EP0295205A1 - Process for pad dyeing or finishing with continuous fixation of textile materials - Google Patents

Abstract

Dyeing or finishing process characterized in that textile materials are impregnated with a scarf with aqueous dyeing or finishing baths, which contain, in addition to graft polymers, which can be obtained from a product adding an alkylene oxide to an at least trivalent aliphatic alcohol having from 3 to 10 carbon atoms and methacrylamide or acrylamide, and then fixing the dyes or the primer is carried out continuously by microwave treatment for 5 to 30 seconds. The process allows an excess of water on all textile materials and rapid fixation by microwaves.

Description

The present invention relates to a process for dyeing or finishing by padding textile materials capable of being treated with products which are fixed continuously by means of microwaves.

The method is characterized in that the textile materials are impregnated with a scarf with aqueous dyeing or finishing baths, which additionally contain grafted polymers, which can be obtained from a product d addition of an alkylene oxide to an at least trivalent aliphatic alcohol having 3 to 10 carbon atoms and methacrylamide or acrylamide, and the fixing of the dyes or of the primer to continue with a microwave treatment for 5 to 30 seconds.

The preferred graft polymers are those which can be obtained by graft polymerization of methacrylamide, or in particular acrylamide, on an adduct of 4 to 100 moles, preferably 40 to 80 moles, of oxide of propylene on alcohols having 3 to 6 carbon atoms and having 3 to 6 valences. These alcohols can be straight chain or branched. As an example, mention may be made of glycerol, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, mannitol, or sorbitol.

Other suitable graft polymers are those which can be obtained by grafting methacrylamide or acrylamide onto adducts of mixtures of ethylene oxide and propylene oxide, or alternatively of ethylene oxide alone, on the polyvalent alcohols mentioned.

Particularly suitable have been shown to be grafted polymers based on acrylamide and adducts of 40 to 80 moles of propylene oxide on 1 mole of glycerin.

It is advantageous that the grafted polymers used according to the invention contain 2.5 to 50% by weight of the adduct defined as the base chain and 50 to 97.5% by weight of acrylamide or methacrylamide grafted in as long as side chains.

Preferably, the grafted polymers have 2.5 to 30% by weight of the alkylene oxide adduct according to the definition and 70 to 97.5% by weight of methacrylamide or in particular of acrylamide. It is even more preferable for the level of amide in the grafted polymer to be from 80 to 97.5% by weight.

Among these products, particular preference is given to those which contain, as basic chain, 4 to 20% by weight of the adduct of 40 to 80 moles of propylene oxide over 1 mole of glycerin and 80 to 96% by weight of acrylamide.

The percentages indicated are relative to the total graft polymer.

The preparation of the grafted polymer used according to the invention is carried out according to the methods known per se, and suitably, as follows: the polymerization is carried out, in the presence of catalysts, and suitably at a temperature of 40 to 100 ° C, of (1) an adduct of an alkylene oxide on an at least trivalent aliphatic alcohol having 3 to 10 carbon atoms, with (2) acrylamide or methacrylamide. This gives predominantly grafted polymers in which the alkylene oxide adduct forms the base chains, and which contains, grafted on particular carbon atoms, acrylamide or methacrylamide in the form of side chains.

As catalysts, it is suitable to use initiators, organic or preferably inorganic, forming free radicals. Organic initiators suitable for the production of poly radical merization are for example symmetrical peroxydicarbonates, butyl peroctoate, butyl perbenzoate, peracetates or peroxydicarbamates. Suitable inorganic initiators are hydrogen peroxide, perborates, persulfates, or peroxydisulfates.

The preferred initiator or activator is potassium peroxydisulfate.

These catalysts can be introduced in an amount of 0.05 to 5% by weight, advantageously from 0.05 to 2% by weight, and preferably from 0.1 to 1% by weight, relative to the starting product.

The graft polymerization is advantageously carried out under an inert atmosphere, for example in the presence of nitrogen.

The graft polymerization products appear as a very viscous mass. By dissolution and dilution with water, gelatinous products can be prepared having a dry content of, for example, 0.5 to 20% by weight, preferably 2 to 20% by weight. For the preservation and / or improvement of the storage stability of the aqueous solutions of grafted polymers obtained, preservatives can be added, such as for example chloracetamide, N-hydroxymethylchloracetamide, pentachlorophenolates, alkali metal nitrites. , triethanolamine, or, preferably, monomethyl ether of hydroquinone, or alternatively an antibacterial agent, such as for example sodium azothhydride or else surface active quaternary ammonium compounds, which have one or more two alkylaliphatic residues. It is also more advantageous to introduce mixtures of these preservatives and germicidal compounds.

The particularly preferred graft polymer solutions obtained, having a content of 2 or 3 up to 5%, have at 25 ° C. a viscosity of 3,000 to 150,000, preferably from 20,000 to 120,000, and in particular from 40,000 to 80,000 mPas (milli Pascal second). The polyalkylene oxide adducts used for the preparation of the grafted polymers generally have a molecular weight of between 400 and 6,000, and preferably between 3,000 and 4,500.

The amounts of graft polymers introduced into the dye baths can vary within wide limits. In this way, quantities ranging from 3 to 50 g, preferably from 5 to 40 g and in particular from 8 to 20 g, have proved to be advantageous, in the form of aqueous solutions in concentration ranging from 3 to 10%, per liter. dye bath.

The process according to the present invention is suitable for applying both chemical substances and also dyes to textile substrates, such as, for example, combed, spun, plain fabrics, terry, velvet, carpets, knits or tablecloths. These substrates include all the usual natural and synthetic fibrous materials, such as cotton, hemp, linen, ramie, regenerated cellulose, cellulose acetate (2 1 / 2- or triacetate), polyester, polyacrylonitrile, polyamide, wool, silk, polypropylene, or mixtures of various fibers such as polyester-cellulose or polyester-wool mixed fabrics.

For the dyeing according to the present invention, all the usual classes of dyes are considered, for example dispersion dyes, substantive dyes, reactive dyes, acid dyes, basic dyes, as well as suitable mixtures, customary in practice, of such dyes. Examples of colorants are described in Color Index, 3rd edition, 1971, volume 4.

As chemical substances which can be applied according to the present invention, all chemical substances suitable for their introduction into the textile industry are considered, such as finishing agents, protective agents, binding agents, purification agents, finishes. as well as optical brighteners. As an example, consider the application of antistatic, hydrophobic, flame retardant, crease-resistant agents, for ease of maintenance, starching, anti-fouling, or elimination of soiling.

The process according to the invention is preferably suitable for dyeing textiles made from or containing cellulose, the textile materials being subjected, after the padding step, to a microwave treatment process, in order to fix the dye applied. .

The fixing of the dye is short-lived and is carried out continuously by means of microwaves. After impregnation with the dye bath and scarfing, the material is subjected to irradiation in a microwave field to heat the fabric and keep it at the temperature necessary for fixing the dyes or other chemical substances on the textile fibers. .

This microwave treatment is carried out in an apparatus consisting of a magnetron microwave generator of known type, equipped with a multiple serpentine waveguide terminated by a charge of water. This waveguide can be of the so-called "split" type, the fabric to be treated moving at constant speed through slots arranged longitudinally in the side walls of the waveguide. Preferably, a waveguide of the so-called "source-slit" type is used, provided with a system of multiple slits in the upper wall of the waveguide, either oblique or parallel to the guide and offset with respect to its axis, the tissue moving in the stretched state at a fixed distance from the waveguide, depending on the wavelength of the microwave generator, and at constant speed. A protection device (circulator) is interposed between the generator output and the waveguide to prevent reflected waves from damaging the magnetron. The whole is surrounded by a Faraday cage to protect operators against microwave radiation.

The microwave treatment can last from 5 to 30 seconds. Preferably, 5 to 18 seconds are sufficient. By microwave, we mean electromagnetic waves (radio waves) in the frequency range which goes from 300 to 30,000 MHz (mega hertz), and preferably from 800 to 4000 MHz, and of a power which can vary between 0.8 and 25 kW (kilo watts) preferably between 800 and 3500 watts.

As cellulosic material, such materials consisting of regenerated cellulose or in particular natural cellulose, such as, for example, fibranne, silk-viscose, hemp, flax, jute, or preferably cotton, as well as mixtures of fibers, for example those made of polyamides / cotton, or in particular of polyester / cotton.

The cellulosic material can then be present in the most diverse stages of treatment, in particular however in the form of fabric or knitted fabric, such as for example tubular knitted fabric. You can use both an unbleached product and a pretreated product.

As regards the dyes for dyeing cellulosic materials, these are substantive dyes, or above all reactive dyes, usually used for dyeing cellulosic textile materials.

As substantive dyes, the usual direct dyes are suitable, for example those which appear in "Color Index", 3rd edition (1971) volume 2, pages 2005-2478, under the name of "Direct Dyes".

By reactive dyes is meant the usual dyes which generate a chemical bond with cellulose, for example those which appear in "Color Index", in volume 3 (3rd edition, 1971), pages 3391-3560, and in volume 6 (3rd revised edition, 1975), pages 6268-6345, under the name "Reactive Dyes".

The amount of dyes is generally determined according to the desired intensity and suitably amounts to between 0.1 and 100 g per liter of bath, preferably between 5 and 60 g / l of bath.

Alkaline reactive compounds for fixing the dye are introduced, for example sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, borax, aqueous ammonia , or an alkali-generating product, such as sodium trichloroacetate. As an alkali, a mixture consisting of an aqueous solution of sodium silicate and an aqueous solution of sodium hydroxide at 30% has proven to be particularly good. The pH value of the alkali-containing dye bath is generally from 7.5 to 13.2, preferably from 10.5 to 12.5.

The textile materials can also be natural or synthetic polyamides such as wool, silk, nylon 6, 66 and their mixtures, including polyamides with modified affinity.

These polyamide materials are capable of being dyed with anionic dyes. For these dyes, these are, for example, salts of monoazo, disazo, or polyazo dyes, including formazan dyes, containing heavy or preferably non-metallized metals, as well as anthraquinones, xanthenes, nitrates, triphenylmethanes, naphthoquinone dyes. imines and phthalocyanines. The anionic nature of these dyes may be due to the mere formation of metal complexes and / or preferably to the presence of acid substituents, forming salts, such as carboxylic groups, sulfuric ester and phosphonic ester groups, phosphonic acid groups or sulfonic acid groups. These dyes can also present in their molecule what are called reactive groups, which form a covalent bond with the material to be dyed. Preference is given to so-called non-metallic acid dyes. The latter preferably contain only one sulfonic group, and optionally another water-solubilizing group, but not forming salts, such as the amide or alkylsulfonyl groups.

Dyes with a metal complex 1: 1, or preferably 1: 2, are also particularly advantageous. The 1: 1 metal complex dyes preferably have one or two sulfonic acid groups. As metal, they contain a heavy metal atom, such as for example copper, nickel, or in particular chromium.

The 1: 2 metal complex dyes contain, as central atom, a heavy metal atom, such as for example a cobalt atom or in particular a chromium atom. Two complexing components are linked to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules. In this case, the two dye molecules taking part in the formation of a complex can be identical or different from each other. 1: 2 metal complex dyes can for example contain two Azomethine molecules, one molecule of disazo dye and one molecule of monoazo dye, or preferably two molecules of monoazo dye. The azo dye molecules may have water-soluble groups, such as, for example, amide groups, alkylsulfonyl groups, or the acid groups mentioned above. Preferred are the 1: 2 complexes of cobalt or chromium of monoazo dyes, which have amide, alkylsulfonyl groups, or altogether only one sulfonic acid group.

Mixtures of anionic dyes can also be used. Mixtures of at least two or three anionic dyes are particularly advantageous for the preparation of solid dichromy or trichromy dyes.

The amount of anionic dye added to the bath is determined by the desired intensity of the colors. In general, amounts between 0.01 and 25 are recommended, in particular between 0.1 and 15 g / liter of bath.

Dye baths can contain mineral acids, such as sulfuric acid or phosphoric acid; organic acids, advantageously lower aliphatic carboxylic acids, such as, for example, formic acid, acetic acid, or oxalic acid, and / or salts, such as, for example, ammonium acetate, ammonium, sodium hydrogen phosphate, potassium hydrogen phosphate, potassium acetate, sodium acetate. The acids are used above all for adjusting the pH of the baths used in accordance with the invention, which pH is generally between 4 and 7.5, preferably between 4.5 and 6.5.

In addition, the dye baths can still contain the usual electrolytes, dispersants, anti-foaming agent and wetting agents.

The object of the present invention is also a process for dyeing synthetic textile materials with cationic or dispersed dyes. Synthetic textile materials which can be dyed according to the invention are, for example, cellulose ester fibers, such as 2 1/2 cellulose acetate or triacetate fibers, synthetic polyamide fibers, eg those based on ε-caprolactam, adipic acid and hexamethylenediamine, ω-aminoundecanoic acid; aromatic polyamide fibers, which are derived from poly (metaphenyleneisophthalamide), polyacrylonitrile fibers including "Modacryl" fibers, modified acid polyester fibers, and in particular linear polyester fibers. Among these, the fibers of cellulose esters, polyamides and polyesters are preferably dyed with dispersed dyes and the polyacrylonitrile fibers, the fibers of modified acid polyesters and the aromatic polyamide fibers are preferably dyed with dyes cationic.

The term linear polyester fibers should be understood to mean synthetic fibers, which are obtained by condensation of terephthalic acid with ethylene glycol or butylene glycol or isophthalic or terephthalic acid with 1,4-Bis- ( hydroxymethyl) -cyclohexane as well as the copolymers of terephthalic and isophthalic acids and ethylene glycol. The linear polyester hitherto used almost exclusively in the textile industry consists of terephthalic acid and ethylene glycol. The commercial types of acrylonitrile polymers and copolymers are part of the acrylic fibers which can be dyed by the process according to the invention. In the case of acrylonitrile copolymers, the suitable content of acrylonitrile is at least 80 percent by weight, based on the weight of the copolymer. The modified acid polyester fibers are, for example, polycondensation products of terephthalic acid or isophthalic acid, of ethylene glycol and of 1,2- or 1,3-dihydroxy-3- (3-sodiumsulfopropoxy) -propane, 2,3-dimethylol-1- (sodiumsulfopropoxy) -butane, 2,2-bis- (3-sodiumsulfopropoxyphenyl) -propane or 3,5-dicarboxy-benzenesulfonic acid or sulfonated terephthalic acid, 4-methoxybenzene sulfonated carboxylic acid or diphenyl- 4,4′-sulfonated dicarboxylic.

The fiber materials can be mixed with each other in weaving or with other fibers and used as such, eg blends of polyacrylonitrile / polyester, polyamide / polyester, polyester / cotton, polyester / viscose and polyester / wool.

The cationic dyes which are suitable for the process according to the invention can belong to different classes of dyes. In particular, these are the usual salts, for example chlorides, sulphates or metal halides, such as double zinc chloride salts of cationic dyes, the cationic nature of which is provided, for example by carbonium, oxonium group, sulfonium or especially ammonium. Examples of such chromophoric systems are azo dyes, especially monoazo or hydrazone dyes, diphenylmethane, triphenylmethane, methine or azomethine dyes, coumarin, ketonimine, cyanine, azine, xanthene, oxazine or thiazine dyes. Finally, it is also possible to use colored salts from the series of phthalocyanines or anthraquinones with an external onium group, for example an alkylammonium or cycloammonium group as well as colored salts of benzo-1,2-pyran which contain cycloammonium groups.

The dispersed dyes to be used, which are very slightly soluble in water and which are present in the bath for the most part in the form of a fine dispersion, can belong to the most diverse classes of dyes, for example dyes. acridone, azo, anthraquinone, coumarin, methine, perinone, naphthoquinoneimine, quinophthalone, styryl or nitrates.

According to the invention, mixtures of cationic or dispersed dyes can be used.

The cationic and dispersed dyes are preferably used in an amount of 0.5 g to 50 g per liter of bath.

The dyeing process according to the invention can also be used for the whitening of undyed textile materials with optical brighteners suitable for all the substrates indicated above. In this case, polyester or cellulosic fiber materials are preferably treated with optical brighteners dispersed or soluble in water, depending on the nature of the substrate to be treated. The whitening can be combined with a bleaching process.

Optical brighteners can be anionic or cationic or water dispersible and belong to any class of brighteners. In particular, this is coumarin, triazolcoumarin, benzocoumarin, oxazine, pyrazine, pyrenoline, diphenylpyrazoline, stilbene, styrylstilbene, triazolylstilbene, bisbenzoxazolylethylene, stilbene-bis-benzoxazoles, phenylstilbene-benzazene , benzofuran, benzimidazoles and naphthalimides.

It is also possible to use mixtures of optical brighteners according to the invention.

It has often proved advantageous to add to the dyeing or finishing bath, in addition to the graft polymerization products, commercial wetting agents which are stable with respect to alkalis, for example sulfonates of d ester. polycarboxylic acid such as dihexyl sulfosuccinate or dioctyl sulfosuccinate; alkylarylsulfonates having a straight or branched alkyl chain of at least 6 carbon atoms, such as for example dodecylbenzenesulfonates, or preferably alkylsulfonates whose alkyl chain contains from 8 to 20 carbon atoms, such as for example dodecylsulfonates or pentadecylsulfonates. The sulfonates mentioned as wetting agents are generally present in the form of alkali metal salts, in particular however in the form of sodium salts or alternatively of ammonium salts.

The amounts of wetting agents added to the padding bath vary at best between 1 and 10 g, preferably between 1.5 and 5 g, per liter of bath.

The padding baths are best prepared in advance by dissolving or dispersing the dye and by adding the graft polymerization product. Depending on the colorant used, the dye baths may contain other usual additives, for example electrolytes, such as for example sodium chloride or sodium sulfate, alkali or acid as well as urea , oxidants, glycerin, leveling agents, crosslinking agents and usual defoaming agents and / or sodium formate. Optionally, they can also contain a thickening agent, such as for example alginates, starch ether, polyacrylic acid or even carob flour ether.

With the method according to the invention, an increase in the absorption of the dye bath of up to 40% is attained, and this results in rapid fixation by microwaves and also an increase in dye yields. Already, by adding small amounts of the graft polymerization product according to the definition, an increase in the wash-out rate is obtained and then significantly better dye yields.

In addition, uniform and intense dye samples are obtained, which are characterized by a regular appearance of the fabric. Furthermore, the fastnesses of the dyes, such as for example the fastness to light, the fastness to rubbing and the fastness to humidity, are not negatively influenced by the introduction of the defined graft polymerization product.

The object of the present invention is also a bleaching process preferably for cotton with an aqueous padding bath containing the graft polymerization product, a peroxide, the hydroxide of an alkali metal, a surfactant and minus a stabilizer characterized in that the cotton is impregnated with the bleaching bath and the impregnated cotton is subjected to the treatment by means of microwaves.

• (A) un agent d'oxydation inorganique comme p. ex. un peroxyde, des persels tels que le persulfate de sodium, cependant de préférence l'eau oxygénée, notamment sous forme commerciale de solutions aqueuses concentreés,
• (B) l'hydroxyde d'un métal alcalin, de préférence de l'hydroxyde de potassium ou de sodium,
• (C) un ou plusieurs tensio-actifs généralement non-ioniques, éventuelle­ment en mélange avec un ou plusieurs tensio-actifs anioniques tels que des produits d'addition d'alcools gras et/ou d'alkyl-phenols sur un alkylène-oxyde,
• (D) au moins un stabilisateur de peroxyde choisi dans le groupe des esters éventuellement oligomères de l'acide hydroxyethane-1,1-di­phosphonique, d'acides aminopoly(alkylène-phosphoniques), d'acides alkane-polyphosphoniques ou d'acides polyaminocarboxyliques comme p.ex. l'acide diethylène-triamine-pentaacétique et ses sels, en particulier ses sels de magnésium, de composés polyhydroxylés tels que l'acide gluconique et ses sels de métal alcalin ou son γ-lactone et d'un silicate de métal alcalin tel que le silicate de sodium.

The bleaching baths used both in the conventional bleaching processes and in the bleaching process according to the present invention are per se known and described, for example, in European patent 0 082 823 and in Swiss patent applications Nos 3141/85- 7 and 3142 / 85-9. They usually contain

• (A) an inorganic oxidizing agent such as p. ex. a peroxide, persalts such as sodium persulfate, however preferably hydrogen peroxide, especially in the commercial form of concentrated aqueous solutions,
• (B) the hydroxide of an alkali metal, preferably potassium or sodium hydroxide,
• (C) one or more generally nonionic surfactants, optionally in admixture with one or more anionic surfactants such as adducts of fatty alcohols and / or of alkyl phenols on an alkylene oxide,
• (D) at least one peroxide stabilizer chosen from the group of optionally oligomeric esters of hydroxyethane-1,1-diphosphonic acid, aminopoly (alkylene-phosphonic) acids, alkane-polyphosphonic acids or polyaminocarboxylic acids such as, for example, diethylene triamine pentaacetic acid and its salts, in particular its magnesium salts, of polyhydroxylated compounds such as gluconic acid and its alkali metal salts or its γ-lactone and of a silicate of alkali metal such as sodium silicate.

In addition, the bleaching baths can advantageously contain as optional components a hydrotropic agent, eg urea, a magnesium salt, eg MgCl₂ optionally in the form of hexahydrate, a precipitation inhibitor of alkaline earth salts, eg an optionally partially hydrolysed polymaleic acid, an antifoam or deaerating agent such as higher alcohols, in particular isopropanol, n-octanol, ethyl hexanol or trimethyl hexanol and / or commercial silicone oils.

The quantities of whitening preparations which can be added to the padding bath vary at best between 2 and 30 g per liter of bath, preferably be 5 and 20 g / l.

In the following preparation methods and examples, the percentages, when there is no other indication, are given by weight. The quantities relate, for the dyes, to commercial products, that is to say cut, and for the adjuvants, to the pure substances. The five-digit numbers of the Color Index (CI) are taken from the 3rd edition of the Color Index.

Preparation methods Procedure 1:

A solution of 22.5 g of acrylamide, 2.5 g of an adduct of 52 moles of propylene oxide on 1 mole of glycerin, and 0.04 g of potassium peroxydisulfate, in 200 g of water is heated to 50 ° C., with stirring and with nitrogen sweeping, and maintained for 3 hours at this temperature. A solution of 0.03 g of potassium peroxydisulfate in 40 g of water is dropped therein dropwise for 60 minutes, and the very viscous solution is diluted by adding 300 ml of water within 30 minutes . Then the reaction mixture is kept for 5 hours at 50 ° C., then 0.6 g of hydroquinone monomethyl ether and 0.12 g of sodium azothhydride is added thereto, then the mixture is cooled to room temperature while stirring. 565 g of a gel are obtained, the polymer content of which is 4.4%. This gel has a viscosity, measured at 25 ° C, of 112957 mPas.

Procedure 2:

A solution of 71.25 g of acrylamide, 3.75 g of a propylene oxide and glycerin adduct having an average molecular weight of 4200, and 0.09 g of potassium peroxydisulfate in 600 g of a dg is prepared. with water, this solution is heated to 50 ° C. with stirring and with nitrogen sweeping, and it is kept for 3 hours at 50 ° C. The viscosity of the solution gradually increases. A solution of 0.06 g of potassium peroxydisulfate in 120 g of water is dropped therein dropwise over 60 minutes. About 10 minutes after the start of the drip, the viscosity of the solution becomes so high that, for the next 20 minutes, 600 g of water must be added. After the end of the dropwise addition of the potassium peroxydisulfate solution, the solution is still maintained, the viscosity of which continues to increase, at 50 ° C. for 5 hours, while diluting with 400 g of additional water. added in portions. 1.7 g of hydroquinone monomethyl ether are added, the mixture is cooled to room temperature while stirring, and 1794 g of a free-flowing gel are obtained, which has a polymer content of 4.3%. This gel has a viscosity, measured at 25 ° C, of 64,202 mPas.

Procedure 3:

A solution of 71.25 g of acrylamide, 3.75 g of an adduct of propylene oxide and pentaerythritol having an average molecular weight of 3550, and 0.09 g of potassium peroxydisulfate, in 600 g of water is heated to 50 ° C, with stirring and flushing with nitrogen, and kept at 50 ° C for 3 hours. The viscosity of the solution gradually increases. A solution of 0.06 g of potassium peroxydisulfate in 120 g of water is dropped dropwise over the course of 60 minutes. For about 30 minutes after the end of the dropwise addition, the viscosity of the solution increases. 600 g of water are therefore added to it during the following 20 minutes. Then the solution is further maintained, the viscosity of which increases regularly, for 4 hours at 50 ° C., it is then diluted with 400 g of additional water, 3.4 g of triethanolamine are added thereto, it is cooled to room temperature while with stirring, and 1793 g of a still fluid gel are obtained, having a solid content of 4.0%. This gel has a viscosity, measured at 25 ° C, of 75,300 mPas.

Procedure 4:

A solution of 17.8 g of acrylamide, 0.94 g of an adduct of 70 moles of propylene oxide and 6 moles of ethylene oxide over 1 mole of glycerin, and 0.025 g of peroxydisulfate of potassium, in 250 g of water, is heated to 50 ° C., with stirring and with nitrogen sweeping, and maintained for 3 hours at this temperature. The temperature of the solution is raised over 20 minutes to 60-63 ° C, until the viscosity increases significantly, and then cooled to 55 ° C. The solution is maintained, the viscosity of which becomes increasingly high, for 5 hours at 55 ° C. A solution of 0.45 g of chloroacetamide and 0.45 g of hydroquinone monomethyl ether in 177 g of water is then added to the viscous solution, and 446 g of a gel are obtained, the product content of which is graft polymerization is 4.2%. This gel has a viscosity, measured at 25 ° C, of 96,750 mPas.

Procedure 5:

If the adduct indicated in procedure 4 is replaced by another adduct of 53 moles of propylene oxide on 1 mole of trimethylolpropane, 446 g of a gel having a content of 4.2% graft polymerization product. This gel has a viscosity, measured at 25 ° C, of 19,500 mPas.

Procedure 6:

A solution of 17.24 g of acrylamide, 4.31 g of an adduct of 70 moles of propylene oxide on 1 mole of glycerin, and 0.035 g of potassium peroxydisulfate, in 200 g of water , is heated to 50 ° C., with stirring and with nitrogen sweeping, and maintained at this temperature for 4 hours. The solution, whose viscosity continues to increase, is then heated at 55 ° C for 5 hours. A solution of 0.4 g of chloroacetamide and 0.4 g of hydroquinone monomethyl ether in 291 g of water is added to the gel, and 513 g of a gel having a polymer content of 4.2 are obtained. %. This gel has a viscosity, measured at 25 ° C, of 25,750 mPas.

Procedure 7:

A mixture of 15.1 g of acrylamide, 6.5 g of an adduct of 70 moles of propylene oxide on 1 mole of glycerin, and 0.025 g of potassium peroxydisulfate, in 200 g of water , is heated to 50 ° C., with stirring and with nitrogen sweeping, and maintained for 3 hours at this temperature. The solution, whose viscosity continues to increase, is then heated at 55 ° C for 5 hours. A solution of 0.4 g of chloroacetamide and 0.4 g of hydroquinone monomethyl ether in 291 g of water is added to the gel, and 512 g of a gel having a polymer content of 4 are obtained. , 2%. This gel has a viscosity, measured at 25 ° C, of 16,300 mPas.

Procedure 8:

A mixture of 13 g of acrylamide, 8.7 g of an adduct of 70 moles of propylene oxide on 1 mole of glycerin, and 0.015 g of potassium peroxydisulfate, in 150 g of water, is heated, with stirring and with nitrogen sweeping, to 50 ° C., and maintained at this temperature for 4 hours. The solution, which becomes more and more viscous, is then heated for 2 hours at 65 ° C, and again for 3 hours at 60 ° C. A solution of 0.4 g of chloroacetamide and 0.4 g of hydroquinone monomethyl ether in 347 g of water is added to the gel, and 519 g of a gel which has a polymer content of 4 are obtained, 2%. This gel has a viscosity, measured at 25 ° C, of 15582 mPas.

Application examples Example 1: Dyeing of cotton

10 g d'un produit de polymérisation par greffage préparé selon le mode opératoire 2,
2 g d'un agent mouillant,
60 g de sulfate de sodium anhydre
15 g de bicarbonate de sodium
5 g d'acide méta-nitrobenzènesulfonique (sel de sodium)A cotton corduroy fabric weighing 280 g / m² is impregnated with a scarf at 25 ° C with an aqueous solution containing per liter:

10 g of a graft polymerization product prepared according to procedure 2,
2 g of a wetting agent,
60 g anhydrous sodium sulfate
15 g sodium bicarbonate
5 g meta-nitrobenzenesulfonic acid (sodium salt)

For an immersion time of 1.6 seconds and a cylinder pressure of 1.8 bar, a take-up rate of 102% is obtained.

The substrate is then subjected to the action of the microwave field of a slit-source waveguide powered by a magnetron microwave generator with a frequency of 2450MHz (mega hertz) and a power 2500 watts. The strip of fabric impregnated with dye baths passes at a distance of 12.2 cm from the waveguide, the speed of movement being adjusted so as to achieve a residence time in the microwave field of 12 seconds. After washing, rinsing and drying, a burgundy shade dye is obtained which is characterized by the regular appearance of its tablecloth.

Example 2: Tincture of PES / CO>

0,2 g du colorant de formule (103)
10 g d'un produit de polymérisation par greffage préparé selon le mode opératoire 2
3 g d'un agent mouillant
10 g d'un agent épaississant à base d'acide polyacrylique
50 g d'urée
15 g de bicarbonate de sodiumA mercerized polyester / cotton gabardine fabric (50:50) weighing 160 g / m² is impregnated with a scarf at 25 ° C with a bath which contains, per liter:

0.2 g of the dye of formula (103)
10 g of a graft polymerization product prepared according to procedure 2
3 g of a wetting agent
10 g of a thickening agent based on polyacrylic acid
50 g urea
15 g sodium bicarbonate

For an impregnation time of 2 seconds and a cylinder pressure of 1.8 bar, a bath absorption rate equal to 95% is obtained.

The tissue is then irradiated continuously using microwaves of 2500 watts power (frequency of 2450 MHz) for 9 seconds. After this treatment, the substrate is rinsed cold and then washed at 85 ° C and then rinsed again in the cold.

A very shiny turquoise dye is obtained, characterized by very good leveling.

EXAMPLE 3 Dyeing of the Wool

10 g d'un produit de polymérisation par greffage préparé selon le mode opératoire 2
50 g d'urée
5 g d'un agent épaississant de commerce à base d'acide polyacrylique.A woolen cloth is impregnated in a scarf at 25 ° C with a bath, which contains, per liter

10 g of a graft polymerization product prepared according to procedure 2
50 g urea
5 g of a commercial thickening agent based on polyacrylic acid.

The pH is fixed at 6.5 using acetic acid.

The take-up rate obtained is 110% calculated on the weight of the dry fabric (cylinder pressure: 1.5 bar).

The fabric is then irradiated continuously for 12 seconds using 2500 watt microwaves (frequency 2450 MHz), then rinsed and dried.

An intense blue coloration is obtained, characterized by its very good leveling.

EXAMPLE 4 Dyeing of the Polyacrylic Fibers

10 g d'un produit de polymérisation par greffage préparé selon le mode d'opération 2
10 g d'un agent épaississant du commerce
5 g de diéthanolamide d'acides gras du coprahA knit of polyacrylic fibers is impregnated with a scarf at 25 ° C using an aqueous solution, which contains per liter

10 g of a graft polymerization product prepared according to procedure 2
10 g of a commercial thickening agent
5 g coconut fatty acid diethanolamide

The pH is brought to 4.5 by means of acetic acid.

For an immersion time of 2 seconds and a cylinder pressure of 1.8 bar, the absorption rate of the bath is equal to 108%.

The fabric is then subjected to continuous treatment with a microwave power of 2500 watts (frequency 2450 MHz) for 14 seconds, then washed at 70 ° C. and then rinsed cold.

We obtain a very beautiful brown coloration characterized by its very beautiful unison and its regular appearance.

Example 5: Azuration of cotton in the bleaching bath.

8 g d'un produit de polymérisation par greffage préparé selon le mode opératoire 2
2 g de silicate de sodium
8 g de soude caustique
40 g d'eau oxygénée 35 %,
5 g d'un mélange d'esters monomères et oligomères méthyliques de l'acide hydroxyéthane-1,1-diphosphonique (solution aqueuse à 50 %).A cotton cloth having previously undergone a scouring treatment is impregnated with a scarf at 25 ° C. with a bath which contains, per liter

8 g of a graft polymerization product prepared according to procedure 2
2 g sodium silicate
8 g caustic soda
40 g of 35% hydrogen peroxide,
5 g of a mixture of monomeric esters and methyl oligomers of hydroxyethane-1,1-diphosphonic acid (50% aqueous solution).

The absorption rate of the bath calculated on the weight of dry matter is 103% for a cylinder pressure of 1.2 bar and an impregnation time of 2 seconds.

The impregnated fabric is then irradiated continuously for 12 seconds using microwaves with a power of 2500 watts (frequency 2450 MHz). Following this last treatment, the tissue is rinsed at 50 ° C and then at 25 ° C is then dried.

A very good optical brightening effect is obtained.

EXAMPLE 6 Azuration of the Polyester

5 g d'un produit de polymérisation par greffage préparé selon le mode opératoire 2
10 g d'un produit de copolymérisation constitué d'amide acrylique et l'acide 2-acrylamido-2-méthyl propanesulfonique (1:1)
5 g du sel d'ammonium de l'ester sulfate acide du produit d'addition de 2 moles d'oxyde d'ethylène sur 1 mole de nonylphenol.A polyester fabric is impregnated with a scarf at 25 ° C using a bath which contains, per liter

5 g of a graft polymerization product prepared according to procedure 2
10 g of a copolymerization product consisting of acrylic amide and 2-acrylamido-2-methyl propanesulfonic acid (1: 1)
5 g of the ammonium salt of the acid sulfate ester of the addition product of 2 moles of ethylene oxide on 1 mole of nonylphenol.

The carrying rate calculated on the weight of dry matter is 80% for an immersion time of 1.2 seconds.

The substrate is then treated continuously using microwaves with a power of 2500 watts (frequency 2450 MHz) for a period of 17 seconds, then rinsed and dried.

We obtain a very beautiful optical brightening effect.

EXAMPLE 7 Bleaching of Cotton

An ecru tubular cotton knit weighing 280 g / m² is impregnated with the scarf using an aqueous bath, which contains per liter
8 g of a graft polymerization product prepared according to procedure 2
5 g of a mixture of monomeric esters and methyl oligomers of hydroxyethane-1,1-diphosphonic acid (50% aqueous solution)
2 g sodium silicate
8 g caustic soda and
40 g of hydrogen peroxide 35%

For an impregnation time of 2.5 seconds and a cylinder pressure of 2.0 bars, a bath absorption rate of 130% is obtained (calculated on the weight of the dry matter).

The impregnated fabric is then subjected for 15 seconds to microwave irradiation (frequency 2450 MHz / power 2500 watts).

After rinsing at 95 ° then 25 ° C, the fabric is dried.

A very good whitening effect is obtained.

Example 8: Cotton sizing

A mercerized cotton poplin is impregnated at 25 ° C with a scarf with an aqueous bath which contains per liter
50 g of N, N′-dimethylol-dihydroxyethylene-urea
2.0 g of a mixture consisting of a polyethylene wax and an ethoxylated derivative of a fatty amine
18 g Catalyst consisting of magnesium chloride
10 g of a polymerization product, by grafting prepared according to procedure 2
10 g of the ammonium salt of the acid sulphate ester of the addition product of 2 moles of ethylene oxide over 1 mole of nonylphenol.

For an immersion time of 1.8 seconds and a cylinder pressure of 1.4 bar, we obtain a bath absorption rate equal to 98% calculated on the weight of dry matter.

The substrate thus impregnated is then subjected to continuous treatment using microwaves with a power of 2500 watts (frequency 2450 MHz) for a time of 25 seconds.

A very good wrinkle-resistant effect is obtained.

Claims (15)

1. A process for dyeing or finishing textile materials, characterized in that the textile materials are impregnated with a dye or aqueous finish bath, which additionally contains a graft polymerization product obtained from an adduct of an alkylene oxide on an aliphatic alcohol at least trivalent having 3 to 10 carbon atoms and acrylamide or methacrylamide, and in that the operation is then carried out fixing the dye or primer continuously using a microwave treatment for 5 to 30 seconds. 2. Method according to claim 1, characterized in that the padding bath contains a graft polymerization product obtained from an addition product of 4 to 100 moles of propylene oxide on a trivalent to hexavalent alkanol, having 3 to 6 carbon atoms, and acrylamide or methacrylamide. 3. Method according to one of claims 1 and 2, characterized in that the graft polymerization product contains from 2.5 to 50% by weight of the defined addition product and from 50 to 97.5% by weight of 'grafted acrylamide or methacrylamide, related to the graft polymerization product. 4. Method according to claim 3, characterized in that the graft polymerization product contains from 2.5 to 30% by weight of the adduct and from 70 to 97.5% by weight of grafted acrylamide, based on graft polymerization product. 5. Method according to one of claims 1 to 4, characterized in that the padding bath contains a graft polymerization product obtained from acrylamide and an addition product of 40 to 80 moles of oxide of propylene on 1 mole of glycerin. 6. Method according to claim 5, characterized in that the graft polymerization product contains from 4 to 20% by weight of the addition product of 40 to 80 moles of propylene oxide on 1 mole of glycerin and 80 to 96 % by weight of grafted acrylamide, based on the graft polymerization product. 7. Method according to one of claims 1 to 6, characterized in that the padding bath contains the graft polymerization product in an amount of 5 to 40 g, preferably from 8 to 20 g, per liter, in the form of an aqueous solution of 3 to 10%. 8. Method according to one of claims 1 to 7, characterized in that the fixing of the dye or finish, carried out by means of microwave, has a duration of 5 to 18 seconds. 9. Method according to one of claims 1 to 8, characterized in that dyed textile materials consisting entirely or partially of cellulose fibers with substantive or preferably reactive dyes. 10. The method of claim 9, characterized in that the padding bath contains, in addition to the graft polymerization product, a wetting agent stable to alkalis. 11. Method according to one of claims 1 to 8, characterized in that dyed textile materials consisting entirely or partially of natural or synthetic polyamide fibers with anionic dyes. 12. Method according to one of claims 1 to 8, characterized in that dyed textile materials consisting entirely or partially of polyesters with dispersed dyes. 13. Method according to one of claims 1 to 8 characterized in that dyed textile materials consisting entirely or partially of polyacrylonitrile fibers with cationic dyes. 14. Method according to one of claims 1 to 13 characterized in that the absorption rate of the bath in the padding step is between 60 and 200%, preferably 85 and 140%. 15. A bleaching process, preferably for cotton, characterized in that the textile substrate is impregnated by padding with an aqueous bath, which contains an inorganic oxidizing agent, preferably a peroxide, a graft polymerization product obtained at from an adduct of an alkylene oxide on an aliphatic alcohol at least trivalent having 3 to 10 carbon atoms and acrylamide or methacrylamide, the hydroxide of an alkali metal, a tensio- active and at least one stabilizer, and in that a treatment of the textile substrate is then carried out in the microwave for 5 to 30 seconds.