Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
  • D06P1/228—Indigo
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
  • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/58—Material containing hydroxyl groups
  • D06P3/60—Natural or regenerated cellulose
  • D06P3/6025—Natural or regenerated cellulose using vat or sulfur dyes

Definitions

• 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.
• 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.
• 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.
• 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.
• 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.
• oxidizing agents for example potassium permanganate (KMnO 4 )
• the dye and / or the colored cellulose layer can be removed and / or degraded.
• oxidizing agents for example potassium permanganate (KMnO 4 )
• 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.
• 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).
• 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).
• indigo is sublimated at temperatures of 150 ° C to 230 ° C (transferred from the solid to the gas phase) and deposited on the substrate.
• 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.
• 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.
• the Salt & Pepper effect is considered characteristic of denim goods.
• 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.
• 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.
• 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.
• indigo as a denim dye
• reasons for the primary use of indigo as a denim dye include, among others:
• vat dye is a vat dye, and only with such the ring dyeing of the warp yarn in the commonly practiced form succeeds.
• 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.
• Indigo can be bleached, inter alia, in a sodium hypochlorite (with hypochlorite) or with potassium permanganate (KMn0 4 ), whereby local lightening effects are possible.
• 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.
• 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).
• "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.
• SLS static light scattering
• 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.
• 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.
• 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.
• 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.
• rheology 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.
• 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.
• 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 / Sp
• 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.
• 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 ⁇ m with a microtome (for example RM 2255 from Leica) Thickness can be produced.
• 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.
• 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.
• 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).
• the average lightening ( ⁇ ) 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 ⁇ 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.
• defined conditions standard illuminant D65, illuminance 1000 lux
• the image is analyzed using Adobe® Photoshop CS3 and the number of relatively brightest and darkest pixels in the RGB color space is counted.
• 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.
• 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.
• 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 (en
• 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.
• 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.
• 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 ( ⁇ ) determines the degree of lightening.
• CIE Datacolor International SF 600 Plus
• 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.
• 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.
• the color strength ratio to the standard denim product of Reference Example 1 was 92.3% at 610 nm.
• 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 ⁇ .
• the maximum penetration depth of the printing paste in the thread cross-section was determined to be 78%.
• the color strength ratio to the standard denim product of Reference Example 1 was 90.8% at 610 nm.
• 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 ⁇ .
• the penetration depth of the print paste in the thread cross-section was determined to be 22%.
• the color strength ratio to the standard denim product of Reference Example 1 was 91.6% at 610 nm.
• the penetration depth of the printing paste in the cross section of the thread was determined to be 19%.
• the color strength ratio to the standard denim product of Reference Example 1 was 95.0% at 610 nm.
• the penetration depth of the print paste in the thread cross-section was determined to be 38%.
• Example 2 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 penetration depth of the printing paste in the cross section of the thread was determined to be 27%.

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Citations (14)

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• 2015
  • 2015-09-25 DE DE102015218510.9A patent/DE102015218510A1/de not_active Withdrawn
• 2016
  • 2016-09-16 BR BR112018005739A patent/BR112018005739A2/pt not_active Application Discontinuation
  • 2016-09-16 WO PCT/EP2016/071935 patent/WO2017050646A1/de active Application Filing
  • 2016-09-16 CN CN201680054390.8A patent/CN108138435A/zh active Pending
  • 2016-09-16 EP EP16766548.8A patent/EP3353343A1/de not_active Withdrawn
  • 2016-09-16 MX MX2018003510A patent/MX2018003510A/es unknown
• 2018
  • 2018-03-20 CO CONC2018/0002872A patent/CO2018002872A2/es unknown

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