EP3387183A1 - Behandlung von textilmaterial - Google Patents

Behandlung von textilmaterial

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Publication number
EP3387183A1
EP3387183A1 EP16808682.5A EP16808682A EP3387183A1 EP 3387183 A1 EP3387183 A1 EP 3387183A1 EP 16808682 A EP16808682 A EP 16808682A EP 3387183 A1 EP3387183 A1 EP 3387183A1
Authority
EP
European Patent Office
Prior art keywords
acid
vol
sulfate
fabric
phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16808682.5A
Other languages
English (en)
French (fr)
Inventor
Christian Bruno SCHIMPER
Paul Sebastian PACHSCHWÖLL
Hubert HETTEGGER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Acticell GmbH
Original Assignee
Acticell GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Acticell GmbH filed Critical Acticell GmbH
Publication of EP3387183A1 publication Critical patent/EP3387183A1/de
Withdrawn legal-status Critical Current

Links

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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/13—Fugitive dyeing or stripping dyes
    • D06P5/132—Fugitive dyeing or stripping dyes with oxidants
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B11/00—Treatment of selected parts of textile materials, e.g. partial dyeing
    • D06B11/0093—Treatments carried out during or after a regular application of treating materials, in order to get differentiated effects on the textile material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B11/00—Treatment of selected parts of textile materials, e.g. partial dyeing
    • D06B11/0093—Treatments carried out during or after a regular application of treating materials, in order to get differentiated effects on the textile material
    • D06B11/0096—Treatments carried out during or after a regular application of treating materials, in order to get differentiated effects on the textile material to get a faded look
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D06C7/04—Carbonising or oxidising
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/005—Laser beam treatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/153—Locally discharging the dyes with oxidants
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/10—After-treatment with compounds containing metal
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/13—Fugitive dyeing or stripping dyes
    • D06P5/131—Fugitive dyeing or stripping dyes with acids or bases
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/151—Locally discharging the dyes with acids or bases

Definitions

  • the present invention relates to non hazardous methods to improve the treatment of a fabric and specifically to increase the abrasion intensity of laser treated fabric.
  • Fabric such as denim
  • a wet process such as a stone and/or enzyme process are applied to the fabric, typically after the fabric has been transformed into a garment, to create a faded and/or worn look.
  • an enzyme wash in combination with an agitation element, such as stones or rocks removes color from a ridged blue denim fabric to develop a contrasting pattern of variable color intensities creating a stonewashed look.
  • the faded areas of the denim fabric can correspond to where stones or rocks contact the fabric during the enzyme washing process.
  • a CO2 laser treatment has been used for several years for surface designing of patterns.
  • the CO2 laser treatment is a dry treatment and can be applied to textile materials as an alternative to conventional dry and wet treatments such as hand sanding, sand blasting, stone washing and bleaching, for achieving faded look and worn out effects.
  • US 5,567,207 discloses a method for making and fading textile with lasers.
  • the laser is used to simulate conventional laundering techniques, such as stone washing, ball washing and acid washing, without the use of water or chemicals.
  • the laser burns the surface of the denim fabric. Depending on the intensity of the laser every color from blue or black to complete white can be achieved. The lighter the bleaching effect is, the more dramatic is the fiber damage, which can cause breaking of the fabric.
  • US 6,819,972 discloses a laser method to simulate the abrasion effect of a worn look.
  • the patent teaches to define a desired pattern of color alterations to be formed on a garment by selecting a plurality of areas on a display and to associate a level of abrasion with each area.
  • the patent further teaches to change the energy density per unit time along a single scan line in order to achieve the feathering required to simulate the worn look.
  • Lasers operating in this fashion can simulate the worn look, but the garments often need to be processed after the laser treatment with hand sanding and/or potassium permanganate in order to improve abrasion intensity and pattern characteristics.
  • the laser time may exceed several minutes with a conventional 100 - 200 watt laser in order to achieve the required energy intensity.
  • Higher power lasers from 500 to 2,500 watts can on the one hand significantly reduce the time, but on the other hand require larger capital investments.
  • a method for changing the color of a fiber, yarn, fabric or garment in order to obtain a vintage look wherein said fiber, yarn, fabric or garment is subjected to a treatment with a nitrogen salt in presence of an acid catalyst or treatment conditions which induce acid formation.
  • the present invention relates to a method for increasing the color of a dyed textile material comprising the steps of:
  • a further embodiment of the invention relates to a method as described above, wherein the nitrate salt is an organic or inorganic nitrate salt.
  • a further embodiment of the invention relates to the method as described above, wherein the inorganic nitrate salt is selected from the group consisting of
  • Bi(NO 3 ) 3 FNOs, CINOs, Xe(NO 3 ) , Ce(NO 3 ) 3 , Ce(NO 3 ) 4 , Gd(NO 3 ) 3 .
  • a further embodiment of the invention relates to the method as described above, wherein nitrate salt is Mg(NO 3 ) 2 , KNO 3 , LiNOs, NaNO 3 , AI(NO 3 ) 3 , Ca(NO 3 ) 2 ,
  • Fe(NO 3 ) 3 Cu(NO 3 ) 2 , Zn(NO 3 ) 2 , Co(NO 3 ) 2 , or (NH 4 ) 2 Ce(NO 3 ) 6 .
  • a further embodiment of the invention relates to the method as described above, wherein the nitrate salt is applied in solution, wet or dry form.
  • a further embodiment of the invention relates to the method as described above, wherein the acid catalyst is selected from the group consisting of organic or inorganic compounds, i.e. organic or inorganic chlorides, sulfates, phosphates, borates, fluorides, acid forming esters, amino acid hydrochlorides, and Lewis acid chlorides.
  • the acid catalyst is selected from the group consisting of organic or inorganic compounds, i.e. organic or inorganic chlorides, sulfates, phosphates, borates, fluorides, acid forming esters, amino acid hydrochlorides, and Lewis acid chlorides.
  • a further embodiment of the invention relates to the method as described above, wherein the nitrate salt is applied on local parts of the fabric.
  • a further embodiment of the invention relates to the method as described above, wherein the nitrate salt is applied on local parts of the fabric in a way
  • a further embodiment of the invention relates to the method as described above, wherein the acid catalyst is selected from the group consisting of
  • a further embodiment of the invention relates to the method as described above, wherein the Lewis acid chloride is ferric chloride, zinc chloride, lithium chloride, copper chloride, magnesium chloride or aluminum chloride and a sulfate as
  • manganese sulfate and the phosphate is a monosodium phosphate, disodium phosphate, monopotassium phosphate, dipotassium phosphate, monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, ammonium
  • polyphosphate monoammonium phosphate, diammonium phosphate, monocalcium phosphate, dicalcium phosphate, disodium pyrophosphate, trisodium pyrophosphate, tetrasodium pyrophosphate, sodium triphosphate, penta potassium triphosphate.
  • a further embodiment of the invention relates to the method as described above, wherein the acid catalyst is provided as a buffered substance.
  • a further embodiment of the invention relates to the method as described above, wherein the acid catalyst is capsuled.
  • a further embodiment of the invention relates to the method as described above, wherein the treatment is carried out by a temperature of below 65 °C, or at a temperature of below 90 °C, or at higher temperature where applicable, if the acid catalyst decreases the activation temperature in comparison to the pure nitrate compound.
  • a further embodiment of the invention relates to the method as described above, wherein the aqueous solution comprises Mg(NO3)2, optionally another nitrate compound (e.g. AI(NO3)3) and an acid, e.g. tartaric acid.
  • Mg(NO3)2 optionally another nitrate compound (e.g. AI(NO3)3)
  • an acid e.g. tartaric acid.
  • a further embodiment of the invention relates to the method as described above, wherein the aqueous solution comprises AI(NO3)3 and toluenesulfonic acid.
  • a further embodiment of the invention relates to the method as described above, wherein the pH of the aqueous solution is higher than 2.
  • a further embodiment of the invention relates to the method as described above, wherein the pretreatment is carried out at a temperature of about 10 to 90 °C, or at a temperature of about 10 to 60 °C, or at a temperature of about 10 to 50 °C or at room temperature.
  • a further embodiment of the invention relates to the method as described above, wherein the pretreatment step is carried out in the presence of a sulfate and/or chloride compound.
  • a further embodiment of the invention relates to the method as described above, wherein optionally an auxiliary agent is used.
  • a further embodiment of the invention relates to the method as described above, wherein the auxiliary agent is present in an amount of 0.01 -15 vol%.
  • a further embodiment of the invention relates to the method as described above, wherein the auxiliary agent is selected from the group consisting of another nitrate, softener, brightening agent, plastic, natural and synthetic polymers, silicates, silica, a thickening agent, dyestuff used as a marker dye, a wetting agent, a
  • a further embodiment of the invention relates to the method as described above, wherein the fabric is dyed with a sulphur dye, reactive dye, direct dye, VAT dye, basic dye, pigment dye, or natural dye or a mixture thereof.
  • a further embodiment of the invention relates to the method as described above, wherein the fabric is indigo dyed.
  • a further embodiment of the invention relates to the method as described above, wherein wherein the AL value between the untreated and treated part is greater than 2 (L stands for the lightness in the CIE 1976 Lab color space).
  • a further embodiment of the invention relates to the method as described above, wherein the laser beam is applied to the fabric to change the color intensity to value ranges of L from 15-40 to 30-60, or from 15-30 to 30-60.
  • a further embodiment of the invention relates to the method as described above, wherein the Lab color space lightness value ranges for L of from 20 to 60 are achieved by laser treatment.
  • One embodiment of the invention relates to a method to increase the color value of laser treated fabric by mixing a nitrate salt with a buffer compound containing a phosphoric acid and corresponding salts of this acid, applying this solution to a fabric, drying the fabric in a dryer by selecting the temperature in such a way that the bleaching reaction does not take place in a significant way during the drying step (e.g. less than 60 °C), and applying a laser beam to the fabric to generate nitrogen oxide compounds, which attack the indigo dye and thereby create a color value change.
  • One embodiment of the invention relates to a method to increase the color value of laser treated fabric by mixing a nitrate salt with an acid catalyst, applying this solution to a fabric, drying the fabric in a dryer by selecting the temperature in such a way that the bleaching reaction does not take place in a significant way during the drying step (e.g. less than 60 °C) and applying a laser beam to the fabric to generate nitrogen oxide compounds which attack the indigo dye and thereby create a color value change.
  • a significant way during the drying step e.g. less than 60 °C
  • One embodiment of the invention relates to a method to increase the color value of laser treated fabric by mixing a nitrate salt with an acid catalyst, applying this solution to a fabric, drying the fabric in a dryer by selecting the temperature in such a way that the bleaching reaction does not take place in a significant way during the drying step (e.g. less than 60 °C) and applying a laser beam in several passages (same or different pattern) to the fabric to generate nitrogen oxide compounds, which attack the indigo dye and thereby create a color value change.
  • Fibers may be spun into yarns or combined to non-woven fabric, yarns may be woven or knitted into fabric and fabric may be cut and sewn into garments. All materials may be treated with methods used in the textile industry (e.g. ozone treatment, etc.) in continuous or batch processes in such a way that the nitrate compound is not washed away from the material.
  • a laser beam is applied to the previously treated material in a single passage or in several passages (same or different pattern) to the fabric to generate nitrogen oxide compounds which attack the indigo dye and thereby create a color value change.
  • One embodiment of the invention relates to a method to increase the color value of laser treated fabric by applying a solution comprising 20 - 35 vol% nitrate salt, optionally about 0.1 - 2 vol% of a different nitrate salt, and about 5.0 - 35.0 vol% acid catalyst, to a fabric, drying the fabric in a dryer at temperatures less than 60 °C, applying a laser beam to the denim to generate nitrogen oxide compounds which attack the indigo dye and thereby create a color value change.
  • One embodiment of the invention relates to a method to increase the color value of laser treated fabric by applying a solution comprising 20 - 30 voi% Mg(NO3)2, optionally about 0.01 - 2 vol% of another nitrate salt and about 1.0 - 20.0 vol% tartaric acid to a fabric, drying the fabric in a dryer or oven at temperatures less than 60 °C, and then applying a laser beam to generate nitrogen oxide compounds, which attack the indigo dye and thereby create a color value change.
  • One embodiment of the invention relates to a method to increase the color value of laser treated fabric by using a solution comprising about 5 - 20 vol% AI(NO3)3, optionally about 5 vol% butyl diglycol, mixing it with a solution of about 10 - 35 vol%
  • One embodiment of the invention relates to a method to increase the color value of laser treated fabric by using a solution comprising about 10 vol% AI(NO3)3, optionally about 5 vol% butyl diglycol, mixing it with a solution of about 30 vol%
  • One embodiment of the invention relates to a method to increase the color value of laser treated fabric by applying a solution comprising about 0.1 - 20 vol%
  • AI(NO3)3 optionally about 5 vol% butyl diglycol, and about 0.01 - 35 vol% toluenesulfonic acid to the fabric depending on the intensity of the desired effect, and drying the fabric (e.g. dryer, oven, fan, air dry, etc.) by selecting the temperature in such a way that the bleaching reaction does not take place in a significant way during the drying step (e.g. less than 60 °C), applying a laser beam to the fabric to generate nitrogen oxide compounds, which attack the indigo dye and thereby create a color value change.
  • drying the fabric e.g. dryer, oven, fan, air dry, etc.
  • a further embodiment of the invention relates to a method to increase the color value of laser treated fabric by applying a solution comprising about 0.1 - 20 vol% AI(NO3)3, optionally about 5 vol% butyl diglycol, and about 30 vol% toluenesulfonic acid to the fabric depending on the intensity of the desired effect, and drying the fabric (e.g. dryer, oven, fan, air dry, etc.) by selecting the temperature in such a way that the bleaching reaction does not take place in a significant way during the drying step (e.g. less than 60 °C), applying a laser beam to the fabric to generate nitrogen oxide compounds, which attack the indigo dye and thereby create a color value change.
  • a solution comprising about 0.1 - 20 vol% AI(NO3)3, optionally about 5 vol% butyl diglycol, and about 30 vol% toluenesulfonic acid to the fabric depending on the intensity of the desired effect
  • drying the fabric e.g. dryer, oven, fan, air dry, etc.
  • One embodiment of the invention relates to a method to increase the color value of laser treated fabric by applying a solution comprising an aluminum based nitrate salt, optionally a wetting agent, and toluenesulfonic acid to the fabric, drying the fabric, applying a laser beam to the fabric to generate nitrogen oxide compounds, which attack the indigo dye and thereby create a color value change.
  • One embodiment of the invention relates to a method to increase the color intensity of laser treated fabric by mixing a magnesium based nitrate salt with buffer compound containing a phosphoric acid and the corresponding salt of this acid, and applying this solution to fabric, and drying the fabric in a dryer at temperatures less than 60 °C, and applying a laser beam to the fabric to change the color intensity to value ranges of L from 15-40 to 30-60.
  • One embodiment of the invention relates to a method to increase the color intensity of laser treated fabric by mixing a magnesium based nitrate salt with catalyst, and applying this solution to fabric, and drying the fabric in a dryer at temperatures less than 60 °C, and applying a laser beam to the fabric to change the color intensity to value ranges of L from 15-30 to 30-60.
  • One embodiment of the invention relates to a method to increase the color intensity of laser treated fabric by mixing a magnesium based nitrate salt with catalyst, and applying this solution to fabric, and drying the fabric (e.g. dryer, oven, fan, air dry, etc.) by selecting the temperature in such a way that the bleaching reaction does not take place in a significant way during the drying step (e.g. less than 60 °C), and applying a laser beam to the fabric to change the color intensity to value ranges of L from 15-30 to 30-60.
  • a magnesium based nitrate salt e.g. dryer, oven, fan, air dry, etc.
  • One embodiment of the invention relates to the use of an aqueous solution applied to fabric to increase the color value of laser treated fabric.
  • One embodiment of the invention relates to the use of an aqueous solution containing magnesium salt and at least one of a buffer or a catalyst, and applying the aqueous solution to fabric to increase the color value of laser treated fabric.
  • One embodiment of the invention relates to a method to achieve Lab color space value ranges for L from 15 to 100.
  • One embodiment of the invention relates to a method to achieve Lab color space lightness value ranges for L of from 20 to 60 by laser treating fabric that has been pretreated with magnesium salt mixed with either a buffer or catalyst.
  • One embodiment of the invention relates to a method to increase the Lab color space lightness value L by 2 points by laser treating the fabric that has been pretreated with magnesium salt mixed with either a buffer or catalyst compared to the untreated fabric.
  • One embodiment of the invention relates to a method to increase the Lab color space lightness value L by 2 points by laser treating the fabric that has been pretreated with nitrate salt mixed with either a buffer or catalyst compared to the untreated fabric.
  • One embodiment of the invention relates to a method as described above wherein the drying step b) results in a color change that is lower than a lightness value of the fabric by 2 points.
  • One embodiment of the invention relates to an article obtained by a method as described above.
  • a further embodiment of the invention relates to the method as described above, wherein the applied compounds are non-hazardous.
  • a further embodiment of the invention relates to the method as described above, including the use of a thickening agent to increase the viscosity of the solution by at least 10%.
  • a further embodiment of the invention relates to the method as described above, wherein the thickening agent is a polymer.
  • a further embodiment of the invention relates to the method as described above, wherein the drying temperature is kept below a critical temperature which would cause the reaction to proceed with a noticeable color value effect.
  • a further embodiment of the invention relates to the method as described above, wherein the ratio of the buffer to the magnesium salt ranges from 3: 1 to 1 :10.
  • a further embodiment of the invention relates to the method as described above, wherein the concentration of the catalyst ranges from 0.1 % to 10%.
  • a further embodiment of the invention relates to the method as described above, including the use of a wetting agent in a concentration of 0.1 -5% to increase the penetration of the solution.
  • a further embodiment of the invention relates to the method as described above, including the use of a softening agent in a concentration of 0.1 -20% to increase the penetration of the solution.
  • a further embodiment of the invention relates to the method as described above, wherein the softening agent is a polymer.
  • a further embodiment of the invention relates to the method as described above, wherein the softening agent is a glycol derivative.
  • a further embodiment of the invention relates to the method as described above, wherein one auxiliary agent is a plastic compound (e.g. PMMA, PVC, PE, PP, each in modified and unmodified form, etc.).
  • a plastic compound e.g. PMMA, PVC, PE, PP, each in modified and unmodified form, etc.
  • a further embodiment of the invention relates to the method as described above, wherein one auxiliary agent is a silica/silicate compound (e.g. amorphous or crystalline S1O2, sodium silicate etc.).
  • a silica/silicate compound e.g. amorphous or crystalline S1O2, sodium silicate etc.
  • a further embodiment of the invention relates to the method as described above, wherein the aqueous solution comprises about 25 vol% of a nitrate salt, a of phosphate buffer from about 1.0 to 10 vol% and optionally any auxiliary agent ranging from 0.01 to 20 vol%.
  • the above said auxiliary agent is selected from the group consisting of another nitrate, a softener, brightening agent, plastic, natural and synthetic polymers, S1O2, silicates, a thickening agent, dyestuff used as a marker dye, a wetting agent, a complexing agent, a dispersing agent, and a buffer solution derived from the salt of an acid and the corresponding acid.
  • a further embodiment of the invention relates to the method as described above, wherein the solution comprises an organic (nitro-)compound, which is releasing NOx after laser activation and/or other heat activation.
  • a further embodiment of the invention relates to the method as described above, wherein the solution comprises a compound, which increases the laser energy uptake of the treated material.
  • a further embodiment of the invention relates to the method as described above, wherein the solution comprises a compound, which changes the laser light scattering/adsorbing/emitting behavior on the surface of the material.
  • a further embodiment of the invention relates to the method as described above, wherein the solution comprises a compound, which gets cleaved/activated in a first step by a laser treatment and the resulting products are eventually inducing the actual nitrate bleaching mechanism.
  • a further embodiment of the invention relates to the method as described above, wherein the aqueous solution comprises about 25 vol% of a nitrate salt, of about 1.0 to 10 vol% KAI(SO 4 )2 and optionally any auxiliary agent ranging from 0.01 to 20 vol% where the agent can be selected from the group nitrates, polymers, marker dyes, complexing agents, wetting agents, softening agents and dispersing agents.
  • One embodiment of the invention relates to a fabric obtained by a method as described above.
  • the invention discloses a novel combination of a non hazardous chemical treatment to denim followed by a laser treatment which together provide the abrasion intensity to simulate the worn out look on denim jeans without the use of the
  • magnesium salt Mg(NO3)2 can generate compounds that oxidize the indigo dye in denim and produce bleached effects.
  • the respective relevant chemical reaction is:
  • the chemical reaction generates nitrogen oxides which attack or oxidize the Indigo dye at the denim.
  • the NO2 can be a variety of nitrogen oxide (NOx) compounds, such as N 2 O, N 2 O 3 , NO 2 , N 2 O 4 , NO 3 , N 2 O 4 , N 2 O 5 , NO 3 , N 2 O 6 and NO.
  • NO x is hazardous by itself but it is either consumed by the indigo or evaporated and
  • the magnesium salt is applied to denim and then the treated denim is heated at temperatures of about 140 °C for about 20 minutes.
  • the activation energy to promote the chemical reaction is dependent upon both time and temperature. So applying a laser process to the denim treated with the magnesium salt will not generate the chemical reaction and thus will not produce a bleached effect even though the laser temperature is much higher than 140 °C.
  • Laser systems are used in fashion design, pleating, cutting and modification of fabric surface to impart some special finish. Laser fading works with better precision and higher productivity but also have some drawbacks.
  • the laser works by creating extensive heat. Within the focused region, the material is subject to very intensive heating within a very small region and time. Laser energy is absorbed as heat and the material rapidly heats leading to melting as a phase change from solid to liquid takes place.
  • Irradiation may be applied by a laser device that emits light through a process of optical amplification based on the stimulated emission of electromagnetic radiation.
  • Nd:YAG lasers many fiber lasers and the most powerful laser diodes emit near-infrared light. There are comparatively few laser sources for the mid- and far-infrared spectral regions. CO2 lasers can emit at 10.6 pm and some other wavelengths in that region.
  • UV lasers for the generation of ultraviolet light faces various challenges; nevertheless, there are a few kinds of ultraviolet lasers which can directly generate UV light: some bulk lasers (e.g. based on cerium-doped crystals such as Ce:LiCAF), fiber lasers, laser diodes (mostly GaN-based), dye lasers, excimer lasers, and free electron lasers.
  • some bulk lasers e.g. based on cerium-doped crystals such as Ce:LiCAF
  • fiber lasers e.g. based on cerium-doped crystals such as Ce:LiCAF
  • laser diodes mostly GaN-based
  • dye lasers e.g. based on excimer lasers, and free electron lasers.
  • the pretreated textile material is placed under a laser device and then scanning a laser beam having a selected wavelength, power density, pulse width, and repetition rate over the textile material until the desired degree of fading and/or worn appearance or the selected pattern is achieved.
  • the laser may be a q-switched Nd:YAG laser with a wavelength of about 1064 nanometers, although other lasers, such as CO2 gas lasers or excimer gas lasers may be utilized.
  • the wavelength of the laser is chosen to give optimal dye photo- decomposition without affecting the textile material.
  • the scanning of the laser beam over the textile material may be controlled by galvanometric mirror, acousto-optic deflector, deflector, magneto-optic beam deflector, polygon mirror, or a moving holographic optical element.
  • Other possible wavelengths for other laser sources range between 190 nanometers to 10600 nanometers.
  • An excimer laser may operate effectively at wavelengths of 196 nm to 235 nm, or a CO2 laser may operate effectively at 10600 nanometers.
  • the wavelength of the laser should be chosen such that it is strongly absorbed by the dye to be faded but not by the textile material.
  • the range of pulse duration used has been from 5 nanoseconds to 100 microseconds, with the best results being from 20 to 350 nanoseconds.
  • Other variables, such as the pulse energy, peak power, scan speed, dot pitch, and energy density play an important factor in the degree of photo-decomposition and the avoidance of damage to the textile material.
  • variable parameters may include the laser beam having a repetition rate from 1 hertz to 500 MHz (500x10 6 hertz), a pulse duration between approximately 10 fs (10x10- 15 seconds) to 500 ms (500x10 3 seconds), the laser beam may have a continuous output beam and is classified as a cw laser, a pulsed laser, or the laser beam have a scan speed of 1 mm per minute to 500 meter/second, and a dot pitch between 0.1 urn to 5 meters.
  • the textile material is less damaged, e.g. prevents burned surface of the fibers or less damage to synthetic fibers.
  • Further advantages of the present invention are a working environment in a continuous process, faster cycle times and fewer cycles conducted over the textile material, or less laser power needed, which again leads to less damages of the textile material and better chemical uptake (e.g. dyeability) of the laser treated areas.
  • One embodiment of the invention relies upon the non hazardous magnesium salt chemical and its reaction to generate the NO x compounds, but in addition, mixing the salt with a buffer to both lower the activation temperature and to control the pH value at a non-hazardous level.
  • a buffer for example, one preferred buffer is HsPO 4 +
  • Another embodiment of the invention is to use a two component solution consisting of the acid and its corresponding salt.
  • Another embodiment is to use an aqueous solution of a nitrate salt and buffer.
  • Another embodiment of this invention relies upon the magnesium salt chemical reaction to generate the NO x compounds, but in addition, mixing the salt with a catalyst to decrease the reaction temperature and to control the pH value.
  • Another embodiment of this invention is to achieve a non hazardous solution according to the Globally Harmonized System of Classification and Labeling of
  • GLS Chemicals
  • REACH SVHC list the Restricted Substance Lists of various Labels like Levi Strauss & Co, and GOTS, the Global Organic Textile Standard. If the material gets a hazardous sign in the MSDS, it is classified as hazardous. If the material is listed in the RSL list it is not allowed in the manufacturing plant because it is deemed hazardous.
  • textile material or “fabric” are used interchangeably and refer to fibers, yarns, fabrics, flexible knitted, woven or non-woven material consisting of a network of natural or artificial fibers (yarn or thread).
  • the textile material may be used in production of further goods (cloths, garments, carpets, bags, shoes, jewelry, furnishings, artifacts, etc.).
  • the textile material is finished colored denim.
  • the method may be applied to a variety of garments including jeans, jean jackets, jean skirts, jean shorts, jean dresses, jean vests, corduroy and twill garments. The method may also be applied on other fabrics besides denim fabrics.
  • the textile material may be dyed or coated with a dye, preferably with a natural or synthesized dye.
  • the fabrics are dyed with an indigo dye, which may be a natural or synthesized indigo dye, or sulphur black dye.
  • the yarns of the fabrics are dyed with sulphur black dyes, a combination of indigo dye and sulphur black dye or a combination of sulphur black below, in-between and on top of the indigo dye on the yarn.
  • the textile material may consist of cellulosic material (e.g. natural fibers like bast fibers (e.g. jute, flax, hemp, etc.), leaf fibers (e.g.
  • sisal, etc. seed fibers (e.g. cotton, etc.), or other fibers like bamboo, etc., or man-made fibers like lyocell type, viscose and rayon type, or modal type, cupro type, acetate type), and in special cases also fibers based on proteins (e.g. soja, casein, fibroin, sericin, etc.), starch and glucose (e.g. polylactide fibers, etc.), alginates and chitosanes, but not limited to, and may be used in a combination of synthetic fiber types derived from polycondensation (e.g. polyester, polyethyleneterephtalate, polyamide, polyimide, polyamide-imid, polyphenylensulfide, aramide, etc.), polymerization (e.g. polyacrylonitrile,
  • polycondensation e.g. polyester, polyethyleneterephtalate, polyamide, polyimide, polyamide-imid, polyphenylensul
  • polytetrafluorethylene polyethylene, polypropylene, polyvinylchloride, etc.
  • fibers produced by polyaddition procedure e.g. polyurethane, etc., but not limited to.
  • the nitrogen compound may be an organic nitro- or nitrate-compound like an aliphatic, aromatic, heterocyclic or a biochemical organic compound selected from the group consisting of alkanes, alkenes, alkynes, cyclic compounds, as well as ally!-, alkyl-, arylcompounds, alcohols, aldehydes, esters, ethers, ketones, carbohydrates, or inorganic nitrates of heavy metals or of an alkali-metal, alkaline earth metal, or one of the boron group, carbon group, nitrogen group, chalcogens, halogens, noble gases, as well as from the group of transition metals, Lanthanides and Actinides.
  • a biochemical organic compound selected from the group consisting of alkanes, alkenes, alkynes, cyclic compounds, as well as ally!-, alkyl-, arylcompounds, alcohols, aldehydes, esters, ethers, ketones,
  • the nitrogen compound is a nitrate salt which is selected from the group consisting of Mg(N03)2, KNO3, L1NO3, AI(N03)3, Ca(N0 3 ) 2 , Fe(N0 3 )3, Cu(N0 3 ) 2 , Zn(NO 3 ) 2 , Co(N0 3 ) 2> (NH 4 ) 2 Ce(NO 3 )6, NaNOs, RbNO 3 , CsNOs, Be(N0 3 ) 2 , Sr(N0 3 ) 2 , Ba(N0 3 ) 2 , Sc(NO 3 )3, Ti(NO 3 )4, Zr(N0 3 ) 4 , VO(N0 3 ) 3 , Cr(NO 3 )3, Mn(NO 3 ) 2 , Co(N0 3 )3, Ni(NO 3 ) 2 , Pd(N0 3 ) 2 , AgNOs, Cd(N0 3 ) 2 , Hg 2
  • the nitrate salt is selected from the group consisting of Mg(N0 3 ) 2 , UNO3, AI(NO 3 )3, Fe(N0 3 )3, Zn(N0 3 ) 2 , Ce(N0 3 )3, Ce(N0 3 )4, as well as their respective salts with nitrite.
  • the nitrate salt may be used in a concentration of higher than 0.5 g/L, limited by its solubility in the solvent. In one embodiment a mixture of nitrate salts is used. In one further embodiment the nitrate salt or mixture is used in a dry form, e.g. as a powder.
  • solvents are polar and/or low-polarity solvents as primary solvents or as mixtures or emulsions in any desired ratio, such as water, alcohols, fatty alcohols, aliphatic fatty alcohols, aromatic fatty alcohols, amines, octylamines, cyclic amines, hydrocarbon solvents, naphthenic solvents, paraffinic solvents, aromatic derivatives such as diisopropylnaphthalene, glycols, polyglycols, esters, branched monoesters, oleic esters, benzoic esters, lactic acid esters, myristic acid esters, palmitic acid esters, fatty acid esters in general, propylene glycol acetates, dipropylene glycol ether acetate, polyethylene glycol acetates, diethylene glycol monobutyl ether acetate, glycol ethers, polypropylene glycol esters, tripropylene glycol monomethyl ether,
  • the acid may be an Arrhenius acid, Bronsted-Lowry acid or a Lewis acid, chemically characterized as monoprotic or polyprotic acids or salts thereof which may be mineral acids (inorganic acids) or organic acids like sulfonic acids or salts thereof, aliphatic or aromatic carboxylic acids, amino acids, halogenated carboxylic acids and vinylogous carboxylic acid or salts thereof.
  • the acid may be selected from the group consisting of sulfuric acid, hydrochloric acid, fluorosulfuric acid, phosphoric acid, fluoroantimonic acid, fluoroboric acid,
  • trichloroacetic acid ascorbic acid, aspartic acid, and mandelic acid. Mixtures of two or more of these compounds may also be used, as well as in a combination with corresponding salts to form buffer solutions.
  • the acid catalyst may be for example selected from the group consisting of organic or inorganic compounds, i.e. organic or inorganic forms of chlorides, sulfates, phosphates, borates, fluorides, Lewis acid chlorides, such as ferric chloride, zinc chloride and aluminum chloride, magnesium chloride, ammonium chloride, potassium aluminum sulfate, ammonium sulfate, maleate ester, an amino acid hydrochloride, such as glycine hydrochloride, glutamic acid hydrochloride, betaine hydrochloride, alanine hydrochloride, valine hydrochloride, lysine hydrochloride, arginine
  • organic or inorganic compounds i.e. organic or inorganic forms of chlorides, sulfates, phosphates, borates, fluorides, Lewis acid chlorides, such as ferric chloride, zinc chloride and aluminum chloride, magnesium chloride, ammonium chloride, potassium aluminum sulfate, ammonium
  • Suitable acid catalysts include organic acids such as citric acid and tartaric acid.
  • Magnesium chloride, ammonium chloride, zinc chloride, zinc fluoroborate and zinc nitrate are suitable (weak) acids, as well as water soluble salts of mono-, di-, tri- and polyphosphates (e.g. monosodium phosphate, disodium phosphate, trisodium phosphate, monopotassium phosphate, dipotassium phosphate, tripotassium
  • phosphate monomagnesium phosphate, dimagnesium phosphate, trimagnesium phosphate, ammonium polyphosphate, monoammonium phosphate, diammonium phosphate, triammonium phosphate, monocalcium phosphate, dicalcium phosphate, tricalcium phosphate, disodium pyrophosphate, trisodium pyrophosphate, tetrasodium pyrophosphate, sodium triphosphate, pentapotassium triphosphate), and
  • pyrophosphates or organophosphates which are esters of phosphoric acid and phytinic acid and their corresponding salts; as well as complexing agents which may be but not limited to selected from the list of methylglycindiacetic acid, ethylenediaminetetraacetic acid, L-glutamic acid ⁇ /,/V-di acetic acid tetra sodium salt, alanine-/V,AAdiacetic acid trisodium salt, diethylene triamine pentaacetic acid, nitrilotriacetic acid, ethylene glycol tetraacetic acid, ethylenediamine-/V,/V-disuccinic acid, poiycarboxylates, zeoiithes, and phosphonates. Mixtures of two or more of these compounds may also be used, as well as in combination to form buffer solutions.
  • Preferred solute concentrations of the acid depend upon the particular acid catalysts used. Lower concentrations of highly active compounds may be used to avoid unwanted acid damage to the fabric and higher concentrations of less active compounds.
  • the solution of the acid together with the nitrate is preferably an aqueous solution, but it may be also applied in separate steps or in a mixture of the pure substances in powder form. One or more components may be encapsulated in the solution or the solid form.
  • the textile material may be evenly or unevenly impregnated with this composition using any of the conventional techniques.
  • the application of one or more components together or in separate form on the fibers, yarns, fabrics or garments may be performed by immersion, padding, spraying, brushing, printing, foaming, sponging, other contact methods like stone and/ or powder carrier, but not limited to, at any stage of processing.
  • the aqueous solution is sprayed on the raw or desized denim garment on limited areas, or covering all parts of the garment, to create localized bleached effects simulating wear areas on the jeans or applied on prepared shaped motif to jeans or fabric which can be subsequently washed to highlight the applied areas.
  • the solution may be applied on fabric form by immersion or as a one side application by printing (e.g. as block printing or roller cage printing), spraying, foaming, or a kiss roll on all areas of the application side or on limited areas of the application side.
  • the acid catalyst may be applied in a concentration of higher than 0.01 g/L, limited by its solubility in the solvent. In one embodiment a mixture of acids may be used.
  • the ratio of acid catalyst to the nitrate salt in the reaction mixture is in the range of about 75: 1 to 1 : 100, preferably in the range of about 20: 1 to 1 :20, more preferably in the range of 5: 1 to 1 :20, most preferred in the range of 1 : 1 to 1 :5.
  • one or more further catalysts may be added to the reaction mixture such as for example a sulfate compound, phosphate compound, ammonium compound and/or a chloride compound, or mixtures thereof.
  • the method is carried out in the presence of a sulfate, a phosphate and/or chloride catalyst.
  • the sulfate may be selected from the group consisting of MgSO 4 , Ce(SO 4 ) 2 , VOSO 4 , FeSO 4 , Fe 2 (SO 4 ) 3 , CuSO 4 ,
  • the phosphate may be selected from the group of calcium, sodium, potassium and ammonium phosphates such as NaH 2 PO 4 , Na 2 HPO 4 , KH 2 PO 4 , K 2 HPO 4 , Ca(H 2 PO 4 ) 2 , CaHPO 4 , Na 2 H 2 P 2 O 7 , Na 3 HP 2 O 7 , NasPsOio, K5P3O10, (NH 4 )H 2 PO 4 , (NH 4 ) 2 HPO 4 .
  • the chloride may be selected from heavy metal chloride such as for example from ZnCI 2 , FeC , FeCI 2 , CuCI 2 , MnCI , CoCI 2 , NiCI 2 or AlCb.
  • the textile material is treated with
  • the textile material is treated with
  • Mg(NO3) 2 in the presence of tartaric acid and optionally another nitrogen compound for about 20 min at a temperature of about 60 °C.
  • the textile material is treated with an aqueous solution comprising at least one nitrate salt - depending on the cation species - in a concentration of about 1 - 80 vol%, or of about 5 - 75 vol%.
  • the aqueous solution comprises at least one nitrate compound in a concentration of about 1 vol%, 2.5 vol%, 5 vol%, 7.5 vol%, 10 vol%, 15 vol%, 18 vol%, 20 vol%, 25 voi%, 26.6 vol%, 28 vol% 30 vol%, 32.5 vol%, 35 vol%, 38.5 vol%, 40 vol%, 42.5 vol%, 45 vol%, 47.5 vol%, 50 vol%, 51 vol%, 52 vol%, 55 vol%, 57 vol%, 60 vol%, 62.5 vol%, 65 vol%, 67.5 vol%, 70 vol%, 72.5 vol%, or 75 vol%.
  • the aqueous solution comprises at least one nitrate salt in a concentration as stated about, wherein said nitrate salt is selected from the group consisting of Mg(N0 3 ) 2 , UNO3, AI(N03) 3 , Ca(N0 3 )2, Fe(N0 3 ) 3 , Cu(NO 3 ) 2 , KNO3, NaNOs, (NH 4 ) 2 Ce(NO 3 )6, Co(NO 3 ) 2 , or Fe(NO 3 ) 2 , or hydrates thereof.
  • the aqueous solution may also comprise auxiliary agents.
  • the aqueous solution comprises at least one nitrate salt in a concentration as stated above and at least one acid catalyst in a concentration of about 0.01 vol%, 0.05 vol%, 1.0 vol%, 1.25 vol%, 1.5 vol%, 1.75 vol%, 2.0 vol%, 2.25 vol%, 2.5 vol%, 2.75 vol%, 3.0 vol%, 3.25 vol%, 3.5 vol%, 3.75 vol%, 4.0 vol%, 4.25 vol%, 4.5 vol%, 4.75 vol%, 5.0 vol%, 5.25 vol%, 5.5 vol%, 5.75 vol%, 6.0 vol%, 6.25 vol%, 6.5 vol%, 6.75 vol%, 7.0 vol%, 7.25 vol%, 7.5 vol%, 7.75 vol%, 8.0 vol%, 8.25 vol%, 8.5 vol%, 8.75 vol%, 9.0 vol%, 9.25 vol%, 9.5 vol%, 9.75 vol%, 10.0 vol%, 1 1.0 vol%, 12.0 vol%, 13.0 vol%, 1
  • the aqueous solution comprises at least one nitrate salt and at least one acid catalyst in a concentration as stated above, wherein said acid catalyst is selected from the group consisting of MgSO 4 , Ce(SO 4 )2, VOSO 4 , FeSO 4 , Fe 2 (SO 4 ) 3 , ZnCb, FeC , CuCb, FeCb, AlCb, LiNO 3 , CaCb, NaCI, KCI, LiCI, SrCb, MgCb, (NH 4 ) 2 SO 4 , CuSO 4 , LbSO 4 , NH 4 AI(SO 4 ) 2 , KAI(SO 4 ) 2 , ZnSO 4 , NaH 2 PO 4 , Na 2 HPO 4 , KH 2 PO 4 , K 2 HPO 4 , Zn 3 (PO 4 ) 2 , Ca(H 2 PO 4 ) 2 , CaHPO 4 , Na 2 H 2 P 2 O 7 , Na 3 HP
  • the aqueous solution may also comprise auxiliary agents.
  • the aqueous solution comprises at least one nitrate salt in a concentration as stated above and at least one acid catalyst in a concentration of about 0.01 vol%, 0.05 vol%, 1 .0 vol%, 1 .25 vol%, 1 .5 vol%, 1 .75 vol%, 2.0 vol%, 2.25 vol%, 2.5 vol%, 2.75 vol%, 3.0 vol%, 3.25 vol%, 3.5 vol%, 3.75 vol%, 4.0 vol%, 4.25 vol%, 4.5 vol%, 4.75 vol%, 5.0 vol%, 5.25 vol%, 5.5 vol%, 5.75 vol%, 6.0 vol%, 6.25 vol%, 6.5 vol%, 6.75 vol%, 7.0 vol%, 7.25 vol%, 7.5 vol%, 7.75 vol%, 8.0 vol%, 8.25 vol%, 8.5 vol%, 8.75 vol%, 9.0 vol%, 9.25 vol%, 9.5 vol%, 9.75 vol%, 10.0 vol%, 1 1 .0 vol%,
  • the aqueous solution comprises at least one nitrate salt in a concentration as stated above and at least one acid catalyst, wherein said acid catalyst is selected from the group consisting of methanesulfonic acid (CH3SO3H), phosphoric acid, citric acid, tartaric acid, oxalic acid, HCI, maleic acid, H 2 SO 4 , lactic acid, succinic acid or malonic acid.
  • the aqueous solution may also comprise auxiliary agents.
  • the aqueous solution comprises at least one nitrate salt, at least one acid in respective concentrations as stated above and optionally auxiliary agents.
  • the aqueous solution comprises at least one nitrate salt, optionally at least one acid catalyst in respective concentrations as stated above and a thickening agent in a concentration of about 0.01 - 1 vol%, of about 0.05 - 0.75 vol%, or of about 0.1 - 0.5 vol%.
  • the thickening agent is modified starch, modified cellulose, alginate or xanthan gum, but also hyaluronic acid, gelatine (collagen), pectin, agar (agarose), guar gum, gum arabic, carrageenan, locust bean gum (galactomannan), tragacanth and gellan gum.
  • the aqueous solution comprises at least one nitrate salt, optionally at least one acid catalyst, and additionally auxiliary chemical agents in a concentration of about 0.001 - 25 vol%, of about 0.01 - 7.7 vol%, or of about 0.025 - 5.0 vol%.
  • the auxiliary component in respective concentrations as stated above is selected from the group consisting of a nitrate, softener, brightening agent, plastic, a thickening agent, dyestuff used as a marker dye, a wetting agent, a complexing agent, a dispersing agent, and buffer components being derived from the salt of an acid and/or the corresponding acid.
  • the aqueous solution comprises at least one nitrate salt, optionally at least one acid and optionally a thickening agent in respective concentrations as stated above and additionally auxiliary chemicals in a concentration of about 0.001 - 10 vol%, of about 0.05 - 7.7 vol%, or of about 0.1 - 5.0 vol%.
  • the auxiliary component is selected from the group consisting of a polysorbate, alkyl polygucoside, methyl red, chromene red, monosodium phosphate, disodium pyrophosphate, tetrasodium diphosphate, butyl diglycol, sodium dodecyl sulate, sodium olefin sulfonate, sodium laureth sulfate, sodium lauryl ether sulfate, alanine-/V,/V-diacetic acid trisodium salt, glutamine-/V,/V-diacetic acid trisodium salt, DMSO and sulfolane.
  • Respective softeners are fatty alcohol polyglycol ether, acrylic acid, 3,5,7-trimethyldecane, soap, triglycerides, polydimethylsiloxane,
  • cyciopentasiioxan emulsifiers, Iignosulfonate, cationic surfactants, anionic surfactants, esterquats, ionic liquids, sodium 2-ethylhexyl sulfate, 2-methyl-2,4-pentanediol, tributyl phosphate, triisobutyl phosphate, 1 -hydroxyethane-1 ,1 ,-diphosphonic acid (HEDP), 2,2-dimethyl-1 ,3-propanediol.
  • Oxidizers as respective additives could be peroxides, peroxy acids and/or persulfates.
  • the aqueous solution comprises Mg(NO3)2, another nitrate compound and optionally a complexing agent. Tartaric acid is added to create the used/vintage look.
  • the aqueous solution comprises about 26 vol% Mg(NO3)2, about 0.05 - 0.1 vol% of another nitrate compound and added to create the used/vintage look.
  • the composition may further include about 0.01 - 15 vol% of at least one auxiliary agent selected from the group consisting of a nitrate, a thickening agent, dyestuff used as a marker dye, a wetting agent, a complexing agent, a dispersing agent, and a buffer solution being derived from the salt of an acid and the corresponding acid.
  • a further embodiment of the invention relates to the use of an aqueous composition comprising at least one nitrate salt and optionally at least one acid and/or auxiliary agent for the treatment of textile material in order to obtain a used and/or vintage look.
  • a further embodiment of the invention relates to the use of an aqueous composition comprising at least one nitrate salt and at least one acid catalyst for the treatment of textile material in order to obtain a used and/or vintage look, wherein the acid catalyst is selected from the group consisting of MgSO 4 , Ce(SO 4 )2, VOS0 4 , FeSO 4 , Fe 2 (S0 4 ) 3 , ZnCI 2 , FeC , CuCb, FeCb, AlCb, LiNO 3 , CaCb, NaCI, KCI, LiCI, SrCb, MgCb, (NH 4 ) 2 SO 4 , CuSO 4 , LbSO 4 , NH 4 AI(SO 4 ) 2 , KAI(SO 4 ) 2 , Zn 3 (PO 4 ) 2 ,
  • a further embodiment of the invention relates to the use of an aqueous composition comprising at least one nitrate salt and at least one acid catalyst for the treatment of textile material in order to obtain a used and/or vintage look, wherein the acid catalyst is selected from the group consisting of methanesulfonic acid, citric acid, tartaric acid, oxalic acid, HCI, maleic acid, H 2 SO 4 , lactic acid, or malonic acid or mixtures thereof.
  • a further embodiment of the invention relates to the use of an aqueous composition comprising at least one nitrate salt and at least one acid catalyst for the treatment of textile material in order to obtain a used and/or vintage look, wherein the acid catalyst and/or acidic buffer component is selected from the group consisting of MgSO 4 , Ce(SO 4 ) 2 , VOSO 4 , FeSO 4 , Fe (SO 4 ) 3 , ZnCb, FeCb, CuCb, FeCb, AlCb, CaCb, NaCI, KCI, LiCI, SrCb, MgCb, (NH 4 ) 2 SO 4 , CuSO 4 , Li 2 SO 4 , NH 4 AI(SO 4 ) 2 , KAI(SO 4 ) 2 , Zn(NO 3 ) 2 , NaH 2 PO 4 , Na 2 HPO 4 , KH 2 PO 4 , K 2 HPO 4 , Ca(H 2 PO 4 ) 2 , CaHPO 4 , Na
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 26 vol% Mg(NO3)2, about 0.05 vol% of another nitrate, about 2.0 vol% tartaric acid and optionally about 0.01 vol% chelating agent for the treatment of textile material in order to obtain a used look, a vintage look or a change in the color, optionally on preselected areas of the textile material.
  • the colour value changes and can be measured in a ⁇ _ value of 2 between the untreated and treated part.
  • L stands for the lightness in the CIE 1976 Lab color space.
  • a color value means the lightness or darkness of the color of the desired effect which can also be referred to as color intensity or the degree of whiteness or degree of brightness.
  • isatin anthranilic acid (2-aminobenzoic acid) and carbamic acid are formed due to the general oxidation reaction of indigo by the combined nitrate and acid treatment.
  • Other reaction products are 5-nitroisatin, 5- nitrosalicylic acid and picric acid, which are formed due to the specific oxidation of indigo by the action of nitrate compounds.
  • These products may be analyzed e.g. by means of NMR, liquid chromatography or gas chromatography after appropriate sample preparation or derivatization, respectively, of the mentioned products.
  • anhydroglucose units of the denim material may be esterified on positions 2, 3 and/or 6 by action of the nitrate compound under given conditions.
  • dispersants e.g. dispersants, wetting agents, surfactants, softener, thickening agents, plastics, colorants, tinting agents, silicones, levelling agents, antifoams, antimigration agents, antibackstaining agents, softeners, stabilizers and optical brightening agents.
  • additives are well known to experts in the field and can be chosen according to commonly used concentrations depending on the desired effect, e.g. 0.001 - 10 vol%.
  • Colorants may be selected from but not limited to dispersing dyes, acid dyes, basic dyes, vat dyes, Sulphur dyes, azoic dyes like methylene red and others.
  • Food dyes like Fast Green FCF, Erythrosine, Tartrazine, Sunset Yellow FCF, Citrus Red 2, Orange B, Quinoline Yellow, Carmoisine, Ponceau 4R, Patent Blue V, Green S, Allurared AC, , Amaranth, Anthocyane,
  • auxiliaries or their ingredients may be selected from but not limited to Tween 20, butyl diglycol, sodium dodecyl sulate, sodium olefin sulfonate, sodium laureth sulfate, sodium lauryl ether sulfate, alanine-/V,/V-diacetic acid trisodium salt, glutamine-/V,/V-diacetic acid trisodium salt, DMSO and sulfolane.
  • Respective softeners are fatty alcohol polyglycol ether, acrylic acid, 3,5,7-trimethyldecane, soap,
  • triglycerides polydimethylsiloxane, cyclopentasiloxan, emulsifiers, lignosulfonate, cationic surfactants, anionic surfactants, esterquats, ionic liquids, sodium 2-ethylhexyl sulfate, 2-methyl-2,4-pentanediol, tributyl phosphate, triisobutyl phosphate, 1 - hydroxyethane-1 ,1 ,-diphosphonic acid (HEDP), 2,2-dimethyl-1 ,3-propanediol.
  • Oxidizers as respective additives could be peroxides, peroxy acids and/or persulfates.
  • Thickening agents may be selected from but not limited to products which are commonly used in textile auxiliaries, food additives, cosmetics and personal hygiene products, i.e. starch and modified starches, cellulose and modified cellulose (i.e.
  • alginates i.e. sodium-, potassium-, ammonium-, propylenglycol alginate
  • Other chemicals may be added to impart more desirable improvement of the substrate in hand feel or other properties like softness, waterproofing, anti-microbial or microbe reducing chemicals, encapsulated perfumes, etc., or co-solvents (alcohols, ketones, nonionic solvents, ionic solvents, ionic liquids, etc.).
  • a denim fabric was subjected to a singeing treatment, a skewing treatment and a preshrinking treatment. Then, a thickened aqueous solution comprising an acid and a nitrate compound was applied to the surface.
  • a denim fabric was subjected to a singeing treatment, a skewing treatment, a preshrinking treatment and a desizing treatment. Then, a thickened aqueous solution comprising an acid and a nitrate compound was applied to the surface by printing.
  • a denim fabric was subjected to a singeing treatment, a skewing treatment, a preshrinking treatment and a desizing treatment. Then, an aqueous solution comprising an acid compound was applied by immersion and dried. The treated fabric is sewed to a garment and a nitrate salt containing solution is applied by spray to the garment.
  • a denim fabric was subjected to a singeing treatment, a skewing treatment, a preshrinking treatment and a desizing treatment. Then, an aqueous solution comprising an acid catalyst compound is applied to the surface by kiss-roll and dried. The treated fabric is sewed to a garment and a nitrate containing solution is applied by spray to the garment.
  • a denim fabric was subjected to a singeing treatment, a skewing treatment, a preshrinking treatment and a desizing treatment. Then, an aqueous solution comprising a nitrate compound is applied by immersion and dried. The treated fabric is sewed to a garment and an acid compound containing solution is applied by spray to the garment.
  • the color changing effect in such pretreated denim fabrics is then generated with irradiation, e.g. by a laser treatment (e.g. as disclosed in US2016263928, US2016060807, US2015343568, US2015298253, US2015121965, and
  • a denim fabric was subjected to a singeing treatment, a skewing treatment and a preshrinking treatment. Then, an aqueous solution comprising an acid and a nitrate compound is applied by immersing or only to the surface (e.g. kiss roll, knife application, foaming, etc.). The effect is generated during a subsequent laser treatment.
  • a denim fabric was subjected to a singeing treatment, a skewing treatment, a preshrinking treatment, an ozone treatment and/or a laser treamtent. Then, an aqueous solution comprising an acid and a nitrate compound is applied by immersion or only to the surface (e.g. kiss roll, knife application, foaming, etc.). The effect is generated during a subsequent laser treatment.
  • a denim yarn is immersed in a solution comprising the acid and the nitrate. Subsequently the yarn is sized and woven to a fabric. The effect is generated during a subsequent laser treatment.
  • a solution comprising the acid and the nitrate is applied to denim yarn by a kiss roll, foaming or spray. Subsequently the yarn is sized and woven to a fabric. The effect is generated during a subsequent laser treatment.
  • a raw denim garment was abraded by laser or hand sanding to mark specific used look areas. Subsequently a solution containing nitrate and acid is sprayed or applied by brush or sponge on the abraded areas.
  • a raw denim garment was desized and dried. Subsequently a solution containing nitrate and acid is sprayed or applied by brush or sponge on the abraded areas.
  • a raw denim garment is used as it is, or desized, and/or stonewashed, and or ozone treated, and/or enzyme washed and dried. Subsequently a solution containing nitrate and acid is sprayed or applied by brush or sponge on specific areas of the garment.
  • a raw denim garment is used as it is, or desized, and/or stonewashed, and/or ozone treated, and/or enzyme washed and dried. Subsequently a solution containing a nitrate salt is applied to the garment and dried. Subsequently a solution containing an acid catalyst is applied by brush or sponge on specific areas of the garment.
  • a raw denim garment is used as it is, or desized, and/or stonewashed or enzyme washed and dried. Subsequently a solution containing an acid catalyst is applied to the garment and dried. Subsequently a solution containing a nitrate salt is applied by brush or sponge on specific areas of the garment.
  • Pumice stones are soaked in a solution containing an acid and a nitrate salt and subsequently agitated with a denim garment in a tumbler.
  • a denim garment is wetted and placed together with a powder containing nitrate salt and acid catalyst (if needed together with a filler material like sand, perlite, etc.) in a bag and agitated until the effect is created.
  • Examples according to [00141] to [00158] are subsequently rinsed with water, washed under acidic conditions (e.g. pH ⁇ 5) and/or basic conditions (e.g. pH > 10) at cold and/or warm conditions (e.g. 30-90°C) and a combination thereof.
  • acidic conditions e.g. pH ⁇ 5
  • basic conditions e.g. pH > 10
  • cold and/or warm conditions e.g. 30-90°C
  • Tables 1 to 7 depict compositions in aqueous solutions which are applied to fabrics.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Coloring (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP16808682.5A 2015-12-10 2016-12-09 Behandlung von textilmaterial Withdrawn EP3387183A1 (de)

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EP15199315 2015-12-10
EP16159022 2016-03-07
PCT/EP2016/080371 WO2017097953A1 (en) 2015-12-10 2016-12-09 Treatment of textile material

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