyl ether, glycol mono-butyl ether, diglycol ethyl monoether, diglycol butyl monoether,

  butyrolactone and N-methylpyrrolidone.

  In the process according to the invention, the ratio of the bath is preferably from 1: 1 to 1: 100, in particular from

  1: 4 to 1: 100, more particularly 1: 4 to 1:30.

  The reactive dyes used in the process according to the invention are preferably azo dyes, anthraquinone dyes, metalliferous complex dyes and phthalocyanines, above all water-soluble dyes which can be fixed by exhaustion to a p H from 8 to 12.5 at a temperature of 20 to C The most preferred reactive dyes

  those containing at least one mono or di-

  chlorotriazinyl, monofluorotriazinyl, mono or

  difluoropyrimidine, fluorochloropyrimidine, dichloro-

  quinoxaline, (methylsulfonyl) (chloro) (methyl) pyrimidine

and sulfatoethylsulfonyl.

  According to a preferred embodiment of the invention, the composition according to the invention is added to the bath at the beginning of the dyeing process. The salt is then added before or after the addition of the dye, in solid form or in the form of a dye. concentrated aqueous solution After dyeing, the alkali is added in portions to the bath, preferably in the form of a concentrated aqueous solution. After the addition of alkali, the process is continued for another 5 to 60 minutes.

  the substrate and washed according to the usual methods.

  The textile materials used in the dyeing process of the invention are those made of natural or regenerated cellulose, optionally mixed with synthetic fibers, for example polyester. The process according to the invention is particularly suitable for dyeing cross rolls, which have

  tendency to give non-reproducing dyes

tible and unified.

  The process of the invention can be carried out with any machine suitable for exhaust dyeing, for example dyeing machines for yarns, jiggers or jet dyeing machines.

can operate in long or short bath.

  The following examples illustrate the present invention without in any way limiting its scope. All parts are by weight and temperatures are indicated in degrees Celsius.

percentages by weight.

Example 1

  In a yarn dyeing machine 1600 parts of an aqueous bath containing 0.5 part of the condensation product of Example 1 of Swiss Patent No. 660,828, hereinafter referred to as "Product A" (a condensation product), are introduced. sulfonated ditolyl ether derivative), 0.6 part of borax and 100 parts of sodium sulphate. The mixture is heated to 400 and 100 parts of cotton fabric are added. A solution of 3.3 parts of CI dye is added to the bath. Reactive Red 147 in 100 parts of water and heating is continued at 40 for 30 minutes 5 times 7 parts of a 2.5% solution of NaOH are then added at intervals of 5 minutes and the dyeing is continued another 40 minutes at 400 After washing, rinsing and drying, a very red dye is obtained

united and reproducible.

  In the following Table 1, the degree of fixation of the dyeing of Example 1 was compared with that of a dye produced in the same manner but without Product A.

T A B L E A U 1

  Time O 5 10 15 20 30 60 (min) Degree of fixation O 39 66 82 91 97 100 without the Product A Degree of fixation with the product A O 14 30 42 62 86 100

  Degree of fixation O = beginning of alkali addition.

Example 2

  The procedure is as described in Example 1, but 3.3 parts of CI Reactive Blue 209 dye are used instead of 3.3 parts of CI Reactive Red 147 dye. A solid and reproducible blue dye is obtained. Table 2 below indicates the degree of fixation of the dye of Example 2 and that of dyeing performed under the same conditions in the absence of Product A.

T A B L E A U 2

  Time O 5 10 15 20 30 60 (min) Degree of fixation O 37 64 79 92 99 100 without the Product A Fixing degree O 13 25 38 56,5 84 100 with the Product A

Example 3

  In 1600 parts of an aqueous bath heated to 40 and containing 2 parts of the following composition (Composition I)

  17.6% of a condensation product of diethyl ether

  sulfonated lily, 0% borax (10.2% sodium tetraborate), 0% glycerin and 22.4% water and 100 parts sodium sulfate, 100 parts of a cotton fabric are added to the bath 100 parts of an aqueous solution of 1.1 parts of the dye C I. Reactive Yellow 125 and dyeing is continued for another 30 minutes at 400. Then, at intervals of 5 minutes, 5 times 5 parts of a solution are added After washing, rinsing and drying, a dyed fabric is obtained in a very consistent and reproducible yellow shade. In the following Table 3, the degree of fixation of the dyeing of Example 3, as well as the degree of fixation of an identical dye carried out without the composition I, were indicated.

T A B L E A U 3

  Time O 5 10 15 20 30 60 (min) Degree of fixation O 33 64 83; 592.5 100 100 without the composition I Degree of fixation O 14 21 37 54 91 100 with the composition I In the place of the composition I, it is possible to use the same quantity of one of the compositions II and III

  as defined in the description.

  In Example 3, it is also possible to use 2 parts of a polydiphenylsulfone neutralized with ammonia and marketed under the trademark Nylofixan P, instead of Composition I.

Example 4

  To 1600 parts of an aqueous bath heated to 60, 2 parts of composition III containing 0% of a condensation product of sulphonated ditolyl ether, 4.0% borax 2.8% urea 7, are added. 8% ammonium sulphate

  0.8% polyacrylic acid of molecular weight

approximately 5000

  0.8% diethylenetriamine penta

  (methylenephosphonic) and 43.8% of water, and 120 parts of sodium sulphate. 100 parts of a cotton fabric are then introduced into the bath, followed by 100 parts of an aqueous solution of 3.1 parts of the dye. CI Reactive Blue 52 The bath is then heated to 980 and dyeing is carried out at this temperature for 30 minutes at intervals of 5 minutes, then 6.4 parts of a 5% aqueous solution of NaOH are added 5 times and after cooling to 40, dyeing is continued for another 40 minutes. After washing, rinsing and drying, a solid and reproducible blue dye is obtained. The degree of fixation of the resulting dye of Example 4 is indicated in the following Table 4, as well as the degree of fixation of an identical dyeing.

carried out without the composition III.

T A B L E A U 4

  Time of fixation without composition Composition III The degree of fixation without Composition III The same good results are obtained using Examples 1 to 4, in place of the dyeing aid used therein, an identical amount of any of the other auxiliaries, Product A or

Compositions I to III.

Claims (21)

  1. A process for dyeing a substrate containing cellulose with reactive dyes, characterized in that it comprises a) the addition in an aqueous bath of one or more dyeing auxiliaries chosen from the condensation products of the ethers sulphonated diphenyls, the condensation products of ditolyl ethers   sulphonated, the condensation products of polydiphenyl-   sulfones with formaldehyde and the condensation products of polyditolylsulfones with formaldehyde, and their salts, b) the introduction of the substrate into the dye bath and the addition of one or more reactive dyes, and c) the fixation of the dye on the substrate, salt being added in step a) or b) of the dyeing process. 2. A process according to claim 1, characterized in that the dyeing aid is a sulphonated diphenyl ether condensation product or the sulphonated ditolyl ether condensation product, in which the phenyl groups are unsubstituted or substituted by halogen.   3. A process according to claim 1 or 2, characterized in that the dyeing aid is a compound of the formula I 103 S) X O x + 25 2 X <-i SO 3) RR R R.   in the form of free acid or in the form of a salt, in which x and y independently signify O or 1, at least one of x and y must be 1, each R is independently hydrogen, halogen or a methyl group, and   n means O or an integer from 1 to 6 inclusive.   4. A process according to claim 3, characterized in that R is hydrogen or a methyl group. 5. A process according to claim 3 or 4, characterized in that the compound of formula I is   form of alkali metal salt or ammonium salt.   6. A process according to claim 1, characterized in that the dyeing aid is the condensation product of dihydroxydiphenylsulfone,   m-xylenesulfonic acid and formaldehyde.   7. A method according to any one of   Claims 1 to 6, characterized in that the quantity   dyeing aid added is from 0.05 to 5 g / l.   8. A process according to any one of   Claims 1 to 7, characterized in that the added salt   in step a) or b) of the dyeing process is selected from   sodium chloride and sodium sulfate.   9. A process according to claim 8, characterized in that the salt is added in step a) of dyeing process   10. A process according to claim 8 or 9, characterized in that the amount of salt used is between 1 and 200 g / i.   11. A method according to any one of   Claims 1 to 10, characterized in that the colorant   reagent is added after the introduction of the substrate into the bath.   12. A process according to any of   Claims 1 to 11, characterized in that the fixation   according to step c) of the process is carried out by addition of alkali after a time of immersion of the substrate in the   bath at least 2 minutes to 1 hour.   13. A process according to claim 12, characterized in that the alkali is sodium hydroxide, sodium carbonate, potassium silicate or sodium phosphate.   14. A method according to any one of   Claims 1 to 13, characterized in that a   alkali metal tetraborate before step c) of the process.   15. A method according to any one of   Claims 1 to 14, characterized in that the method of   Dyeing is an exhaust dyeing process.   16. An aqueous composition comprises a) from 1 to 50% of a dyeing aid chosen from the condensation products of sulphonated diphenyl ethers, the condensation products of the sulphonated ditolyl ethers, the condensation products of polydiphenylsulfones with formaldehyde and the condensation products of polyditolylsulfones with formaldehyde, b) from 1 to 50% of an alkali metal tetraborate, c) from 0 to 30% of a solubilizing agent, and d) from 0 to 80% water.   17. A composition according to claim 16,   characterized in that it contains a complexing agent.   18. A composition according to claim 16 or 17, characterized in that it is chosen from the following compositions 1 to 3: Composition I 17.6% of a sulphonated ditolyl ether condensation product, 0% borax 0% glycerin and 22.4% water; Composition II 22.0% of a condensation product of sulfonated ditolyl ether 24.0% potassium tetraborate tetrahydrate, 0% glycerin 1.5% urea, and 42.5% water; Composition III, 0% of a condensation product of sulphonyl ditolyl ether 4.0% borax 2.8% urea 7.8% ammonium sulphate 0.8% polyacrylic acid having a molecular weight about 5000   0.8% of the sodium salt of diethylene   triaminepenta (methylenephosphonic) and 43.8% water.   19. A composition according to any one of   Claims 16 to 18, characterized in that the agent   solubilizer is selected from urea, thiourea, methanol, ethanol, butanol, glycerine, ethylene glycol, diethylene glycol, sorbitol, glycerin acetate, glycol monoethyl ether, butyl monoethane, glycol, diglycol ethyl monoether, diglycol butyl monoethanol,   butyrolactone and N-methylpyrrolidone.   20. The use of the condensation products of sulfonated diphenyl ethers, condensation products of sulfonated ditolyl ethers, condensation products of polydiphenylsulfones with formaldehyde and condensation products of polyditolylsulfones with formaldehyde, and their salts, such as specified in any of the   Claims 1 to 6, as auxiliary dyes in   processes for dyeing substrates containing cellulose. A substrate containing cellulose, characterized in that it has been dyed by the process   specified in any one of claims 1 to 15.