FR2462511A1 - DYEING PROCESS FOR OBTAINING RESISTANT OR MULTICOLOR EFFECTS ON TEXTILE SUBSTRATES LIKELY TO BE DYED BY ANIONIC DYES - Google Patents

Abstract

THE SUBJECT OF THE INVENTION IS A PROCESS FOR DYING SUBSTRATES LIKELY TO BE DYED WITH ANIONIC DYES. ACCORDING TO THIS PROCEDURE, A SYNTHETIC TANNIN IS LOCALLY APPLIED ON THIS SUBSTRATE, POSSIBLY IN ASSOCIATION WITH ANIONIC DYE OR ANIONIC OPTICAL BRIGHTENER AND, AFTER SUBSTRATING THIS SUBSTRATE TO A PRE-FIXATION, IT IS DYED WITH A LOW BATH RATIO BY MEANING OF D 'ONE OR MORE COLORANTS HAVING GOOD MIGRATION POWER, IT IS WINDED UP AND A ROTATIONAL MOVEMENT UNDER CONDITIONS ALLOWING THE SETTING OF THE DYES.

Description

246251 1

  The present invention relates to a dyeing or printing process for producing resist or multicolor effects on textile substrates that can be dyed with anionic dyes. It is known to obtain multicolored effects, to reserve or dye locally the

  substrate and then submit it to another dye.

  During these processes, the locally applied components for the resist or dye are fixed and the treated substrate is then washed and / or rinsed

  before being subjected to subsequent dyeing.

  In pursuing this research, the Applicant has now found that it is possible to obtain resist or multicolor effects according to a method

  much more economical, including fixing times

  shorter and without any intermediate steps

rinsing or washing.

  The invention more particularly relates to a process for dyeing a textile substrate that can be dyed with anionic dyes, a process according to which 1) a synthetic tannin-based reserve agent is optionally applied to the substrate, optionally in combination with with anionic dye or anionic optical brightener, 2) the components applied in step 1) are prefixed at a temperature of between 100 and 1600 for 30 to 180 seconds, and 3) in the absence of a washing step or rinsing, the substrate is impregnated with a bath of low ratio containing one or more dyes having a good migration power, 4) said substrate is wound, and 5) it is imparted a rotational movement at a temperature between 15 and 60 during 1 to 48

  hours, to fix the dyes.

  As suitable tanninsynthetic for step 1), there may be mentioned a) biphenyl compounds of formula I y1 y2 2 "3 SO3H Y4 (I) in which X represents an oxygen or sulfur atom or a residue -NHCONH-, -NHCO or -CONH-, Y1, Y2, Y3 and Y4 each independently of one another is a hydrogen, fluorine, chlorine or bromine atom or a trifluoromethyl group, at least one of the symbols Y1 , Y2, Y3 or Y4 to represent a halogen atom and at most one of the symbols Y1, Y2, Y3 or Y4 to signify a trifluoromethyl group, and

  Z represents a hydrogen atom, an alkanoyl group,

  amino containing 1 to 6 carbon atoms or a residue

-NHCONH

  Y5 o Y5 and Y6 are each, independently of the other, a hydrogen or halogen atom, a trifluoromethyl group; b) polyhydroxypolyarylpolysulfones as described in German Patent 1,012,070; c) anionic polycondensation products of one or diarylsulfones containing at least one phenolic hydroxy group and a hydroxybenzene sulfonic acid with formaldehyde or a compound capable of releasing formaldehyde, for example as described in German Patent No. 1,619,667 ; d) condensation products of dihydroxydiarylsulfones and benzenesulphonic acids (or the like) with formaldehyde or a compound capable of releasing formaldehyde; (e) sulfonated condensation products of phenol or cresol with formaldehyde; (f) mixed condensates of sulfonated aromatic hydroxy compounds and aralkyl halides with formaldehyde; and (g) condensation products of bisphenol with formaldehyde. these compounds then being sulfomethylated by reaction with the sulphite adduct

with formaldehyde.

  The preferred synthetic tannins are those

  described in (d), in particular condensation products

  of a dihydroxydiphenylsulfone and a xylene sulfonic acid with formaldehyde. These compounds can be obtained, for example by heating to 100 of an aqueous solution containing about one mole

  m-xylenesulfonic acid and 1.1 to 1.6 moles of 4,4'-

  dihydroxydiphenylsulfone or a mixture of 4,4'-dihydro-

  xydiphenylsulfone and 2,2'-dihydroxydiphenylsulfone, with 1.5 to 2.3 moles of formaldehyde. The reaction mixture is heated until all the formaldehyde has reacted and then neutralized to pH 7. The condensation product thus obtained can then be diluted with

some water.

  The amount of synthetic tannin present in the dough or liquor applied in step 1) can vary; this amount will depend on factors such as the method of application and the type of dye used. In general, good results are obtained when the liquor or paste contains from 1 to 60 g per liter, preferably from 5 to 20 g / liter.

synthetic tannin.

  The anionic dyes used for topical application 1) are preferably free of groups capable of reacting with the fibers; it is for example acid dyes or direct dyes. Preferably, an acid dye or a metalliferous complex, especially a 1: 2 metalliferous complex is used. Such dyes may have low or good migration power and are indicated in the Color Index. By way of examples, mention may be made of CI Acid Brown 298, Acid Brown 132, Acid Blue 40, Acid Blue 25, Acid Blue 127: 1, Acid Blue 151, Acid Blue 296, Acid Black 52, Acid Black 132, Acid Green 106, Acid Green 25, Acid Orange 127, Acid Orange 156, Acid Orange 80, Acid Orange 67, Acid Yellow 121, Acid Yellow 151, Acid Yellow 218, Acid Yellow 129, Acid Red 216, Acid Red 299, Acid Red 263

Acid Red 401 and Acid Blue 278.

  A particularly favorite class

  of acidic dyes and metal complexes is that

  taking dyes having a high molecular weight, that is to say a molecular weight between 600 and 1050, preferably 800 and 1050, and containing at least one sulfo group, preferably two sulfo groups in

the molecule.

  Preferred optical brighteners are those having a molecular weight of between about 800 and

  850 and containing at least one sulfo group.

  The local application of the liquor or paste containing the synthetic tannin and optionally one or more anionic optical dyes or dyes can be carried out according to the known methods, according to the desired pattern or at random, for example according to the space-dyeing technique. ), the TAK process or the polychromatic process. This application can be made on a dry substrate or previously moistened. Preferably, the components specified above are applied by means of a paste or a liquor which is printed or applied in the form of drops on the substrate; one can for example proceed by printing the frame or use a device TAK, according to known methods. In addition to synthetic tannin and optionally optical dyes and brighteners, pastes or liquors used for local application may contain the usual additives such as thickeners,

  dispersing agents, wetting agents, etc.

  It is preferable to incorporate a thickening agent in these pastes or liquors in order to adjust their viscosity; the amount of thinner to add depends on the desired effects. The penetration depth of the dyes and the surface of the treated areas depend on the viscosity of the dough or the liquor

  and the nature of the dyes used.

  When the synthetic tannin is used in admixture with an acidic dye under acidic conditions, it is advantageous to add a dispersing agent.

  anionic or nonionic to the paste or liquor.

  Such a dispersing agent can also be brought into play

  when the synthetic tannin is applied alone.

  Suitable dispersing agents are any anionic or nonionic agents used in the textile industry, particularly those capable of forming little or no foam. Anionic dispersing agents are preferably used. Dispersion agents

  Anionic acids are the derivatives of naphthalene

  sulphonic compounds, in particular condensation products

  of a naphthalenesulfonic acid with formaldehyde.

  Such compounds are known and commercially available. In general, the amount of dispersing agent used in the liquor or paste applied in step 1) is preferably between

  1 and 30 g / l, preferably between 2 and 10 g / liter.

  When resist effects are desired, a liquor or paste containing a synthetic tannin and optionally an anionic or nonionic dispersing agent and optionally other additives other than a colorant are applied locally to the substrate. When two-color or multicolored effects are desired, the synthetic tannin is applied to the substrate mixed with one or more dyes and optionally

a dispersing agent.

  According to a preferred variant of the local application 1), a synthetic tannin is applied in association with one or more acid dyes in the form of a liquor or a paste under acidic conditions, the paste or liquor possibly containing an agent anionic dispersion and possibly

a thickening agent.

  The substrate may be in any conventional form, for example in the form of woven or knitted articles, yarns, nonwovens, pile fabrics, carpets, etc. Suitable substrates are those constituting wholly or in part, natural polyamides, for example wool or silk, synthetic polyamides, for example nylon 6, 66, etc., and mixtures thereof, including modified affinity polyamides. The dyeing process according to the invention is particularly suitable for dyeing synthetic polyamides, more particularly for dyeing synthetic polyamide carpets,

  possibly with modified affinity.

  The prefixation step 2) is a heat treatment of the substrate, of short duration, during which the synthetic tannin or synthetic tannin / dye (or optical brightener) carqplex is partially fixed. This fixation is such that, although the synthetic tannin or the complex is not fixed in a manner possibly solid washing, their tendency to migrate is reduced, and, therefore, it does not migrate

  during subsequent background dyeing. This preface

  fixation is preferably carried out for a period

  from 50 to 120 seconds, in particular from 60 to 90 seconds.

  The operation is carried out according to the known methods depending on the dye or agent used, for example by means of saturated steam at a temperature of between 100 and 1050, or by treatment with hot air at a temperature of

temperature around 160.

  The following steps 3), 4) and 5) correspond to

  dent to a bottom dye with a low bath ratio of a textile substrate according to a cold storage method. Suitable dyes having a good migration power, can be used dyes indicated for dyeing substrates may be dyed by anionic dyes, particularly substrates

  polyamide, according to cold storage methods.

  Preferably, acidic dyes having a relatively low molecular weight, for example between 400 and 600, and preferably comprising a single sulfo group, are used. Such dyes are known and mentioned in the Color Index; by way of examples, mention may be made of CI Acid Red 57, Acid Blue 72, Acid Yellow 196 and Acid Orange 156. In certain cases, these dyes with good migration power may carry a second sulfo group in the molecule, for example example in

  the case of metalliferous dyes.

  The base dyeing may be carried out according to known methods, for example by impregnation or padding, in particular as described in

24ú2511

  British Patent Nos. 1,470,981 and 1,371,781. The bath ratio is less than 10: 1; it is preferably between 1: 1 and 5: 1, in particular between 2: 1 and 3: 1. A dye bath containing a surfactant capable of forming a foam or a micro-foam or of giving a bath that is poor in foam or foam-free is used. In addition to the dyes and surfactant, the bath may also contain other commonly used adjuvants such as dye accelerator, carrier, retarder, leveling agent, dispersant, and the like. .. When it is desired to obtain special effects, it is also possible to add a synthetic tannin for example as described above for the application

local 1).

  After applying the dyebath, the substrate is preferably wrapped in a plastic sheet so as to avoid losses, and it is communicated to

  rotation, preferably for 1 to 24 hours, in particular

  at a temperature between 20 and 400.

  The rotation speed is preferably low, for example between 1 and 20 rotations / minute, preferably between 1 and 6 rotations / minute. This regular rotation results in a uniform distribution of the dye bath over the entire substrate. During this period

  rotation is the fixing of dyes.

  After fixation, the substrate may be dried by the usual methods or, if desired, released from the dye bath or residual adjuvants by

washing or spinning.

  Since synthetic tannin forms a complex with the dye or optical brightener to form a bulky molecule with low migration power, reciprocal disgorging is not formed during bottom dyeing.

  despite storage and rotation for 1 to 48 hours.

  The dyes obtained according to the process of the invention are distinguished by good fastness to light, wet and friction. In particular, good results are obtained when dyed according to the method of the invention tuftésen carpets in white unbleached polyamide

or pre-dyed.

  The process according to the invention has all the advantages resulting from short bath dyeing, in particular large planiform substrates, followed by cold storage. It makes it possible to obtain all kinds of colored patterns in an economical way; it is not necessary to rinse or wash between

  prefixing 2) and subsequent basecoat 3).

  In addition, the prefixation treatment is shorter

  than in the processes used until now.

  These are particularly advantageous when dyeing voluminous substrates, for example carpets, thus allowing significant energy savings.

and water.

  The invention also includes textile substrates, particularly polyamide carpets, which

  were dyed according to the new process.

  The following examples illustrate the present invention without in any way limiting its scope. Parts and percentages are by weight and

  temperatures are given in degrees Celsius.

Example 1

  On a velor mat made of polyamide 6 having a polyester support, a paste containing, per 1000 parts: parts of a synthetic tannin containing an acid condensation product, is printed locally.

  m-xylenesulfonic acid and 4,4'-dihydroxy-

  diphenylsulfone with formaldehyde, 4 parts of a commercial dispersion agent based on a condensation product of an acid

24625 11

  naphthalenesulfonic acid with formaldehyde, 3 parts of Acid Red 299 CI dye, parts of a commercially available thickening agent based on etherified flour of carob seeds, 2 parts of a commercial wetting agent based on a sodium alkylsulphate by anicnic groups, and

parts of 60% acetic acid.

  The substrate thus obtained is then treated for 80 seconds with saturated steam. On this carpet is poured, at 15-30, a liquor containing per 1000 parts: 2.8 parts of CI Acid Orange 156 dye, 2.1 parts of Acid Blue 72 CI dye, 2 parts of a commercial nonionic wetting agent. based on an ethylene oxide adduct on a higher alkylphenol, 1 part of a commercially available 1,1-pentylglycol ether, and 60% acetic acid parts. The bath ratio is 2.5: 1. The carpet is then wrapped, wrapped in a polyethylene sheet and protected from air.

  rotation for 20 hours at room temperature.

  After rinsing the carpet, wring it out and dry it.

  This gives a carpet with a green-olive base dye with a red-ruby pattern. This dye has excellent water fastness and precise contours.

Example 2

  A polyamide velor carpet having a polypropylene support is printed with a paste containing, for 1000 parts: parts of the synthetic tannin of Example 1, 2 parts of a commercially available dispersion agent.

  a condensation product of a naphthalene acid

  sulfonic acid with formaldehyde, parts of the thickening agent of example 1, 2 parts of an anionic wetting agent of the trade based on a sodium alkylsulfate, and

parts of acetic acid at 60e.

  The carpet thus obtained is then treated for 80 seconds with saturated steam. On this carpet is applied a liquor containing, for 1000 parts: 2.8 parts of CI Acid Orange 156 dye, 2.1 parts of Acid Blue 72 CI dye, 2 parts of a commercial nonionic wetting agent, base of an ethylene oxide adduct on a higher alkylphenol, 1 part octylphenol pentaglycolic ether, and 60% acetic acid parts. The bath ratio is 2.2: 1. This mat is then rolled up, wrapped in a polythene sheet and protected from air.

  a rotational movement for 20 hours at room temperature

  ambient temperature. The rotation speed is 3 rpm.

  After rinsing the carpet, wring it out and dry it.

  This gives a carpet with a background dye

  olive-green with white reserve effects.

Example 3

  A velvet mat made of polyamide 6 having a polyester support with a liquor identical to that used for printing is printed locally.

local to example 1.

  The substrate thus obtained is then treated

  for 80 seconds with saturated steam. So.

  at 15-30 ', a liquor containing, per 1000 parts: 2.8 parts of the CI Acid Orange 156 dye, 2.1 parts of the Acid Blue 72 dye, 8 parts of the synthetic tannin of Example 1, 2 parts of a commercial nonionic wetting agent based on an ethylene oxide adduct on a higher alkylphenol, 1 part of a commercially available pentaglycol ether of octylphenol, parts 60% acetic acid, and 0.4 parts of a commercial dispersion agent based on a condensation product of an acid

  naphthalenesulfonic with formaldehyde.

  The bath ratio is 2.5: 1. This carpet is then rolled up, wrapped in a polyethylene film and protected from air in the room at room temperature for 20 hours. After having rinsed the carpet, it is wrung out and dried. This gives a carpet with a green-olive base dye having a ruby pattern. This dye has excellent water fastness and

precise outlines.

Claims (16)

CLAIMS CATIONS   A process for dyeing a textile substrate that can be dyed with anionic dyes, characterized in that 1) a stocking agent based on a synthetic tannin, optionally in combination with a synthetic tannin, is applied locally to the substrate. anionic dye or anionic optical brightener, 2) the components applied in step 1) are prefixed at a temperature between 100 and 1600 for 30 to 180 seconds, and 3) in the absence of a washing or rinsing step the substrate is impregnated with a low-ratio bath containing one or more dyes having a good migration power, 4) said substrate is wound, and a rotation movement is imparted at a temperature between 15 and 600 for 1 to 48   hours, to fix the dyes.   2. A process according to claim 1, characterized in that, as synthetic tannin, a compound chosen from among a) biphenyl compounds of formula I is used. oxygen or sulfur atom or a residue -NHCONH-, -NHCO- or -CONH-, Y1, Y2 Y3 and Y4 are each, independently of each other, a hydrogen, fluorine, chlorine or bromine or a trifluoromethyl group, at least one of Yl, Y2, Y3 or Y4 to be a halogen and at most Y1, Y2, Y3 or Y4 to be trifluoromethyl, and Z represents a hydrogen atom, an alkanoylamino group containing from 1 to 6 carbon atoms or a residue Y 6 -NHCONH y5 o Y5 and Y6 each represent, independently of one another, a hydrogen atom or halogen or a trifluoromethyl group; b) polyhydroxypolyarylpolysulfones; c) anionic polycondensation products of diarylsulfones containing at least one phenolic hydroxy group and a hydroxybenzene sulfonic acid with formaldehyde or a compound capable of releasing formaldehyde; d) the condensation products of dihydroxy-diarylsulfones and benzenesulphonic acids (or the like) with formaldehyde or a compound capable of releasing formaldehyde; e) sulphonated condensation products of phenol or cresol with formaldehyde; f) the mixed condensation products of sulfonated hydroxy aromatic compounds and aralkyl halides with formaldehyde, and g) the condensation products of bisphenol with formaldehyde, these compounds then being sulfomethylated by reaction with the adduct of sulphite with formaldehyde.   3. A process according to claim 2, characterized in that the synthetic tannin is a condensation product of a dihydroxydiphenylsulfone   and m-xylenesulfonic acid with formaldehyde.   4. A process according to any one of   Claims 1 to 3, characterized in that the liquor   or the paste applied in step 1) contains from 1 to 60 g / liter synthetic tannin.   5. A process according to any one   Claims 1 to 4, characterized in that the   synthetic tannin is applied in admixture with one or several acid dyes.   6. A process according to any one   Claims 1 to 5, characterized in that the   liquor or paste applied in step 1) contains   in addition an anionic or nonionic dispersing agent.   7. A process according to claim 6, characterized in that the dispersing agent is a condensation product of a naphthalene sulfonic acid. with formaldehyde.   8. A process according to any one of   Claims 6 and 7, characterized in that the liquor   or the paste applied in step 1) contains from 1 to 30 g / l dispersant.   9. A process according to any one of   Claims 1 to 8, characterized in that the   fixation 2) is carried out for a period of 50 to 120 seconds with saturated steam, at a temperature between 100 and 105.   10. A process according to any one   Claims 1 to 9, characterized in that the   dyes used in step 3) and having good potency   migration are acid dyes.   11. A process according to any one   Claims 1 to 10, characterized in that the   bath ratio in step 3) is less than 10: 1.   12. A process according to any one   Claims 1 to 11, characterized in that the   fixation is effected during the rotational movement communicated to the wound substrate for a period of 1 to 24 hours at a temperature between and 40.   13. A process according to any one of   Claims 1 to 12, characterized in that the   substrate capable of being dyed by anionic dyes is constituted, in whole or in part,   natural and / or synthetic polyamides.   14. A process according to claim 13, characterized in that the substrate is present in the shape of a carpet.   Substrates made wholly or in part of natural and / or synthetic polyamides, characterized in that they have been dyed according to   method specified in any of the claims 1 to 12.   16.- Carpets of natural and / or synthetic polyamides, characterized in that they have been dyed by the process specified in any one of the Claims 1 to 12.