EP1021608B1 - Finishing for jeans material - Google Patents

Abstract

An anti-yellowing finishing process for textile, blue-dyed, anti-back-stained, stone-washed and/or bleached denim articles is characterised in that the textile materials are finished in an aqueous medium with protonated fatty acid ester aminoamides and/or hydroxyaminoamides of N-(β-hydroxyethyl)-ethylene diamine, in which the fatty acid radicals contain 12 to 22 carbon atoms, and which are protonated with at least 1.5 equivalents ortho-phosphoric acid per equivalent of basic amino groups.

Description

From EP-A-0230910 textile treatment agents are known which are produced by reacting C _10-22 fatty acids with polyamines and neutralization with a non-oxidizing inorganic acid, with aminoethyl ethanolamine being preferred as the polyamine and phosphoric acid being preferred among the inorganic acids and described in the examples. The acid is used in a defined amount, which is 0.7 to 1.3 acid equivalents per amine equivalent (EP-A-0230910, page 3, line 17), ie in an amount necessary for the dibasic phosphorous acid to achieve an acidic pH -Not enough. If this acid is used in such amounts that an acidic dispersion is formed, this dispersion is unstable and soon separates into two phases of different concentration when standing, which is unsuitable for practical use (production, sale, storage, use). In EP-A-0230910, page 3, line 6, also mentions good odor results. It should be noted here that the phosphorous acid itself is odorless, but in the presence of the other products it emits a strong, bad odor under acidic conditions, which is also unsuitable in practice. For example, use in alkaline wash liquors or thereafter on page 3 in lines 34-35 is mentioned.

EP-A-0230910 is mainly concerned with preventing discoloration or yellowing Textile material, which after finishing, e.g. with a plasticizer, through a final Heat treatment, in particular by a thermosol treatment, as is customary for synthetic fibers, is caused immediately, so that the heat-set material more yellowish or brownish appears.

DE-A-196 03 401 discloses preventing denim from yellowing when stored. According to DE-A-196 03 401, a peroxy compound is applied in conjunction with a plasticizer from an aqueous solution for this purpose. The plasticizers can include condensation products of> C ₁₀ fatty acids with alkanolamines. The condensation products can also be quaternized.

US-A-4 155 710 discloses the use of special quaternized N-oxypropylation products of N, N-bis- [2- (C _8-18 fatty acid acylamino) ethyl] amine to prevent fading of denim. The compounds are applied in aqueous form

"Yellowing of indigo jeanswear", P. Maier et al., Melliand Textile Reports 11/1996, pages 786-787 discloses yellowing-reducing fatty acid condensation products.

A significantly different problem, however, is yellowing, which takes a long time after completion the textile goods which have not been yellowed due to the different treatment stages for their manufacture occurs, and only in so-called "jeans" goods, which essentially contain cellulose (generally containing cotton), woven or knitted in certain ways and on are dyed in a certain way and possibly further processed.

The fabrics used for jeans (denim fabrics) are generally those made from dyed, mostly warp-dyed warp yarn and non-dyed weft yarn, which are mostly woven or knitted so that the dyed part on the right side of the fabric predominates while the undyed part on the left side of the fabric predominates, for example by twill or twill weaving technology (eg ¹ - ₂ or ¹ - ₃ ) or by any other suitable weaving or knitting technique. Indigo dyes are usually used for dyeing, such as Color Index Vat Blue 1 or similar dyes. Through various lightening treatments, such as scrubbing, bleaching and / or washing, the jeans article can be given the familiar, fashionable, worn look. It has now been found, however, that the denim articles (jeans articles) treated in this way turn yellow over time, for example due to the action of constituents of the ambient air, such as ozone, nitrogen oxides, etc., especially in combination with daylight. The yellowing could indeed be removed from the assembled and yellowed goods by suitable washing; such washing operations are normally not carried out by the ultimate seller. Attempts have been made to delay this yellowing effect by using certain equipment, but after a certain period of time which is relatively short for storage and / or sales purposes, the undesirable yellowing occurs. There is therefore a desire to use agents which have a stronger or longer anti-yellowing effect, so that the goods can be stored and / or exhibited for a longer period without yellowing damage and can be offered for sale without any problems.

It has now been found that, using the phosphates defined below, from salt formation of the defined amino compounds with at least 1.5 equivalents of ortho-phosphoric acid per Equivalent basic amino groups, whose dispersions are very stable even under acidic conditions are a surprisingly good improvement in the anti-yellowing effect against these Storage yellowing on jeans goods can be achieved.

The invention relates to the use of the defined phosphates for inhibiting said Yellowing, or the process for anti-yellowing equipment with it

The invention thus relates to a process for the anti-yellowing finishing of textiles, indigo-dyed, washed and / or scrubbed and / or bleached denim articles, the is characterized in that with protonated fatty acid esteraminoamides and / or -hydroxyaminoamides des N- (β-hydroxyethyl) ethylenediamine, in which the fatty acid residues each 12 to 22 Contain carbon atoms, and with at least 1.5 equivalents of ortho-phosphoric acid per Equivalent basic amino groups are protonated, equipped from an aqueous medium.

The protonated fatty acid esteraminoamides and / or hydroxyaminoamides to be used according to the invention are advantageously used in the form of protonated condensates of the C _12-22 fatty acids mentioned with the N- (β-hydroxyethyl) ethylenediamine.

Suitable fatty acids are any conventional, preferably linear, fatty acids with 12 to 22 Carbon atoms, preferably saturated fatty acids, e.g. Lauric acid, myristic acid, palmitic acid, Stearic acid, arachidic acid and behenic acid. Both individual acids and technical ones can be used Acids (acid mixtures) are used, e.g. hydrogenated tallow fatty acid. Among the above Acids are those with 14 to 18 carbon atoms, and also technical mixtures of these Acids, preferred.

The condensates [i.e. Acylation products of N- (β-hydroxyethyl) ethylenediamine] can per se known way by condensation of the fatty acids mentioned with the N- (β-hydroxyethyl) ethylene diamine be produced under water-releasing conditions. For their manufacture advantageously 1 to 2.5, preferably 1.2 to 2.2, in particular per mole of N- (β-hydroxyethyl) ethylenediamine 1.4 to 2 mol of fatty acid used. The condensation is expediently carried out in anhydrous Medium, most simply in the absence of solvents, e.g. at temperatures in the range of 140 to 220 ° C, advantageously under an inert atmosphere (e.g. under nitrogen) and / or optionally under reduced pressure. In addition to the above monoamides, the above Condensates, depending on the molar ratio and condensation conditions, optionally further amides, namely diamides, i.e. at least one fatty acid diamide and / or at least one fatty acid ester diamide of N- (β-hydroxyethyl) ethylenediamine. The acylation product thus prepared hereinafter referred to as "amino condensate" - contains basic in addition to the amide groups Amino groups, which are now at least partially combined with phosphoric acid Protonated amino condensate phosphoric acid salt. The proportion of protonatable basic Amino groups in the amino condensate can be determined by determining the amine number. The Amine number is advantageously in the range from 30 to 100, preferably 50 to 70 mg KOH per g amino condensate. Per mole equivalent of basic amino groups (or amino nitrogen) 0.5 to 1.1, preferably 0.8 to 1, mol of phosphoric acid are advantageously used in the amino condensate used.

The phosphoric acid is advantageously used in the form of an aqueous solution, for example - calculated as orthophosphoric acid H ₃ PO ₄ - as a 1 to 10% by weight solution.

A hydrophilic, nonionic surfactant is advantageously added, preferably with an HLB> 12, for example an adduct of 10 to 70 mol, preferably 25 to 60 mol, of ethylene oxide and 1 mol of C _9-24 fatty alcohol. Suitable fatty alcohols are any conventional, preferably saturated alcohols having 9 to 24, preferably 11 to 18 carbon atoms; for example, linear fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or else branched fatty alcohols, such as synthetic alcohols, for example having 9 to 15 carbon atoms, preferably 11 to 15 carbon atoms. 1 to 30, preferably 2 to 15 parts by weight of surfactant are advantageously used per 100 parts by weight of amino condensate phosphoric acid salt. According to an advantageous procedure, the non-ionic surfactant is mixed with the amino condensate before the addition of the phosphoric acid and then the mixture, preferably as a melt, is advantageously added to the aqueous phosphoric acid. The amount of water in the aqueous phosphoric acid is advantageously chosen so that the concentration of amino condensate phosphoric acid salt in the aqueous preparation is in the range from 5 to 40, preferably 10 to 30,% by weight. The pH of the aqueous dispersions corresponds to the amounts of the components used, especially phosphoric acid, and is predominantly 6 6 in these dispersions, advantageously in the range from 2 to 6, preferably 2 to 4.5, in particular 2.5 to 4.5 . The "amino condensate phosphoric acid salt" here means the reaction product of the phosphoric acid described above with the entire amino condensate.

The above-mentioned fatty acid esteraminoamides and / or fatty acid hydroxyaminoamides protonated with phosphoric acid, advantageously in the form of the protonated amino condensates mentioned, preferably as aqueous formulations as described, can be used for finishing anti-yellowing be used.

The substrates are generally made up from indigo dyed denim Articles (jeans goods) which are treated by known, customary methods, in particular by washing and / or scouring (generally with pumice stones) and / or bleaching in the typical jeans look have been lightened.

The well-known vat dyes are suitable as dyes for dyeing the warp yarn Indigo series, primarily blue dyes, and possibly also indigo-like sulfur dyes, the latter e.g. in combination with blue vat dyes from the Indigo range. For weaving or knitting the yarns are generally sized so that the made-up goods before the Whitening mostly still contains the sizing agent. If necessary, the Fabric with a lubricant, e.g. a sewability improver. These tools can during the whitening treatment, e.g. by washing.

The ready-made denim goods can be made using known processes, tools and Machines - by washing and / or scrubbing and / or bleaching - are brightened.

Known detergents can be used for washing, for example anionic or nonionic. If desired, an enzymatic hydrolytic treatment, for example with hydrolases (for example cellulases), can be carried out at the same time. If an enzymatic treatment is carried out at the same time, non-ionic detergents are advantageously used, for example, optionally end-capped adducts of ethylene oxide and optionally propylene oxide with high molecular weight fatty alcohols, primarily adducts of 5 to 50 moles of ethylene oxide and optionally propylene oxide (with ethylene oxide preferably predominating) to one mole of C _9-18 fatty alcohol.

If desired, additives such as those for desizing can be used for washing can be used, e.g. Sequestering agents - for example polycarboxylic acids, such as polyacrylic acids and their combinations with saccharides or non-polymeric polycarboxylic acids, e.g. Citric acid, Gluconic acid, NTA, EDTA - and / or enzymes (e.g. α-amylases or cellulases) - as they are As is known, biocatalysts can be used for desizing. Such sequestrants are e.g. described in EP-A 0465286, 0465287 and 0433010; suitable enzymes are e.g. in "Textilbetrieb" 1983/07, Volume 101, page 44.

After desizing, if necessary, a scrubbing process can be combined with an enzymatic hydrolytic treatment. Can rub on known abrasives are used, primarily pumice stones or additives with an analog effect.

After desizing and / or after scrubbing, a washing process can, if desired Prevention of back pollution (anti back-staining) or removal of scouring residues be switched on.

The washing process and / or the scrubbing process and, if desired, the hydrolysis process and / or Washing process, if necessary, can be repeated several times to increase the effect.

Known bleaching agents can be used for bleaching, e.g. Oxidizing agents, reducing agents and / or enzymes.

Known oxidizing bleaches, e.g. chlorine, e.g. in Form of hypochlorite (easiest in the form of KClO, e.g. as Javel water), or peroxides like e.g. Hydrogen peroxide, or other per-compounds such as e.g. Potassium permanganate, or suitable Enzymes.

Any reducing agents, such as those used for reducing, are generally suitable for reductive bleaching vat dyes are commonly used in the leuco form, e.g. reducing saccharides, primarily aldose, e.g. Mono- and oligosaccharides.

The treatments mentioned by washing and / or scrubbing and / or bleaching can be combined in one or several stages and / or repetitions. Generally, in the Technique two to six, preferably three or four, treatments carried out among themselves can be the same or different. For example, washed (desized) in a first stage in one or more subsequent stages, e.g. with or without enzymatic treatment be bleached. Abrasion treatment, e.g. with pumice stones, can be in any of these Treatment stages are carried out, preferably together with cellulases.

After the last of these treatment stages, in the same sequence and in the same apparatus, the final treatment according to the invention with the amino condensate phosphoric acid salt defined above respectively.

The treatment according to the invention with the amino condensate phosphoric acid salts defined above is advantageously carried out using an extraction process from an aqueous medium, e.g. with a fleet length as well used for the previous treatments, e.g. 1: 4 to 1:30, preferably 1: 6 to 1:20, where the amino condensate phosphoric acid salts preferably in the form of aqueous dispersions as above described, used. The amino condensate phosphoric acid salts are conveniently in appropriate concentrations based on the substrate used, preferably in a concentration in the range of 0.02 to 4, particularly preferably 0.1 to 2% by weight, based on the dry substrate. The treatment can be carried out under conditions which are conventional per se, e.g. in the temperature range of 15 to 95 ° C, preferably 30 to 60 ° C, and at pH in the acidic to weakly alkaline range, e.g. in the pH range from 3 to 8, advantageously in the pH range from 3 to 7, preferably 4 to 7; are there generally acidic pH, i.e. pH <7, preferred. The pH value can be known Acids, bases and / or buffers are set, e.g. with phosphoric acid, acetic acid, sodium carbonate and / or phosphoric acid mono- or disodium salt. The duration of treatment can be arbitrary vary and will generally the substrate, the equipment used, the product used and chosen according to the desired effect, e.g. in the range of 10 minutes to 1 hour, preferably 15 to 30 minutes, after which the treated goods are removed from the machine and can be suitably dried, e.g. in a drying drum (Tumbler), e.g. at 40 to 80 ° C, or in the air.

The jeans articles treated in this way are characterized by a surprisingly good and long resistance against yellowing, especially as caused by air components (ozone, nitrogen oxides etc.), especially with the participation of daylight.

In the following examples, parts are parts by weight and percentages are percentages by weight; the Temperatures are given in degrees Celsius. "C.I." stands for "Color Index", "kNU" stands for "kilo NOVO Units "and" GTU "stand for" GENENCOR Textile Units ".

example 1

700 parts of stearic acid are heated to 100 ° C. under nitrogen. When this temperature is reached is, 160 parts of N- (β-hydroxyethyl) ethylenediamine are added within 60 minutes and it is on Heated 180 ° C, the condensation reaction with elimination of water, which distilled off is used. 30 minutes after the addition of amine, the pressure is evacuated to 140 mbar and during Condensed for 2 hours under these conditions. The amine number of the condensation product obtained is 62 mg KOH per g condensate. A total of 50 parts of distillate are obtained. Now is cooled to 80 ° C and, after the addition of 60 parts of stearyl poly (40) ethylene glycol ether, is the melt obtained from 70-80 ° C. to a solution of 100 parts of ortho-phosphoric acid (86%) poured in 3130 parts of water from 60 - 70 ° C. After 2 hours at 70 - 80 ° C it is opened Cooled to room temperature. It becomes a stable, white dispersion that can be easily diluted with water obtained, which has a pH of 3.

Application example

1) Entschlichten

2) Scheuern (stone wash)

3) Waschen (anti back-staining)

4) Bleichen

5) Vergilbungshemmende Ausrüstung.

5-step process:

1) Desizing

2) rubbing (stone wash)

3) washing (anti back-staining)

4) bleaching

5) Anti-yellowing equipment.

5 kg of a denim article in the form of (with C.I. Vat Blue 1) indigo-dyed blue jeans are placed in one Front load washing machine D'HOOGE 80 G (rotating drum of 70 cm diameter) given. 50 liters of water at 50 ° C are filled into the machine. After adding 0.3 g / l nonylphenol poly (9) ethylene glycol ether (Wetting agent) and 1 g / l α-amylase of 130 kNU per g (AQUA-ZYME 120L from NOVO) and checking the pH to 6.0 ± 0.5, is heated to 60 ° C and the washing machine is started at 30 rpm. After 15 minutes the bath is drained and the machine is refilled with cold water to the same level. Now it is at 40-45 ° C heated and the pH is adjusted to 5.5 ± 0.2 with a little acetic acid. In addition, 2.5 kg (50% by weight) pumice stones and 25 g (0.5% by weight) acid cellulase from 6500 GTU per g (INDIAGE SUPER GX from GENENCOR) added, the pH is raised again 5.5 checked and the machine is now run for 60 minutes at 40-45 ° C at 30 rpm. Then the bath is drained, the goods are rinsed once at 70 - 80 ° C and then the Refill the machine with water to the same level. There will be 10 g of dodecylbenzenesulfonic acid Sodium salt is added and the machine is run at 60 ° C for 10 minutes. Now the bath is drained and it is rinsed once at 70 - 80 ° C. Then the machine refilled with water to the same level and heated to 40 ° C. Then the pH adjusted to 8.0 ± 0.2 with sodium carbonate and enough Javel water is added that 2 g / l active choir can be titrated. After 15 minutes at 40 ° C it becomes warm (40 ° C) and cold once (Room temperature) rinsed, then filled up again with water to the same level and up 40 ° C heated. After checking the pH to 5-6 with phosphoric acid, 150 g of dispersion added according to Example 1 and it is treated for 20 minutes at 40 ° C. Then the bathroom drained, the denim fabric is unloaded and dried at 70 - 80 ° C in a tumbler.

The goods equipped in this way are highly protected against yellowing caused by the ambient air can be stored in the open air for a long time without significant annoying yellowing.

Claims (10)

1. Process for the yellowing-inhibiting finishing of textile, indigo-dyed, washed and/or stone-washed and/or bleached denim articles, characterized in that the finishing is carried out from aqueous medium with protonated fatty acid esteraminoamides and/or hydroxyaminoamides of N-(β-hydroxyethyl)-ethylenediamine, in which the fatty acid radicals each contain from 12 to 22 carbon atoms, and which are protonated with at least 1.5 equivalents of ortho-phosphoric acid per equivalent of basic amino groups.
2. Process according to Claim 1, characterized in that the protonated fatty acid esteraminoamide and/or hydroxyaminoamide is employed in admixture with at least one fatty acid diamide of N-(β-hydroxyethyl)-ethylenediamine and/or fatty acid esterdiamide of N-(β-hydroxyethyl)-ethylenediamine, in which the fatty acid radicals each contain from 12 to 22 carbon atoms.
3. Process according to one of Claims 1 or 2, characterized in that there is employed an acylation product of N-(β-hydroxyethyl)-ethylenediamine with at least one C_12-20-fatty acid, protonated with at least 1.5 equivalents of ortho-phosphoric acid per equivalent of basic amino groups.
4. Process according to one of Claims 1 to 3, characterized in that there is employed an acylation product protonated with from 0.5 to 1.1 mol of phosphoric acid per mole-equivalent of basic amino groups in the aminocondensate.
5. Process according to one of Claims 1 to 4, characterized in that, in addition, a hydrophilic, nonionogenic surfactant is employed.
6. Process according to one of Claims 1 to 5, characterized in that the products protonated with phosphoric acid are employed in the form of an aqueous dispersion.
7. Process according to Claim 6, characterized in that the products protonated with phosphoric acid are employed in the form of an aqueous dispersion having a pH of from 2 to 6.
8. Process according to one of Claims 1 to 7, characterized in that the finishing is carried out at pH < 7.
9. Process according to one of Claims 1 to 8, characterized in that the denim articles to be treated have been subjected to bleaching.
10. Process according to one of Claims 1 to 9, characterized in that the denim articles to be treated have been subjected to at least one enzymatic treatment.