DE10153295A1 - Temporary finishing of textile, especially synthetic textile, useful for woven, knitted or nonwoven fabric, e.g. clothing, involves surface treatment with hydrogel - Google Patents

Abstract

Method for especially temporary finishing of textiles, especially synthetic textiles, comprises applying a hydrogel to the surface of the textile, especially its fibers. Independent claims are also included for the following: (1) Textiles, especially synthetic textiles, treated in this way; (2) The use of hydrogels (I), which especially are micro- and nano-scale hydrogels, optionally in cationically modified form, for temporary finishing of textiles, preferably synthetic textiles, especially textile clothing; (3) The use of (I) on such textiles as matrix system for moisture absorption, especially with swelling of (I); (4) The use of (I) in laundry and/or other detergents, e.g. laundry after-treatments, especially rinses, sprays or ironing aids; (5) Laundry and/or other detergents, e.g. laundry after-treatments, especially rinses, sprays or ironing aids, containing (I), especially as aqueous dispersion.

Description

The present invention relates to a method for dyeing textiles, especially textile clothing. The present invention further relates to a process for finishing textiles, in particular textile clothing, with matrix or depot systems, the coloring substances contain. Furthermore, the present invention relates to a method for Color refreshment or color intensification of textiles, in particular during a washing and / or post-treatment step.

Likewise, the present invention relates to the after Processed or obtainable textiles according to the invention.

Furthermore, the present invention has compositions especially dispersions, preferably aqueous dispersions, of coloring Subject matter containing matrix and / or depot systems. The present invention also relates to the use of these Composition, especially dispersions, preferably for coloring Textiles, in particular textile clothing, or for finishing (Equipment) of textiles, especially textile clothing, with matrix or Depot systems that contain coloring substances or to refresh the color and / or color intensification of textiles, especially in a washing machine and / or post-treatment process.

The present invention further relates to the matrix or depot systems themselves, which contain the coloring substance (s).

Following the permanent dyeing of textiles today various additives for sealing the dye applied, but which with increasing number of wash cycles lose protective effect. Therefore despite gentle and modern detergents (UWM, Color detergents, mild detergents etc.) especially when washing several times colored, d. H. non-white textiles, color retention and color freshness special problems.

Firstly, due to the swelling of the fibers during the washing process Dye molecules are released, which leads to a gradual fading of the Lead color intensity. On the other hand, e.g. B. detergents containing bleach lead to color fading due to oxidation processes or Deposits of different substances, such as B. of metal ions, a Make the color matt. Particularly inexpensive textiles with subject to reduced or poor (coloring) quality Color bleeding processes, which are additionally caused by photolytic degradation processes when worn can be reinforced. So suffer particularly dark colored, z. B. blue and black textiles significant throughout their life cycle Color minimization. So it may be necessary, especially for dark colored ones Initiate color-refreshing measures for textiles.

It is known from the prior art to add textiles directly of dyes to dye the wash liquor. For example, the DE 198 26 632 C2 a method for treating laundry in a essential uniform, non-white color, for one wash a colored detergent together with a batik color in the wash water Color the laundry as well as a coloring salt with a ratio of batik color too Color detergent 0.05 to 0.2 and with a ratio of coloring salt too Color detergent 0.5 to 1.5 is added. The disadvantage here is that relative large concentrations of color are used in the detergent to compensate for the large loss of color in the wash liquor. On Another disadvantage is that the color is not always sufficient Has affinity for the fibers to be treated or dyed.

It is therefore an object of the present invention to provide a system generate or provide a method to textiles, in particular textile clothing, dye. Such a procedure should also be used Color refreshment or color intensification of colored textiles, d. H. textiles non-white color.

Another object of the present invention is a system to generate or provide a method to textiles, in particular to equip or equip textile clothing with coloring substances, d. H. to color. Such a system or method should in particular also for especially subsequent color refreshment or Color intensification of textiles suitable for non-white color; at such Color refreshment or color intensification should especially the original color of the Textiles e.g. B. in a washing and / or post-treatment step Dyes are strengthened or regenerated. It should - compared to Application of the pure coloring substance in a treatment solution - the Concentration of coloring substance can be significantly reduced and a high affinity of the system for the textiles to be treated to be guaranteed.

The applicant has surprisingly found that the Invention underlying problem can be solved by looking at Textiles or textile fibers, in particular in the form of textile clothing Matrix and / or depot system, which has at least one coloring substance contains, applies.

The present invention relates to a process for dyeing Textiles, especially textile clothing, in which the textile Surface, in particular the fibers of the textiles, a matrix and / or depot system, which contains at least one coloring substance is applied.

Such a method is suitable both for dyeing textiles in general, in particular also for (subsequent) color refreshment or Color intensification of colored or non-white textiles.

According to the invention, the term “textiles” means in particular both fibers and finished textile products (e.g. fabrics, knitted fabrics, nonwovens etc.), for example as a substance or as an already processed product (e.g. Garment). The textiles can be made from any known materials, such as in particular any natural or synthetic materials, e.g. B. cotton, linen, silk, hemp, jute, Sisal, satin, viscose, polyamide, polyester etc. as well as any other known textile materials. Other examples of synthetic textiles are for example textiles, which differ from elastane (EL), elastodes (ED), Fluoro (PTFE), polyacrylic (PAN), modacrylic (MAC), polyamide (PA), aramid (AR), polyvinyl chloride (CLF), polyvinylidene chloride (CLF), polyester (PES), Polyethylene (PE), polypropylene (PP) or polyvinyl alcohol (PVAl) or derive their mixtures.

The method according to the invention is therefore suitable for treatment or Dyeing (e.g. also for subsequent color refreshment or intensification) any natural and synthetic textiles, especially textiles Clothing. It can be used, for example, on textile fabrics, in particular Woven goods such as fabrics, knitted fabrics such as knitted and crocheted or Use textile composites such as felt and nonwovens.

Another object of the present invention is thus a method for finishing (furnishing) textiles, especially textile clothing, with matrix or depot systems that contain coloring substances.

The approach according to the invention therefore consists in the coloring Integrate substance into a matrix or depot system. Subject of The present invention is thus also a matrix or depot system, which is a Depot or a matrix with a coloring substance contained therein includes.

The matrix and / or is preferably used according to the invention Depot system in the form of discrete, i.e. H. individual particles. These particles preferably have a spherical or approximately spherical shape. Particles with average diameters of are preferred according to the invention less than 500 µm, preferably less than 100 µm, particularly preferred less than 10 µm, most preferably less than 1 µm.

The coloring substance is stored in the matrix and / or depot system, embedded, enclosed, encapsulated, incorporated, dissolved, dispersed, adsorbed, chemically and / or physically bound etc.

For example, in the case of a porous matrix and / or depot system the coloring substance in the pores, cavities, cavities etc. of this system be stored. The coloring substance can also, for example be covalently bound to the matrix and / or depot system. The coloring Substance can, for example, also in the matrix and / or depot system be encapsulated (e.g. in the case of polymeric microcapsules as matrix and / or Depot System). Further examples and possibilities for the introduction of Active ingredients in matrix and / or depot systems are known to the person skilled in the art known.

The storage etc. of the coloring substance in the matrix and / or The depot system is therefore of a physical and / or chemical nature.

The coloring or color refreshment or intensification can be temporary or permanent, depending on whether the storage etc. of the coloring substance in the matrix and / or depot system is physical or chemical:
For example, if the coloring substance is chemically (e.g. covalently) bound to the matrix or depot system, the coloring or the color refreshment or intensification takes place in the sense of a temporary effect, since the coloring substance is firmly attached to the matrix or depot system remains bound and cannot penetrate into the textile fabric or into the fibers and thus the dyeing substance cannot itself be bound to the fibers, so that the next time the textiles are washed together with the matrix or depot system that it is tied, is removed again. “Temporary effect”, “temporary finishing” or “temporary finishing” in the sense of the present invention means in particular that the coloring substance applied to the textiles, in particular the textile surfaces or fibers, is bound to the matrix or depot system Shape - initially remains on the textiles (e.g. while the textiles are being worn in the form of clothing), but can then be easily removed again (e.g. during subsequent washing).

In the case of a physical binding of the coloring substance to the matrix or depot system (e.g. through storage, inclusion etc. in the matrix or depot system) is a diffusion of the coloring substance - at least to a certain part - possible from the matrix or depot system, so that the molecules diffusing out of the matrix or depot system the coloring substance in the textile fabric, knitted fabric etc. or in the fibers penetrate and thus can be bound directly to the fibers, so that the next time you wash the textiles, do not use them together with the Matrix or depot system are removed again. In this case this is done Coloring or the color refreshment or intensification in the sense of a permanent effect. "Permanent effect", "permanent equipment" or "Permanent equipment" in the sense of the present invention means in particular that the on the textiles, especially the textile surfaces or Fibers, applied coloring substance also in the subsequent washing remains on the treated textiles.

The loading of the matrix and / or used in accordance with the invention The depot system with the coloring substance or substances takes place in a manner known per se Wise: One way is to add the coloring substance (s) directly to integrate the production into the matrix or depot system incorporate etc. (e.g. in the case of a matrix or depot system based on Polymers the preparation of the polymers, d. H. in polymerization, in Presence of the coloring substance (s)). Furthermore there is Possibility of retrofitting the matrix or depot system with coloring Equip substance, e.g. B. in the case of a matrix or depot system based swellable organic polymers by swelling or soaking them Polymers in a solution or dispersion of the coloring substance or in In the case of liquid coloring substances, alternatively by swelling in them Substances themselves. Likewise, there is the possibility of combinations of apply loading mechanisms described above. Further Loading mechanisms and methods are known per se to the person skilled in the art.

The matrix or Depot systems are systems that contain coloring substances or dyes pull on the textile fibers and surprisingly to a deeper one Color impression result as the same amount of coloring substances or Dyes without the use of the matrix or depot systems.

The concentration of contained in the matrix or depot system coloring substances is preferably 0.001 to 10 wt .-%, in particular 0.001 to 5% by weight, preferably 0.001 to 3% by weight, particularly preferred 0.001 to 1 wt .-%, based on the total weight of the matrix and / or Depot system (based on the solids content).

All come as coloring substances that can be used according to the invention usual coloring substances or those available on the market, especially textile dyes.

The coloring substance is particularly selected from the group of inorganic and organic dyes and color pigments of all kinds, such as in particular direct dyes, reactive dyes and acid dyes, optionally in combination with inorganic and / or organic salts, especially so-called coloring salts.

• - Direktfarbstoffe, wie z. B. anionische Farbstoffe. Diese sind meist dadurch gekennzeichnet, daß sie aufgrund von elektrostatischen Wechselwirkungen, von-der-Waals-Wechselwirkungen, Wasserstoffbrückenbindungen zwischen den Cellulose-OH-Gruppen und dem Farbstoff direkt auf die Faser aufziehen.
• - Reaktivfarbstoffe, die ebenfalls anionischen Charakter haben können und insbesondere aus einer farbgebenden (Farbstoff-)Komponente und einer Reaktivkomponente aufgebaut sein können. Während der Behandlung mit farbstoffenthaltenden Matrix- bzw. Depotsystemen reagiert die Reaktivkomponente mit den funktionellen Gruppen der Faser (z. B. Hydroxygruppen bei Cellulose, Amidgruppen bei Wolle und Polyamiden etc.) und bildet dabei kovalente Bindungen aus.
• - Pigmente die in der Regel in die Faser eingelagert werden und mit einem Bindemittel fixiert werden.
• - Säurefarbstoffe, die insbesondere auf Wollfasern, aber auch auf Casein- und Polyamid-Fasern aus saurem oder neutralem Bad direkt aufziehen. Der Zusatz von Säuren beschleunigt dabei das Aufziehen auf die Fasern. Die Färbung der Wolle beruht auf einer Salzbildung zwischen den basischen Gruppen des Wolleiweißes (z. B. NH₂-Gruppen) und den sauren Gruppen der Farbstoffe (SO₃H-Gruppe, COOH-Gruppe und dergleichen). Daneben können sich aber noch andere Gruppen (Hydroxy-, Azo-, Aldehyd-Gruppen usw.) sowie Adsorptionsvorgänge usw. beteiligen.

The following are particularly suitable as coloring substances or dyes, in particular textile dyes, from the totality of all dyes used for dyeing textiles:

• - Direct dyes, such as B. anionic dyes. These are usually characterized by the fact that, due to electrostatic interactions, von der Waals interactions, they form hydrogen bonds directly between the cellulose OH groups and the dye on the fiber.
• - Reactive dyes, which can also have an anionic character and in particular can be composed of a coloring (dye) component and a reactive component. During the treatment with dye-containing matrix or depot systems, the reactive component reacts with the functional groups of the fiber (e.g. hydroxyl groups in cellulose, amide groups in wool and polyamides etc.) and forms covalent bonds in the process.
• - Pigments that are usually stored in the fiber and fixed with a binder.
• - Acid dyes, which in particular on wool fibers, but also directly on casein and polyamide fibers from acid or neutral bath. The addition of acids accelerates the absorption on the fibers. The color of the wool is based on salt formation between the basic groups of wool protein (e.g. NH ₂ groups) and the acidic groups of the dyes (SO ₃ H group, COOH group and the like). In addition, other groups (hydroxy, azo, aldehyde groups, etc.) and adsorption processes, etc. can also participate.

As far as the matrix or depot system is concerned, the The inventive method used in particular matrix or depot systems that consist of dimensionally stable or plastically deformable particles.

An embodiment is particularly preferred in which the matrix or Depot system is water-insoluble, but is water-dispersible and preferred is also alkali-resistant, in particular not alkali-soluble.

According to a special embodiment, the matrix and / or Depot system hydrophilic. In this case, the coloring substance is also preferred hydrophilic or amphiphilic; this has the advantage that the hydrophilic matrix and / or depot system easily afterwards with the hydrophilic or amphiphilic coloring substances can be loaded.

According to another embodiment, the matrix and / or depot system hydrophobic (e.g. systems or polymers that are determined by certain Precipitation processes are produced, as mentioned below). In this case also the coloring substance is preferably hydrophobic or amphiphilic trained because this is a subsequent loading of the hydrophobic matrix and / or depot system with the hydrophobic or amphiphilic coloring Substances.

According to the invention, the matrix and / or depot system can be one System non-ionic in nature or a system that is cationic is modified (e.g. by a cationic modification in the actual Senses or by absorption of a cationic surfactant). This generally allows good affinity of the matrix and / or depot system textile surfaces or fibers.

The matrix or depot system should in particular be as good as possible Show affinity for textiles (e.g. by a cationic modification or by absorption of a cationic surfactant) in order to respond as well as possible to the textile surface or the fibers.

According to the invention, the matrix or depot system is preferably skin-friendly educated.

For example, the matrix or Depot system be a system based on organic or inorganic polymers.

• - Quellbare (insbesondere mit Wasser quellbare), insbesondere quervernetzte (dreidimensional vernetzte) Polymere (z. B. Hydrogele) auf synthetischer wie natürlicher Basis. Als synthetische Polymere sind insbesondere zu nennen: Poly(meth)acrylsäuren, Poly(meth)acrylate, Poly- (meth)acrylamide, Polyurethane, Polyvinylpyrrolidone, Polyvinylalkohole oder deren Copolymeren. Als natürliche Polymere sind insbesondere zu nennen: Polysaccharide wie gegebenenfalls modifizierte Stärke und Stärkederivate, Dextrine, Agarosen, Agar-Agar, Polypeptide wie Gelatine, Curdlan, Alginsäuren und Alginate, Pektine und Pektinate, Carageenane, Chitosane sowie Cellulose und Cellulosederivate wie Carboxymethylcellulose. Alle diese Polymere können gegebenenfalls auch in kationisch modifizierter Form vorliegen oder aber kationische Moleküle (z. B. Tenside) enthalten. Bevorzugt sind insbesondere quellfähige Hydrogelteilchen, bevorzugt mit mittleren Partikeldurchmessern im gequollenen Zustand im Mikro- und Nanometerbereich, insbesondere mit mittleren Teilchendurchmessern im gequollenen Zustand von weniger als 100 µm, insbesondere weniger als 10 µm, vorzugsweise weniger als etwa 1.000 nm, ganz besonders bevorzugt weniger als 500 nm. Solche Teilchen können bis zu einem Mehrfachen ihres Eigengewichts an Wasser aufnehmen (z. B. bestimmte Polyacrylathydrogele 120 g/g).
• - Durch Fällung hergestellte Polymerpartikel. Hierzu eignen sich insbesondere wasserunlösliche Polymere, wie z. B. Eudragit® (z. B. Eudragit® RS), Ethylcellulose, PVAc sowie dessen wasserunlösliche Copolymere mit PVP, Celluloseacetat etc., die jedoch in wassermischbaren organischen Lösemitteln (Alkohole, Aceton etc.) löslich sind. Beim Fällen der organischen Lösungen, die das Polymer und den Wirkstoff (färbende Substanzen) enthalten, entstehen, gegebenenfalls in Gegenwart geringer Mengen ionischer, bevorzugt kationischer Tenside, feine Partikel, die den Wirkstoff eingeschlossen enthalten.
• - Durch Emulgierung hergestellte Polymerpartikel. Diese Ausführungsform ist besonders für die Formulierung organisch löslicher Wirkstoffe (färbende Substanzen) geeignet. Es eignen sich Polymere, die in nicht wassermischbaren organischen Lösemitteln löslich sind, z. B. Ethylcellulose und andere hydrophob modifizierte Cellulosederivate, Acrylate etc. Die gemeinsamen Lösungen dieser Polymere und der Wirkstoffe werden, gegebenenfalls in Gegenwart geringer Mengen an Tensid, bevorzugt kationisches Tensid, in Wasser emulgiert. Anschließend wird das Lösemittel durch Vakuum abgezogen. Der Wirkstoff wird in die Polymerpartikel eingeschlossen.
• - Mikrokapseln aller Art, insbesondere Mikrokapseln mit polymeren Kapselwänden, die den Wirkstoff (färbende Substanz) einschließen bzw. verkapseln. Erfindungsgemäß geeignete Kapselsysteme haben Kapseldurchmesser im Mikro- und Nanometerbereich. Erfindungsgemäß geeignete Kapselsysteme sind beispielsweise in den folgenden, auf die Anmelderin der vorliegenden Erfindung selbst zurückgehenden deutschen Patentanmeldungen beschrieben: DE 101 01 892.4, DE 101 04 841.6, DE 101 00 689.6, DE 100 37 656.8, DE 100 31 132.6 und DE 100 44 635.3, deren gesamter Inhalt hiermit durch Bezugnahme eingeschlossen ist. Solche Kapseln können polymere Kapselhüllen (z. B. aus natürlichen Polymeren wie Chitosan oder aus synthetischen Polymeren) aufweisen, welche die färbende Substanz als Kapselinneres oder -kern einschließen.
• - Filmbildner. Beispiele für erfindungsgemäß geeignete Filmbildner sind natürliche Polymere wie Chitosan, Ester- und Polyquats, Cellulosederivate, Polyamine etc.

The following systems are particularly suitable as matrix or depot systems which can be used according to the invention:

• - Swellable (in particular water-swellable), in particular cross-linked (three-dimensionally cross-linked) polymers (e.g. hydrogels) on a synthetic and natural basis. The following are particularly mentioned as synthetic polymers: poly (meth) acrylic acids, poly (meth) acrylates, poly (meth) acrylamides, polyurethanes, polyvinylpyrrolidones, polyvinyl alcohols or their copolymers. Natural polymers that should be mentioned in particular are: polysaccharides such as modified starch and starch derivatives, dextrins, agaroses, agar agar, polypeptides such as gelatin, curdlan, alginic acids and alginates, pectins and pectinates, carageenans, chitosans and cellulose and cellulose derivatives such as carboxymethyl cellulose. All of these polymers can optionally also be present in a cationically modified form or else contain cationic molecules (for example surfactants). Particularly preferred are swellable hydrogel particles, preferably with average particle diameters in the swollen state in the micro and nanometer range, in particular with average particle diameters in the swollen state of less than 100 μm, in particular less than 10 μm, preferably less than about 1,000 nm, very particularly preferably less than 500 nm. Such particles can absorb up to a multiple of their own weight in water (e.g. certain polyacrylate hydrogels 120 g / g).
• - Polymer particles produced by precipitation. For this purpose, water-insoluble polymers such as. B. Eudragit® (z. B. Eudragit® RS), ethyl cellulose, PVAc and its water-insoluble copolymers with PVP, cellulose acetate, etc., but which are soluble in water-miscible organic solvents (alcohols, acetone, etc.). When the organic solutions containing the polymer and the active substance (coloring substances) are precipitated, fine particles are formed, optionally in the presence of small amounts of ionic, preferably cationic, surfactants, which contain the active substance.
• - Polymer particles produced by emulsification. This embodiment is particularly suitable for the formulation of organically soluble active substances (coloring substances). Polymers are suitable which are soluble in water-immiscible organic solvents, e.g. B. ethyl cellulose and other hydrophobically modified cellulose derivatives, acrylates etc. The common solutions of these polymers and the active ingredients are, if appropriate in the presence of small amounts of surfactant, preferably cationic surfactant, emulsified in water. The solvent is then removed by vacuum. The active ingredient is included in the polymer particles.
• - All types of microcapsules, in particular microcapsules with polymeric capsule walls, which enclose or encapsulate the active substance (coloring substance). Capsule systems suitable according to the invention have capsule diameters in the micro and nanometer range. Capsule systems suitable according to the invention are described, for example, in the following German patent applications which go back to the applicant of the present invention: DE 101 01 892.4, DE 101 04 841.6, DE 101 00 689.6, DE 100 37 656.8, DE 100 31 132.6 and DE 100 44 635.3 the entire contents of which are hereby incorporated by reference. Such capsules can have polymeric capsule shells (e.g. made of natural polymers such as chitosan or synthetic polymers) which enclose the coloring substance as the capsule interior or core.
• - film maker. Examples of film formers suitable according to the invention are natural polymers such as chitosan, ester and polyquats, cellulose derivatives, polyamines etc.

According to the invention, the use of hydrogels is particularly preferred as matrix or depot systems. For example, you can either use the Use as a spray by immersing in the appropriate solution or the treatment of textiles in a washing or rinsing cycle Washing machine instead of or in combination with a fabric softener on the Textiles are applied. After a subsequent drying process the hydrogel matrices remain as tiny particles on the textile surface back. The hydrogel dispersions must therefore be such that the individual hydrogel matrices are no longer visible on the textile surface. Hydrogel dispersions with particle diameters are particularly suitable for this in the nanometer or micrometer range. Because hydrogels contain water Systems based on hydrophilic but water-insoluble polymers are known as three-dimensional network, the particles are on the Textile surface after the drying process is much smaller and is in generally only a tenth or less of their original volume. The water absorption capacity of the hydrogel particles is based on a simple swelling process of the matrix systems. An improved wind-up behavior the hydrogel particles can additionally by their cationic modification be achieved. The production of micro and nanoscale Hydrogel dispersions are state of the art and already exist in numerous publications described. Examples of hydrogels suitable according to the invention as matrix or Depot systems are e.g. B. Hydrogels based on polyisopropylacrylamide (P-N- IPAAm) and / or polyethyl methacrylate-co-N-vinylpyrrolidone.

The matrix or depot system is usually in the form of a preferably applied aqueous dispersion. In particular Dispersions are used which contain the matrix or Depot system in concentrations of less than 15 g / l, especially less than 10 g / l, preferably less than 3 g / l, very particularly preferably less than 1 g / l, contained, based on the content of the loaded with coloring substance Matrix or depot system (dry weight) in the dispersion. The Dispersion can already exist as such or if the matrix or Depot system in a dry, especially powder mixture or -Composition is made by adding water (e.g. in situ immediately during use, e.g. in a washing machine).

The systems according to the invention should preferably be used in a washing or Rinse cycle can be applied to the textiles. The one with the coloring Substance-loaded matrix and / or depot system, preferably in the form of a Dispersion, for example in conjunction with a detergent or a laundry treatment agent (e.g. fabric softener) or represent the detergent or laundry treatment agent itself or include.

The matrix or depot system is usually applied by Spray on the textile fibers or by immersing the textiles in the Dispersion. For example, treatment in a washing machine take place, in particular in the washing or rinsing cycle, preferably rinsing cycle, if necessary in combination with a fabric softener.

The textiles treated in this way are then dried. Drying is preferably carried out at ambient temperature or higher Temperatures, especially under normal pressure. This is preferably done Drying under normal pressure and at ambient temperature, in particular at room temperature. Drying can also take place at higher levels Temperatures (e.g. in a tumble dryer) take place. When drying, the Matrix or depot particles not destroyed.

With the method according to the invention, textiles, in particular textile clothing, dyeing and the colors of textiles (afterwards) refresh or intensify.

The present invention thus equally provides a method for (Temporary or permanent) finishing or finishing of textiles with coloring or color refreshing substances using dye-bearing matrix or depot systems (e.g. hydrogels) ready. By the substantive application of these matrix or depot systems is targeted Dye is applied to the fabric and a recoloring process is initiated. As a result, especially in the case of color refreshment, non-white textiles, the color intensity of the textiles increased and the Loss of color or "bleeding" of the colors during the washing process counteracted.

With colored, d. H. Non-white textiles can do the inventive Processes are used to refresh the colors of the textiles intensify if you use the same or for dyeing or to refresh the color uses a color similar to that of the textile. This allows the Textiles are re-dyed, and any local color fading occurs the textiles can be equalized.

The color impression can also be enhanced by the fact that Drawing up the nano- and microscale dye-containing matrix or depot particles, z. B. hydrogel particles, fiber roughening and / or by the change in reflective properties, the color brilliance is intensified.

Compared to the known methods of the prior art, the method according to the invention has a number of advantages:
The coloring substances can be used in conjunction with the matrix or depot system in much smaller concentrations than if pure dyes were used. The effect, in particular the color intensity, is at least equivalent, but usually even higher, at the same concentrations.

With the method according to the invention, textiles can be readily produced color it afterwards, for example the colors more colorful (more colorful) or Refresh non-white textiles. The colors of the textiles can be without Regenerate another several times, namely by repeated or repeated Application.

Since the dyeing or the color refreshment according to the invention during a Washing process or post-treatment process (e.g. during the Fabric softening process), there is no additional step as in the prior art Technology is provided, namely the "re-dyeing" of the textiles in the Washing machine with textile colors separated from the washing process. I.e. According to the invention, washing or laundry post-treatment process on the one hand and dyeing, on the other hand, together in one step be performed. Color washed out by the washing process is, by the application or by the addition of the dye-containing Matrix or depot systems balanced, so that a possibly occurring Color loss is no longer visible.

The matrix or depot system itself also makes useful and achieved favorable effects. For example, when using Hydrogels increased water absorption or absorption of textiles, combined with increased comfort. Furthermore are for example hydrogels as matrix or depot systems not only able to Absorb moisture (such as sweat), but reduce it by the Sweat absorption at the same time the multiplication of microorganisms.

Coloring the textiles or refreshing the color or Color intensification can already be done with relatively low dye concentrations, e.g. B. at Rinse / softener cycle. On conventional, elaborate Post-coloring treatments can be omitted.

The present invention further relates to compositions or formulations, for example dry compositions or Mixtures or dispersions, in particular aqueous dispersions, which previously described, loaded with coloring substances matrix and / or Depot system included. The concentration of with coloring substances loaded matrix and / or depot system (dry weight) preferably less than about 15 g / l, especially less than 10 g / l, preferred less than 3 g / l, very particularly preferably less than 1 g / l, based on the Composition or dispersion.

The compositions according to the invention which do this previously are preferred described, loaded with coloring substances or dyes and / or depot system, as a dispersion, preferably aqueous Dispersion, before. But other forms of application are also possible, e.g. B. gels, Dry mixes, powders etc. The dry formulations or powders can for example, starting from aqueous dispersions using spray or Freeze drying can be made.

The compositions according to the invention, in particular dispersions, or the matrix or depot systems loaded with the coloring substances can in particular in the form of a washing and / or cleaning agent or a laundry after-treatment agent (e.g. fabric softener, laundry spray or ironing aid) are used or as additives to one Detergent and / or cleaning agent or a laundry aftertreatment agent (e.g. fabric softener, laundry spray or ironing aid).

The present invention thus also relates to the use of the compositions according to the invention, in particular dispersions, or the dye-loaded matrix or depot systems according to the invention Treatment, in particular for dyeing or for refreshing the color and / or -Intensification, natural and / or synthetic textiles, in particular textile clothing. The compositions according to the invention, in particular dispersions or the dye-loaded matrix or depot systems are suitable, for example, for use on textiles Flat structures, in particular woven goods such as fabrics, knitted fabrics such as Knitted and knitted fabrics or textile composites such as felt and Nonwovens. They are particularly suitable for dyeing, for example subsequent Dyeing of textiles, in particular textile clothing and / or Color refreshment and / or intensification in textiles, especially textiles Clothing of non-white color.

Another object of the present invention are those with coloring Substances loaded matrix and / or depot systems themselves.

Further configurations and variations of the present invention are for the person skilled in the art when reading the description easily recognizable and realizable without changing the scope of the present invention leaves.

The present invention is based on the following exemplary embodiments illustrates which, however, in no way limit the invention.

EMBODIMENTS Preparation of an aqueous P-N-IPAAm hydrogel dispersion

470 ml of deionized water (fully demineralized water), 7 g of N-isopropylacrylamide, 0.35 g of N, N-methylenebisacrylamide and 0.094 g of sodium dodecyl sulfate are weighed into a 1 liter four-necked flask, and under a N ₂ atmosphere and reflux at 200 rpm heated to 70 ° C. After 30 minutes, 0.28 g of potassium peroxydisulfate in 30 ml of demineralized water are added, and the reaction is ended after a further 4 hours.

The hydrogel particles thus synthesized have one at room temperature Diameter from approx. 200 to 300 nm.

Preparation of an aqueous EMA-VP hydrogel dispersion

480 ml of deionized water, 4.1 g of ethyl methacrylate, 15.9 g of N-vinylpyrrolidone, 5.4 g of alkylarylpolyglycol ether sulfate sodium salt (1%) and 1 g of N, N-methylenebisacrylamide are weighed into a 2-liter four-necked flask and heated to 70 ° C under N ₂ atmosphere and reflux at 200 rpm. After 30 minutes, 0.8 g of potassium peroxydisulfate in 30 ml of demineralized water are added, and the reaction is ended after a further 4 hours. The aqueous hydrogel dispersion is then dialyzed.

The hydrogel particles thus synthesized have one at room temperature Diameter from approx. 100 to 300 nm. By varying the Particle sizes up to 500 nm can be achieved in synthesis conditions.

Immobilization of dyes in hydrogel matrices

The hydrogel dispersion prepared according to Example 1 is suitable (Centrifugation, freeze drying) concentrated. The freeze-dried P- N-IPAAm is mixed with a 2% dye solution in a ratio of 1: 4 and left to swell overnight. Diffusion is uniform Distribution of the dye in the hydrogel matrices and the solution. Possible is also the direct addition of the active ingredient in the hydrogel dispersion.

Simplicol® textile dye 12601 black (Brauns / Heitmann), Basacid® black (anionic 3-component acid dye, BASF) and Remazol® black (reactive dye, Dye Star) with and without the addition of NaCl and Na ₂ SO _{4 were} used as dyes ( see example 5).

Application of hydrogel dispersion on textiles

The application of the according to Example 1 (reference) and Example 3 (with dye) Hydrogel dispersion produced is standardized via a Dipping. The application times are less than 20 minutes, preferably less than 10 minutes; spray application is also suitable, a sufficient amount of hydrogel particles on the textile surface apply.

Test fabrics made of cotton, polyester and satin are used defined dimensions of 8 × 2 cm. These are placed in a lightly stirred, dispersion thermostated at 20 ° C with a solids content of 15 g / l, preferably 0.2 g / l, hung. After application of the hydrogels, the Samples at ambient temperature first in air, for exact Carrying out the tensiometric measurements, dried in a desiccator.

The pulling behavior of the PN-IPAAm hydrogel matrices varies depending on the textile fibers used. For example, when using a PN-IPAAm hydrogel dispersion with a concentration of 15 g / l on cotton 0.6 mg / cm ² hydrogel, on polyester 1 mg / cm ² and on mixed fabrics 0.4 mg / cm ² PN- IPAAm- Hydrogels on.

The hydrogels loaded with dye can be used alone (preferably 40 g of one 4% hydrogel dispersion per rinse cycle) or in combination with Fabric softener in the induction chamber of an ordinary washing machine be dosed. As a detergent for the main wash, 125 g of one ordinary UWM, color or delicate detergent.

Tests on the coloring effect of hydrogel dispersions with different dyes

• - Note 1: ausgezeichnete Farbeffekte
• - Note 2: gute Farbeffekte
• - Note 3: mittlere Farbeffekte
• - Note 4: schwache Farbeffekte
• - Note 5: kein Effekt

Three different types of fabric (cotton, PES, satin) were prepared with the hydrogel dispersions prepared according to Examples 1 and 3, as shown in Example 4 above, by immersion for 10 minutes and dried in air. The hydrogel has been used in both nano and microscale. The dye concentration was 0.008% in solution in all cases. The salt concentration can be used in the range from 0.01% to 20% and is here 10%, preferably 5%. Overall, better results were obtained with NaCl than with Na ₂ SO ₄ . The coloring effect was subsequently determined. Hydrogel dispersions without dye and the sole use of the dye served as reference. The intensity of the dye was characterized according to the following scheme:

• - Grade 1: excellent color effects
• - Grade 2: good color effects
• - Note 3: medium color effects
• - Note 4: weak color effects
• - Note 5: no effect

The results can be summarized as follows:

1. Cotton

The concentration of P-N-IPAAm was 0.2 g / l in each case. Were the Dyes without hydrogel applied to the cotton fabric, so the Coloring results from the test panel with the marks 5 for Simplicolt and Basacid® and rated 4 for Remazol®. In connection with the The dye Basacid achieved a hydrogel grade of 3.5. After applying the Systems Hydrogel-Simplicol®-NaCl, the test textiles were rated 4.2 rated.

2. PES

After using Simplicol® alone, one Score of 4 can be achieved. If you put this dye in the combination with hydrogel and NaCl, the result of the staining performance with the Grade 2. An improvement in the color appearance could also can be achieved with the Basacid® dye. Will the simple treatment of textiles rated with poor success of 4.5, so below Application of the combination of dye and hydrogel (as well optionally NaCl) an improvement to the grade 2.5 can be achieved.

3. Satin

The use of Basacid® was particularly effective for satin fabrics containing hydrogels. Was the reference sample of the pure dye graded only with 4.5, so with hydrogel and Basacid® dye treated tissue samples are graded 2.5. An increase in the Grading from 3 (reference pure dye) to 2 could be achieved with satin samples P-N-IPAAm containing Simplicol® were achieved.

Claims (45)

1. A method for dyeing textiles, in particular textile clothing, characterized in that a matrix and / or depot system which contains at least one coloring substance is applied to the textile surface, in particular the fibers of the textiles. 2. The method according to claim 1, characterized in that the matrix and / or depot system is in the form of discrete particles, in particular with average particle diameters of less than 500 µm, preferably less than 100 µm, particularly preferably less than 10 µm, entirely particularly preferably less than 1 μm. 3. The method according to claim 1 or 2, characterized in that the coloring substance stored in the matrix and / or depot system, embedded, enclosed, encapsulated, adsorbed, chemical and / or is physically bound, incorporated, dissolved and / or dispersed. 4. The method according to any one of claims 1 to 3, characterized in that the concentration of in the matrix and / or depot system contained coloring substance 0.001 to 10 wt .-%, in particular 0.001 to 5% by weight, preferably 0.001 to 3% by weight, particularly preferably 0.001 to 1 wt .-%, based on the total weight of the coloring Substance-loaded matrix and / or depot system. 5. The method according to any one of claims 1 to 4, characterized in that the coloring substance is selected from the group of inorganic and organic dyes and color pigments of all kinds, such as in particular direct dyes, reactive dyes and acid dyes, optionally in combination with inorganic and / or organic Salt. 6. The method according to any one of claims 1 to 5, characterized in that that the matrix and / or depot system made of dimensionally stable or plastic deformable particles. 7. The method according to any one of claims 1 to 6, characterized in that that the matrix and / or depot system is water-insoluble, however is water-dispersible and preferably also alkali-resistant, in particular is not alkali-soluble. 8. The method according to any one of claims 1 to 7, characterized in that the matrix and / or depot system is hydrophilic and / or that the coloring substance is hydrophilic or amphiphilic. 9. The method according to any one of claims 1 to 7, characterized in that the matrix and / or depot system is hydrophobic and / or that the coloring substance is hydrophobic or amphiphilic. 10. The method according to any one of claims 1 to 9, characterized in the matrix and / or depot system is non-ionic in nature or else can be modified cationically. 11. The method according to any one of claims 1 to 10, characterized in that that the matrix and / or depot system is a system based on organic or inorganic polymers. 12. The method according to any one of claims 1 to 11, characterized in that the matrix and / or depot system is a system based on the following compounds: a) swellable, in particular crosslinked, polymers, preferably hydrogels, on a synthetic or natural basis, optionally in a cationically modified form; b) polymer particles produced by precipitation, in particular water-insoluble polymers; c) polymer particles produced by emulsification, in particular polymers which are soluble in water-immiscible organic solvents; and d) microcapsules of all kinds. 13. The method of claim 12, wherein the swellable, in particular cross-linked polymers, preferably hydrogels, derived from synthetic polymers such as in particular poly (meth) acrylic acids, poly (meth) - acrylates, poly (meth) acrylamides, polyurethanes, polyvinyl pyrrolidones, Polyvinyl alcohols or their copolymers or of natural ones Polymers such as, in particular, polysaccharides such as, if appropriate modified starch and starch derivatives, dextrins, agarose, agar agar, Polypeptides such as gelatin, curdlan, alginic acids and alginates, pectins and Pectinates, carageenans, chitosans as well as cellulose and Cellulose derivatives such as carboxymethyl cellulose. 14. The method according to any one of claims 1 to 13, characterized in that that the matrix and / or depot system is skin-friendly. 15. The method according to any one of claims 1 to 14, characterized in that the matrix and / or depot system in the form of an aqueous dispersion is applied. 16. The method according to any one of claims 1 to 15, characterized in that the matrix and / or depot system containing the coloring substance as an aqueous dispersion, preferably in a concentration of less than about 15 g / l, especially less than about 10 g / l, preferably less than about 3 g / l, most preferably less than about 1 g / l, is applied, based on the content of with coloring substance loaded matrix and / or depot system (dry weight) in the dispersion. 17. The method according to any one of claims 1 to 16, characterized in that that the matrix and / or depot system by spraying on the Textiles or by immersing the textiles in the dispersion is applied. 18. The method according to any one of claims 15 to 17, characterized in that the treatment takes place in a washing machine, especially in the Rinse cycle, if necessary in combination with a fabric softener. 19. The method according to any one of claims 15 to 18, characterized in that the matrix and / or depot system as an additive to one Detergents and / or cleaning agents or one Laundry aftertreatment agents, such as in particular a fabric softener, a laundry spray or an ironing aid is used. 20. The method according to any one of claims 15 to 19, characterized in that that the textiles thus treated are then dried, whereby drying preferably under normal pressure and at Ambient temperature or higher temperatures. 21. The method according to any one of claims 1 to 20 for the treatment of natural and / or synthetic textiles, in particular textile clothing. 22. The method according to any one of claims 1 to 21 for use on textiles Flat structures, in particular woven goods such as fabrics, knitted fabrics such as knitted fabrics and knitted fabrics or textile composites such as felt and Nonwovens. 23. The method according to any one of claims 1 to 22 for subsequent dyeing of textiles, in particular textile clothing and / or for Color refreshment and / or intensification in textiles, especially textiles Clothing. 24. Dyed textiles, obtainable by a process according to the claims 1 to 23. 25. Textiles, in particular textile clothing, on their surface, in particular fibers, a matrix and / or depot system, which at least contains a coloring substance, is applied, in particular wherein the Matrix and / or depot system is in the form of discrete particles, in particular with average particle diameters of less than 500 µm, preferably less than 100 μm, particularly preferably less than 10 μm, very particularly preferably less than 1 μm, and / or in particular the coloring substance in the matrix and / or depot system stored, embedded, enclosed, encapsulated, adsorbed, chemically and / or physically bound, incorporated, dissolved and / or dispersed is. 26. Textiles according to claim 25, wherein the concentration of in the matrix and / or the depot system containing coloring substance 0.001 to 10% by weight, in particular 0.001 to 5% by weight, preferably 0.001 to 3% by weight, particularly preferably 0.001 to 1% by weight, based on the Total weight of the matrix and / or loaded with coloring substance Depot system. 27. composition, in particular in the form of a dispersion, of a gel, a powder, a dry composition or mixture, preferably in the form of a dispersion containing a matrix and / or Depot system, especially in the form of discrete particles, preferably with average particle diameters of less than 500 microns, preferably less than 100 µm, particularly preferably less than 10 µm, very particularly preferably less than 1 μm, the matrix and / or depot system contains at least one coloring substance. 28. The composition of claim 27, wherein the coloring substance in the matrix and / or depot system is embedded, embedded, enclosed, encapsulated, adsorbed, chemically and / or physically bound, is incorporated, dissolved and / or dispersed, preferably in amounts of 0.001 to 10% by weight, in particular 0.001 to 5% by weight, preferably 0.001 to 3 wt .-%, particularly preferably 0.001 to 1 wt .-%, based on the Total weight of the matrix and / or loaded with coloring substance Depot system. 29. The composition of claim 27 or 28, wherein the coloring Substance is selected from the group of inorganic and organic Dyes and color pigments of all kinds, such as in particular Direct dyes, reactive dyes and acid dyes, optionally in Combination with inorganic and / or organic salts. 30. The composition according to any one of claims 27 to 29, wherein the Matrix and / or depot system made of dimensionally stable or plastic deformable particles and / or wherein the matrix and / or depot system is hydrophilic and / or wherein the matrix and / or depot system is water-insoluble but water-dispersible and preferably also alkali-resistant, especially not alkali-soluble. 31. The composition according to any one of claims 27 to 30, wherein also the coloring substance is hydrophilic or amphiphilic. 32. The composition according to any one of claims 27 to 31, wherein the Matrix and / or depot system is non-ionic in nature or else can be cationically modified and / or wherein the matrix and / or Depot system a system based on organic or inorganic Is polymer. 33. Composition according to one of claims 27 to 32, wherein the matrix and / or depot system is a system based on the following compounds: a) swellable, in particular crosslinked, polymers, preferably hydrogels, on a synthetic or natural basis, optionally in a cationically modified form; b) polymer particles produced by precipitation, in particular water-insoluble polymers; c) polymer particles produced by emulsification, in particular polymers which are soluble in water-immiscible organic solvents; and d) microcapsules of all kinds. 34. The composition of claim 33, wherein the swellable, in particular cross-linked polymers, preferably hydrogels, derived from synthetic polymers such as in particular poly (meth) acrylic acids, Poly (meth) acrylates, poly (meth) acrylamides, polyurethanes, Polyvinylpyrrolidones, polyvinyl alcohols or their copolymers or from natural polymers such as in particular polysaccharides such as optionally modified starch and starch derivatives, dextrins, agaroses, agar Agar, polypeptides such as gelatin, curdlan, alginic acids and alginates, Pectins and pectinates, carageenans, chitosans as well as cellulose and Cellulose derivatives such as carboxymethyl cellulose. 35. The composition of any one of claims 27 to 34, which is the Coloring substance-containing matrix and / or depot system in the form an aqueous dispersion, preferably with a concentration of less than about 15 g / l, especially less than 10 g / l, preferably less than 3 g / l, very particularly preferably less than 1 g / l, based on the content of matrix-laden with coloring substance and / or depot system (dry weight). 36. Composition according to one of claims 27 to 35 in the form of a Detergent and / or cleaning agent or one Laundry aftertreatment agent, in particular a detergent, a fabric softener, one Laundry sprays or an ironing aid. 37. Use of a composition, in particular dispersion, according to Claims 27 to 36 for the treatment of natural and / or synthetic Textiles, especially textile clothing. 38. Use of a composition, in particular dispersion, according to Claims 27 to 36 for use on textile fabrics, especially woven goods such as fabrics, knitted fabrics such as knitted fabrics and Knitted or textile composites such as felt and nonwovens. 39. Use of a composition, in particular dispersion, according to Claims 27 to 36 for dyeing, in particular subsequent dyeing, of textiles, in particular textile clothing, and / or for Color refreshment and / or intensification in textiles, especially textiles Clothing. 40. Use of a composition, in particular dispersion, according to Claims 27 to 36 for the temporary or permanent equipment of Textiles, in particular textile clothing, with coloring substances. 41. Use of a composition, in particular dispersion, according to Claims 27 to 36 for temporary or permanent equipment (Equipment) of textiles, especially textile clothing, with matrix or depot systems that contain coloring substances. 42. matrix and / or depot system, in particular in the form of discrete particles, preferably with average particle diameters of less than 500 μm, preferably less than 100 μm, particularly preferably less than 10 μm, very particularly preferably less than 1 μm, the matrix and / or depot system at least one coloring substance, preferably contains a dye and / or a color pigment. 43. Matrix and / or depot system according to claim 42, wherein the coloring Substance stored, embedded in the matrix and / or depot system, enclosed, encapsulated, adsorbed, chemically and / or physically bound, incorporated, dissolved and / or dispersed, preferably in Amounts of 0.001 to 10% by weight, in particular 0.001 to 5% by weight, preferably 0.001 to 3% by weight, particularly preferably 0.001 to 1% by weight, based on the total weight of the loaded with coloring substance Matrix and / or depot system and / or wherein the coloring substance is selected from the group of inorganic and organic Dyes and color pigments of all kinds, such as in particular direct dyes, Reactive dyes and acid dyes, optionally in combination with inorganic and / or organic salts. 44. Matrix and / or depot system according to claim 42 or 43, wherein the Matrix and / or depot system made of dimensionally stable or plastic deformable particles and / or wherein the matrix and / or depot system is hydrophilic and / or wherein the matrix and / or depot system is water-insoluble but water-dispersible and preferably also alkali-resistant, especially not alkali-soluble. 45. Composition, in particular washing and / or cleaning agents or Laundry aftertreatment agents, in particular detergents, Fabric softener, laundry sprays or ironing aid, containing a matrix and / or Deposit system according to one of claims 42 to 44.