EP3353343A1 - Textile fabrics with denim-like features - Google Patents

Abstract

The invention relates to a method for dyeing textile fabrics or ready-made textiles, which makes it possible to mimic surface features that are characteristic of denim, and to corresponding textile fabrics or ready-made textiles.

Description

 Textile fabrics with denim-like features

The invention relates to a process for dyeing textile fabrics or made-up textiles, which makes it possible to imitate denim-typical surface features and corresponding textile fabrics or made-up textiles.

Since the beginning of the use of denim goods / jeans in the middle of the 19th century, such products are generally enjoying increasing popularity. Today, the current worldwide market volume is estimated at more than 50 billion US $.

Characteristic of traditional denim goods are, above all, the blue color, their whiteness, the irregular lightening of the product caused by friction / abrasion / dye degradation, as well as the so-called "salt & pepper" effect Indigo as a dye, cotton as a fiber material and the ring dyeing of the yarns, as well as the weaving of a twill weave.

The latter is characterized by the fact that warp and weft threads are located at unequal proportions on both sides of the goods. In the case of classic denim fabric, a yarn dyed blue is used as a warp yarn and a white yarn as a weft yarn, and a warp knit is woven (ie the dyed yarns predominate on the "right side of the warp"), thereby producing a regular denim product Color change from blue / white with a predominant share of blue on the outside, while the inside is predominantly white - the "Salt &Pepper" effect. In addition to this effect, a denim product is also characterized by the possibility of local brightening by chemical, biological or physical treatment and / or a combination of all three variants. For this purpose, the dyeing technique of the warp yarns is critical: The yarns are dyed in a ring dyeing process only externally with indigo, while the yarn core remains white or colorless. In this way, by rubbing (sandblasting, grinding, rubbing in daily use), by enzymatic treatment and / or by treatment with oxidizing agents (for example potassium permanganate (KMnO ₄ )) the dye and / or the colored cellulose layer can be removed and / or degraded. In any case, due to the respective spatially limited treatment, a local lightening comes about, which is due to the visibility of the undyed yarn core or of the dye degradation in the outer layer. These (apparent) signs of wear are the basis for decades of popular, and in denim fashion essential / indispensable, washed-out, vintage, used-look or similar effects.

In particular, the bleachability with potassium permanganate along with the permanent brilliance of the dye limit manufacturers of classic blue jeans on the use of indigo as a dye. However, it seems astonishing that, despite the inflexibility and the relatively high expenditure of time of the classic ring dyeing process, no other dyeing technology for blue-jeans denim production has yet been able to establish itself.

For example, the ring dyeing method is already described in patents at the beginning of the 20th century (US2110595A) and practiced today in only slightly modified form (CA1098258A1, WO1998045521A1). In general, yarns are either dyed in rope (Rope) or fanned side by side (Slasher) in a strongly alkaline dyebath containing reduced leuco-indigo and excess reducing agent (to ensure the solubility of the indigo). The yellow leuco indigo which is still yellow at this point in time will either be replaced by atmospheric oxygen (for example US2110595A) or another Oxidizer (eg CA1098258A1) reoxidized to give blue indigo fixed on the fiber. Due to the low affinity of the leucoindigo for the fiber usually about 5 to 10 staining cycles have to be run through until there is sufficient staining of the edge zone of the fibers (compare DE19628806A1 or DE4406785A1).

One way of saving the reduction and oxidation steps of the indigo and binding the indigo to the yarn surface by means of a binder polymer has recently been described in US20140150187A. Here, the warp yarn is coated with an emulsion copolymer which (presumably) forms covalent bonds with the cellulosic fiber by heat treatment. If this composite is treated either directly following this or after interweaving at temperatures between 60 and 100 ° C. with an indigo-containing dispersion, the dye preferably attracts to the pretreated warp yarn.

However, methods are also known for dyeing flat goods with indigo. DE19628806A and / or DE4406785A, for example, describe in each case processes of planar goods continuously or discontinuously, conventionally, via the intermediate steps of reduction and oxidation, dyeing with leucoindigo. While these methods can save repetitive steps in the dyeing process, they continue to require, analogous to the warp dyeing, the use of redox-chemically active, and toxicologically or ecologically questionable chemicals, and the implementation of at least two process steps for staining (reduction and staining, and the subsequent reoxidation).

Also known is the possibility of uniformly or selectively transfering indigo to tissue by means of sublimation and resublimation steps (for example WO2006045387A or CN201864856U). Here, indigo is sublimated at temperatures of 150 ° C to 230 ° C (transferred from the solid to the gas phase) and deposited on the substrate. While in WO2006045387A the uniform deposition on a cotton fabric is described in CN201864856U the Sa It & Pep per effect by different affinities of polyester and cotton fibers of the corresponding interwoven, and to be dyed with indigo Mischtextiis realized. Due to the absence of binder, it must be assumed that the textile fabrics treated in this way have a moderate degree of authenticity.

On the other hand, WO2014063028A1 describes an alternative process for the preparation of particulate / dispersed dyes, i.a. Indigo, as colorful as possible and at the same time Abfärbe- and light-resistant to bind to any textile fabric. The core of the technical teaching consists in the use of a based on alkyl acrylates or alkyl methacrylates and acrylonitrile copolymer binder. While the aim here is to realize dyeings with as good as possible fastnesses by the use of binders containing acrylonitrile, this document also mentions the possibility of washing processes such as, for example, a "stone-wash", uneven discoloration on treated with this dyeing dispersion To realize goods, but not further occupied.

In particular, the Salt & Pepper effect is considered characteristic of denim goods. To simulate this by application to flat textiles, CN2033825U a system is described which uses a grid for masking any textile substrate before a dye-containing dispersion / solution is sprayed. This approach is taken up in CN 102418294A to apply a printing paste through a screen to a textile.

In summary, it can be said that there are many methods of classic denim production which, however, require often expensive yarn pretreatment. In addition, some approaches have been published which aim to apply dyes, including indigo, to textile fabrics. The object of the present invention is to provide a process for dyeing textile fabrics or made-up goods, and the textile materials produced in this way It is also possible to provide fabrics or ready-made goods themselves which, while avoiding highly reactive and thus toxicologically and / or ecologically harmful chemicals, can be carried out with application methods customary for textile finishing, by means of which in particular goods with a denim-like appearance can be produced.

The above object is achieved in a first embodiment by a process for dyeing textile fabrics and / or made-up textiles, in particular for producing a denim-typical appearance, characterized in that comprising a dispersion of a bleachable dye in a polymeric binder optionally containing water Individual fibers, yarns, textile fabrics and / or made-up textiles brings into contact.

The present invention now allows finishing companies to access the production of goods with denim features, hereinafter referred to as denim imitations, which may even be provided with previously unattainable or hardly realizable fashion effects.

Surprisingly, it has been found that with correct selection and adjustment of the nature and the proportions of pigments, particle sizes, binders, rheology additives (often also referred to as "thickeners") and optionally further additives, pastes and dispersions can be prepared which produce denim imitations enable on a variety of substrates.

The following table gives an overview of the previously mentioned denim features as well as their cause:

Feature generation

blue use of indigo, indigoidic compounds blue / black and / or sulfur black as dyes in classical Color shear denim fabric.

 Salt & Pepper EfUse of dyed warp yarn and non-classic (or otherwise colored) weft yarn when weaving the (warp) twill weave is responsible for the alternating color sequence.

Surface local Frequently produced by mechanical roughening of the brightening ring-dyed warp yarns whose yarn core is still undyed (the so-called "scraping"), and after-treatment with oxidizing or bleaching chemicals (for example KMn0 ₄ ) Alternatively: enzymatic removal of the dyed yarn sheath or the yarn dye.

 Local lightening Caused by the so-called "Stone-wash", that is to say on exposed washing of the finished goods with pumice stones, so that exposed areas are scrubbed more intensively.

The reasons for the primary use of indigo as a denim dye are manifold and include, among others:

1. Indigo is a vat dye, and only with such the ring dyeing of the warp yarn in the commonly practiced form succeeds. In the case of dyeings with vat dyes, these are usually converted into a water-soluble (leuco) form by reduction (occasionally also oxidation), deposit on the fiber or yarn material and / or the textile fabric and are replaced by a subsequent oxidation process (or reduction process) ) are converted back into the water-insoluble form, whereby they are fixed on the substrate with good washing resistance.

2. Indigo can be bleached, inter alia, in a sodium hypochlorite (with hypochlorite) or with potassium permanganate (KMn0 ₄ ), whereby local lightening effects are possible. 3. The unique indigo color, as well as the brilliance and good oxidation resistance of the dye are in demand by the market and can not be readjusted easily by other dyes in combination with the above-mentioned properties.

However, in order to increase flexibility in use, the indigo may still be chemically altered. Such "indigoid dyes" or "indigoid compounds" can be any molecules having a structure similar to the indigo structure (partial) structural unit, for example, an improved solubility, altered shades (G. Voss, M. Gradzielski, J. Heinze, H. Reinke, C. Unverzagt, Helv. Chim. Acta 2003, 86, 1982-2004) and / or advantages in use (EP0889159A2). In addition, "sulfur black" is frequently used to produce darker shades in combination with indigo. "Sulfur black" is also preferably used for the purposes of the present invention.

In the present invention, preference is likewise given to using those dyestuffs customary for the production of classic denim ware, it also being possible to use water-insoluble or any desired pigments and / or dyes or mixtures of different dyes and / or pigments. In the case of the production of denim imitations, at least one of the dyes and / or pigments used should be bleachable.

With the help of static light scattering (SLS) particle sizes can be determined. Here, the particles or the substance to be tested are dispersed in water and on a Horiba LA-920, after a short ultrasonic treatment (about 5 min), using angle-dependent intensity measurements of scattered at the sample laser light (He-Ne laser: 632.8 nm, 1 mW, 50 W) conclusions about the particle size. It has been found that the correct adjustment of the dye particle size is important to produce the desired hue and the optimum brilliance, as well as abrasion resistance, processability and To ensure homogeneity. Too large particles, for example, often appear greyish / dull, while particles that are too fine, in particular nanoparticles, have too low a tinting strength or may be toxicologically questionable.

In order to ensure the adhesion of such dye particles, but also of other additives, to textiles, polymeric binders are frequently used. These are applied to the product in polymerized, prepolymerized or oligomeric and / or monomeric form together with the constituents to be bound and, in the case of the presence of crosslinkable and / or polymerizable groups, are usually cured / crosslinked / fixed following a drying step. In this way, a matrix forms the additives or particles and the substrate together, which ensures good fastness properties.

In the case of the present invention, it is crucial to obtain both the textile character of the substrate and to obtain denim goods comparable to washing and rubbing fastnesses.

Surprisingly, it has been found that with indigo contents of between 10% by weight and 90% by weight, based on the mass of the dried residue of the dispersion, and with selection of suitable binders which are, in addition to indigo, the main constituent of the dispersion, both the textile feel is retained , Good wash resistance can be ensured as well as the dye particles are bleaching or lightening treatment steps sufficiently accessible to produce denim effects can.

From a chemical point of view, binders or binder combinations which are unsubstituted or substituted by vinyl or ethene, butadiene, acrylate, methacrylate, ethyl acrylate, butyl acrylate, vinyl chloride, styrene, silane, siloxane, polyol and / or saccharide are particularly suitable. Monomers and / or urethane, ether, ester, amide, silyl ether, silyl ester, polysaccharide (including cellulose and / or starch) units were contained or at least partially generated from such units. These monomers or components (including the monomers / oligomers or prepolymers / polymers required / necessary for the production of said functional groups) can be present both in the form of physical mixtures and as polymers and / or as copolymers (including alternating, random copolymers, block copolymers) , Also, binders which do not contain the above-mentioned components may be suitable for the invention in combination with one or more binders containing the above components. The binders may be thermoplastics, thermoplastic elastomers and / or elastomers, as well as thermosets.

In any case, however, it is important to ensure sufficient flexibility of the fixed binder matrix, since otherwise the coating may tear or flake off or be removed unintentionally and / or the textile feel may be changed unpleasantly / unwantedly (for example, a "smeary" handle). It has been found that binders and / or binder combinations whose glass transition points (T _g ) are between -40 ° C and + 20 ° C and / or whose E-moduli are between 1.0 MPa-20.0 MPa are advantageous for the application Have flexibility.

In addition to the abovementioned components, the dispersion used in the context of the invention may further known per se in textile chemistry and / or unusual auxiliaries or functional additives, such as rheology ("thickener"), dyes, phosphors, effect pigments, emulsifiers , Preservatives, catalysts, flame retardants, defoamers, leveling agents, wetting agents, reducing agents, oxidizing agents, stabilizers and / or pH regulators.

The process according to the invention described here is much more flexible with respect to the substrate to which it is applied than the warp dyeing usually preceding the denim fabric preparation. Latest- While the dispersion of the invention is limited to the coloration of cotton-containing yarns, the dispersion according to the invention, after adjusting all relevant parameters, such as, for example, the viscosity and / or the choice of the binder suitable for the substrate and optionally further additives, both on individual fibers, yarns, textile fabrics as well as on ready-made textiles can be applied.

Advantageous is the application to single fibers, yarns, textile fabrics and / or made-up textiles containing natural and / or synthetic fibers. Such fibers are, for example, but not exclusively, fibers, the vegetable constituents or components obtained from plant constituents, for example cellulose, in particular cotton and / or cellulose regenerate (for example modal, lyocell, viscose (CV), acetate (CA)) , the animal components or components derived from animal products, such as wool and / or silk, the predominantly chemically produced components such as polyester [for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT)], polyamide [for example, polyamide 6.6 (PA 6.6), polyamide 6 (PA 6)], polyethers [for example polyethylene oxide (PEO), polypropylene oxide (PPO)], polyacrylonitrile (PAN), polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), polyurethane [for example elastane / Spandex (PUE)] and / or polyurea, and / or constitute mixed fibers of various types.

An advantage of the invention is that the method is applicable to a variety of fabrics and / or made-up goods such as woven, knitted, knitted or nonwoven fabrics. Compared to the limitation to fabric in the classic denim production results by the method described here increased flexibility. Particularly advantageous is the use of textile fabrics and / or made-up goods with a clear surface topography and / or exposed areas. Another advantage of the method is that it can be applied to any colored or uncolored goods, making novel, fashionable effects accessible. For example, these can be based on the fact that the dyeing dispersion according to the invention is only partially applied or removed over a larger area than would be necessary for the generation of a salt & pepper effect.

The application may, if appropriate after adaptation of the formulation, be carried out by any method applicable in textile production, in particular by means of forced application methods, such as, for example, spraying, coating, printing, padding, brushing or brushing and / or stripping.

In order to produce some of the characteristics typical of denim goods, classic denim products are subsequently treated after the weaving process or after the finishing. These aftertreatment methods can be roughly subdivided into physical / mechanical, biological and chemical processes. The mechanical methods include, for example, the so-called "stone-wash", washing the finished goods in a washing drum / washing machine additionally pumice stones or other abrasives were added to scrub more exposed areas, and roughening using one or more abrasive utensils, For example, sand or sandpaper for local surface lightening, laser treatment for destroying the dye and / or tinting, subsequent staining with a dye, biological treatment steps include, in particular, enzymatic treatments, for example with cellulases, amylases, laccases, and / or catalases for the surface Degradation of the cellulose, bleaching of the dyestuff and / or removal of peroxide residues Denim-typical chemical aftertreatment steps concern, above all, but not exclusively, the bleaching of the dyestuffs: hypochlorites, peroxides and / or are frequently used for this purpose he potassium permanganate, which are added to a washing process and / or locally sprayed and removed after a contact time again. The basis for the fact that in the case of classic denim goods with the help of the various post-treatment steps contrasts can be strengthened and accentuations can be set, lies among other things in the ring coloring of the warp yarns. Because only by the superficiality of the coloring of the yarns, which leaves the yarn core undyed, or in the original color, succeeds with the aid of suitable post-treatment steps, the sufficient degradation or removal of the colored cellulose components and / or the indigo or the dyes themselves, so that original yarn core can emerge or becomes visible.

Surprisingly, it has been found that textile fabrics and / or ready-made textiles can be obtained by applying the process according to the invention, in which the yarns on the side facing the application of the dispersion are comparable to commercial ring-dyed warp yarns in terms of the penetration depth of the color pigments. This penetration depth of the color pigments can be determined, for example, by dissecting individual yarns from the fabric, embedded in a resin matrix (for example Eurelon 950) by known methods, and cross-sections of 14 to 20 μm with a microtome (for example RM 2255 from Leica) Thickness can be produced. Under the light microscope, the areas of the yarn cross section are visible with dye pigment deposits and the maximum penetration depth of the pigment can be given in relation to the total diameter of the yarn. It has been found that a denim-like behavior is then present when the maximum penetration depth is less than 60%, in particular less than 50%, preferably less than 40% of the yarn diameter.

Thus, sufficient fastness and abrasion resistance are ensured in the final product, while denim-typical post-treatment steps can still be used to produce habitual denim features or new effects. A very important feature for denim products is the already mentioned Salt & Pepper effect. This results in classic denim fabric from the warp twill weave using warp and weft yarns of different colors.

It has surprisingly been found that the application of the dyeing dispersion according to the invention in combination with one and / or several suitable aftertreatment steps customary for denim goods results in an anisotropic distribution of the dye particle binder matrix on the product, and thus one, the salt & pepper effect of classic denim goods , produces very similar effect. Thus, the term "anisotropy" here describes the random or irregular, as opposed to the uniform-full-area and / or regular repeat patterns existing partial distribution of dye particle binder matrix composite on the substrate Salt & Pepper effect necessary, on the other hand, the basis of other denim-typical effects, such as created by grinding and / or bleaching lightened surfaces, which are surrounded by less and / or non-lightened surfaces (for example, used to create "used look "/" Vintage look "- effects or for accentuation).

To quantify this anisotropy, two methods have been developed: One of these methods is based on the comparison of the average brightness of aftertreated, ie the Salt & Pepper effect shown or bleached / brightened, and non-aftertreated, ie not showing the Salt & Pepper effect or not and / or less bleached / lightened, textile surfaces. Color comparisons in the device-independent CIE standard valence system (CIE-XYZ) color space are based on these comparisons. In this color space, all colors are expressed by values for the norm valences (imaginary colors) X, Y and Z, where the value Y is an expression for the brightness represents (the higher, the brighter). This value is always present at the points showing the salt & pepper effect and / or bleached / lightened the visibility of the unstained or differently colored substrate changed, in most cases increased. On the one hand, the amount of this change (ΔΥ) depends, of course, on the intensity of the aftertreatment. On the other hand, in a noninventive embodiment of the process, for example in the case of excessive dyeing of the yarns or too strong embedding of the indigo or dye pigments in the binder matrix, little to no lightening effect (based on the color of the dye applied with the dyeing dispersion) is present. If, on the other hand, bleaching / lightening is too high, the Salt & Pepper effect is also inadequate. Accordingly, the average lightening (ΔΥ) of at least one dyeing dispersion-removing or -treatment-treated surface of a textile fabric according to the invention and / or a made-up fabric according to the invention compared to an untreated surface, on the fabric side colored with the dispersion according to the invention, is at least 5, preferably at least 7.5, more preferably at least 10, optionally in each case up to 100, preferably up to 80, particularly preferably up to 60. It has additionally been found that ΔΥ in an article produced according to the invention is comparable to that of a conventionally produced denim article Color intensity, fiber composition, fabric construction and basis weight often not more than 5, usually not more than 10 and practically never deviates more than 15 units up or down.

The other method is the direct determination of the Salt & Pepper effect: It is crucial that the characteristic of this effect, ie the clearly delineated juxtaposition of light and dark points in anisotropic distribution, in a correlated with the impression of the human observer by counting the brightest and darkest pixels of a photographic shot is quantified. This is possible by determining the brightest and darkest points within a certain tolerance range, whereby it was found that the impression of a Salt & Pepper effect only arises for the viewer when the recording has a certain minimum proportion of the relatively brightest and darkest points, and these in turn make up a certain minimum proportion of all pixels.

The denim article to be assessed is laid flat and photographed under defined conditions (standard illuminant D65, illuminance 1000 lux) at an angle of 65 ° so that a picture with 2000 x 2000 pixels is obtained when a 60 mm x 60 mm piece of goods is taken. For example, the image is analyzed using Adobe® Photoshop CS3 and the number of relatively brightest and darkest pixels in the RGB color space is counted.

These relatively brightest and darkest points are detected in the ^Adobe® Photoshop CS3 via the Threshold tool, so that the reference points are selected so that each additional 0.2% or more of the pixels are still selected Below the lightest or darkest reference points defined in this way, the "wand" tool becomes all pixels with the tolerance value 70 or the percentage of these pixels in the total number of all pixels determined.

It has been found that the viewer then has a salt and pepper effect if at least 10% of all pixels contained in the image section are assigned to the brightest and at least 10% to the darkest pixels, and their sum is at least 20%, preferably at least 35% particularly preferably at least 45%, in each case up to 100%, preferably up to 85%, particularly preferably up to 70% of all pixels contained in the image.

Thus, the present invention relates to a new universally applicable process for the application of indigo or indigo-like (indigoid) dyes / pigments, which is characterized in that it is both in the area, as well as ready-made / garment, both on cotton, as also on any other fiber materials, both on white goods, as well as on dyed textiles and both by printing, coating, spraying, brushing or other application forms can be applied and subsequently aftertreatment steps (such as bleaching (enzymatic, chemical or physical) and / or "stone-wash") allowed , which are used today for the production of commercial denim goods.

An essential feature of the invention is the combination of the advantages of known methods: it is a method which is based on application techniques common in the textile industry, warp dyeing-analogous penetration depths are realized, and denim-customary and novel effects can be realized with known after-treatment steps , Thus, inter alia, textile fabrics and / or made-up goods with a denim-typical appearance can be produced.

Examples:

Reference Example 1

A commercial, pure indigo-dyed denim fabric (100% CO, 3/1 twill, 12 oz, desized) was subjected to a standard scraping pretreatment (240 grit sandpaper applied to foam block, block manually 3 times in a sanding motion of about 6500 Pa Apply pressure over the surface to be bleached). Subsequently, a rectangular area of 120 cm ^{2 was} marked and covered at the edges against the adjacent surfaces with adhesive film. This area was uniformly sprayed with 2 g of an aqueous solution of 20 g / l potassium permanganate (0.38 normal) and the fabric sample was then weighed to control the amount applied. After a residence time of 20 minutes at room temperature, the swatch was subjected to wash-down with untreated denim fabric as the ballast of a neutralization wash combined with stone-wash (45 ° C for 30 minutes at 1.5 g / l Bis (hydroxylammonium) sulfate (DENIMCOL PEX), 1 g / L of a neutral cellulase formulation (Beizym TOP HC) and 0.8 g / L antibackstaining agent (DENIMCOL CLEAN SMX) at a pumice loading of 200% of the weight of the product and a liquor ratio of 1: 8 Then, it was rinsed three times cold at a liquor ratio of 1:10 and then tumble-dried The Y-value according to CIE (Datacolor International SF 600 Plus-CT, Aperture 30 mm) was determined on the pattern obtained on and next to the spray-treated area LAV, measuring angle 10 °, 4-fold measurement, standard light calibration D 65) and the difference (ΔΥ) determines the degree of lightening.

This resulted in a value of ΔΥ = 19.2.

In the assessment of the Salt & Pepper effect, a proportion of 21.9% brighter and 34.3% darker pixels (sum 56.2%) was determined. Reference Example 2

A commercial, pure indigo-dyed denim fabric (73% CO, 27% PES, 3/1 twill, 10.8 oz, desized) was sanded, bleached and washed in an analogous manner as in Reference Example 1. Of the samples thus obtained, the Y value according to CIE (Datacolor International SF 600 plus CT, aperture 30 mm LAV, measuring angle 10 °, quadruple measurement, calibration standard light D 65) was measured in each case on and next to the spray-treated surface determined from the difference (ΔΥ) the degree of lightening.

This resulted in a value of ΔΥ = 24.6.

In the assessment of the Salt & Pepper effect, a proportion of 27.2% brighter and 22.0% darker pixels (total 49.2%) was determined

Comparative Example 1

An undyed cotton fabric of analogous construction as Reference Example 1 (100% CO, 3/1 twill, 12 oz, not desized) was coated with a no-binder printing paste containing 10.0 wt% of an aqueous indigo pigment dispersion (BEZEMA Indigo AXX FL.) And 1.0% by weight emulsifier (TUBIGAT A 60), adjusted to 16,000 mPa s with a rheology additive (TUBIVIS DL 600), printed.

Printing conditions: squeegee speed: 6 m / min

Squeegee diameter: 12 mm

Squeegees: 1

The color strength ratio to the standard denim product of Reference Example 1 was determined from the ratio of the K / S values and was 90.6% at 610 nm.

Already during the scraping pretreatment with sandpaper, however, there was a strong detachment of the applied indigo pigment.

The material was unusable. Comparative Example 2

The same cotton fabric as in Comparative Example 1 was coated with a printing paste containing as binder agent 60.0% by weight of TUBIFAST AS 4087 FF, 10.0% by weight of an aqueous indigo pigment dispersion (BEZEMA Indigo AXX FL.) And 1.0% by weight of emulsifier (TUBIGAT A 60), adjusted to 16,000 mPa s with a rheology additive (TUBIVIS DL 600), printed under the same conditions as Comparative Example 1.

The color strength ratio to the standard denim product of Reference Example 1 was 92.3% at 610 nm.

 The sample was sanded, bleached and washed in an analogous manner as in Reference Example 1.

 Scraping pretreatment with sandpaper showed only a slight lightening of the color intensity of the print; after complete treatment, a value of 4.1 was measured for ΔΥ.

In the assessment of the Salt & Pepper effect, a proportion of 5.9% brighter and 40.3% darker pixels (total 46.2%) was determined.

Comparative Example 3

The same cotton fabric as in Comparative Example 1 was sprayed with a dispersion without the addition of a rheology additive containing as binder agent 5% by weight of TUBIFAST AS 4087 FF and 5.0% by weight of an aqueous indigo pigment dispersion (BEZEMA Indigo AXX FL). The spraying operation was carried out so that a uniform level application of 25 wt.% Of the aqueous formulation based on the basis weight of the fabric was carried out. The color strength ratio to the standard denim product of Reference Example 1 was 90.4% at 610 nm.

The sample was sanded, bleached and washed analogously as in Reference Example 1.

The whitening achieved with the scraping pretreatment with sandpaper was low, but after complete treatment, a value of 24.3 was found for ΔΥ.

The maximum penetration depth of the printing paste in the thread cross-section was determined to be 78%.

In the assessment of the Salt & Pepper effect, a proportion of 4.4% brighter and 58.0% darker pixels (total 62.4%) was determined.

example 1

The same cotton fabric as in Comparative Example 1 was mixed with a printing paste containing, as binder, 10% by weight of TUBIFAST AS 4087 FF, 10.0% by weight of an aqueous indigo pigment dispersion (BEZEMA Indigo AXX FL.) And 1.0% by weight of emulsifier (TUBIGAT A 60), adjusted to 16,000 mPa s with a rheology additive (TUBIVIS DL 600), printed under the same conditions as Comparative Example 1.

The color strength ratio to the standard denim product of Reference Example 1 was 90.8% at 610 nm.

The sample was sanded, bleached and washed analogously as in Reference Example 1.

The scraping pretreatment with sandpaper achieved the expected lightening of the color intensity of the print, after complete treatment a value of 18.8 was found for ΔΥ. The penetration depth of the print paste in the thread cross-section was determined to be 22%.

In the assessment of the Salt & Pepper effect, a proportion of 19.4% brighter and 23.0% darker pixels (total 42.4%) was determined.

Example 2

The same cotton blended fabric as in Comparative Example 2 was adjusted to 16,000 mPa s with a printing paste containing as binder 7% by weight of Primal TR 934 HSC and as the dye component 10.0% by weight of an aqueous indigopigment dispersion (BEZEMA Indigo AXX FL.) with a rheology additive (TUBIVIS DL 600), printed under the same conditions as Comparative Example 1.

The color strength ratio to the standard denim product of Reference Example 1 was 91.6% at 610 nm.

The sample was sanded, bleached and washed analogously as in Reference Example 1.

 For scraping pretreatment with sandpaper, after completion of the treatment, Δ Wert was found to be 20.6.

The penetration depth of the printing paste in the cross section of the thread was determined to be 19%.

In the assessment of the Salt & Pepper effect, a share of 14.3% brighter and 21.7% darker pixels (total 36.0%) was determined. Example 3

The same cotton fabric as in Comparative Example 1 was mixed with a printing paste containing, as binder, 10% by weight of TUBIFAST AS 4087 FF, 10.0% by weight of an aqueous indigo pigment dispersion (BEZEMA Indigo AXX FL.) And 1.0% by weight of emulsifier (TUBIGAT A 60), adjusted to 5,000 mPa s with a rheology additive (TUBIVIS DL 600), printed under the same conditions as Comparative Example 1.

The color strength ratio to the standard denim product of Reference Example 1 was 95.0% at 610 nm.

The sample was sanded, bleached and washed analogously as in Reference Example 1.

For scraping pretreatment with sandpaper, after completion of the treatment, Δ Wert was found to be 16.3.

The penetration depth of the print paste in the thread cross-section was determined to be 38%.

In the assessment of the Salt & Pepper effect, a proportion of 17.4% brighter and 34.7% darker pixels (total 52.1%) was determined.

Example 4

The same cotton fabric as in Comparative Example 1 was sprayed with the printing paste of Example 2 diluted with water in a mass ratio of 1: 1. The spraying was carried out so that a uniform level application of 22 wt.% Of the aqueous formulation based on the basis weight of the fabric was carried out. The color strength ratio to the standard denim product of Reference Example 1 was 88.4% at 610 nm.

The sample was sanded, bleached and washed analogously as in Reference Example 1.

 For scraping pretreatment with sandpaper, after complete treatment, the value for ΔΥ was found to be 24.3.

The penetration depth of the printing paste in the cross section of the thread was determined to be 27%.

In the assessment of the Salt & Pepper effect, a proportion of 27.8% brighter and 24.6% dark pixels (total 52.4%) was determined.

Table measured values

Claims

claims: 1. A process for dyeing textile fabrics and / or made-up textiles, in particular for producing a denim-typical appearance, characterized in that a dispersion of a bleachable dye in an optionally water-containing polymeric binder with individual fibers, yarns, fabrics and / or put into contact made-up textiles. 2. The method according to claim 1, characterized in that one uses a dispersion containing indigo and / or indigoid dyes. 3. The method according to claim 1 or 2, characterized in that the dispersion has an indigo content of at least 10 wt.%, In particular at least 25 wt.%, Preferably at least 40 wt.%, Each with up to 50 wt.%, In particular up to 70% by weight, preferably up to 90% by weight, based on the dried residue of the dispersion. 4. The method according to any one of claims 1 to 3, characterized in that one uses a dispersion, wherein the indigo particles have an average size distribution (D50) of up to 100 pm, in particular up to 10 μιτι, preferably up to 1 pm and / or D95 Values of less than 150 μm, in particular less than 15 μm, preferably less than 1.5 μm. 5. The method according to any one of claims 1 to 4, characterized in that one uses fibers, yarns, fabrics and / or made-up textiles containing natural and / or synthetic fibers. 6. The method according to any one of claims 1 to 5, characterized in that one uses fibers selected from cotton, wool, polyester, polyurethane, polyurea, polyamide, elastane and / or Cellus loseregeneratfasern. 7. The method according to any one of claims 1 to 6, characterized in that one uses textile fabrics and / or made-up goods, which are selected from woven, knitted, knitted fabrics and / or nonwovens. 8. The method according to any one of claims 1 to 7, characterized in that one uses unstained and / or colored starting material. 9. The method according to any one of claims 1 to 8, characterized in that the surface of the fibers of the textile fabrics and / or the finished goods, in particular the surface of the yarns of the textile fabric and / or the finished goods, particularly preferably the surface of the textile fabrics and / or the finished goods by forced application methods, preferably by printing, coating, spraying and / or brushes with the dispersion brings into contact. 10. The method according to any one of claims 1 to 9, characterized in that one or more binders are used, which are selected from water-soluble, emulsifiable and / or dispersible polymers or copolymers, of which at least one binder optionally substituted butadiene, acrylate -, ethyl acrylate, butyl acrylate, urethane, ether, ester, silyl ether, silyl ester, amide, vinyl chloride, methacrylate, styrene, silane, siloxane, saccharide and / or polysaccharide (including celluloses and / or starches) components and / or was at least partially synthesized from such units. 11. The method according to any one of claims 1 to 10, characterized in that one uses polymeric binder whose Glasumwand- temperature (T _g ) between -40 ° C and +20 ° C and / or their E-modules between 1.0 MPa and 20 MPa. 12. The method according to any one of claims 1 to 11, characterized in that one uses dispersions, the per se known auxiliaries, in particular rheology additives, dyes, phosphors, effect pigments, catalysts, emulsifiers, preservatives, flame retardants, defoamers, leveling agents, wetting agents, Reducing agent, oxidizing agent, stabilizers and / or pH regulators included. 13. The method according to any one of claims 1 to 12, characterized in that following the aforementioned process step, the textile fabric and / or the finished textile one or more known per se treatments selected from grinding, bleaching, lasering, Tinting, enzymatic treatment and / or washing with or without addition of stones and / or enzymes. 14. Textile fabrics and / or made-up goods, in particular those with a denim-typical appearance, comprising in the region of the surface of the fibers, in particular / preferably in the region of the surface of the yarns of the textile fabric and / or the finished goods, particularly preferably in the field the surface of the textile fabrics and / or the finished goods, most preferably on the surface of a fabric side of the fabric and / or the finished goods have an anisotropic distribution of indigo and / or indigoid dyes in a polymeric binder. 15. Textile fabrics and / or made-up goods according to claim 14, characterized in that the penetration depth of the dye particles in the surface less than 1 mm, in particular less than 250 μιη preferably less than 50 pm. 16. Textile fabrics and / or made-up goods according to claim 14 or 15, characterized in that the penetration depth of the Dye particles not more than 60% of the thread diameter, in particular less than 50%, preferably less than 40%. 17. Textile fabrics and / or made-up goods according to claim 14 to 16, characterized in that the average lightening (ΔΥ) of at least one Färbbedispersion-removing or destructive aftertreated surface of the textile fabric and / or the finished goods in comparison to a untreated surface on which dyed with the dispersion of the invention side, at least 5, preferably at least 7.5, more preferably at least 10.