WO2017097952A1 - Treatment of textile material - Google Patents

Treatment of textile material Download PDF

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Publication number
WO2017097952A1
WO2017097952A1 PCT/EP2016/080370 EP2016080370W WO2017097952A1 WO 2017097952 A1 WO2017097952 A1 WO 2017097952A1 EP 2016080370 W EP2016080370 W EP 2016080370W WO 2017097952 A1 WO2017097952 A1 WO 2017097952A1
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WO
WIPO (PCT)
Prior art keywords
acid
vol
nitrate salt
phosphate
sulfate
Prior art date
Application number
PCT/EP2016/080370
Other languages
French (fr)
Inventor
Christian Bruno SCHIMPER
Paul Sebastian PACHSCHWÖLL
Hubert HETTEGGER
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
Priority to EP16819018.9A priority Critical patent/EP3387184A1/en
Publication of WO2017097952A1 publication Critical patent/WO2017097952A1/en
Priority to US16/004,276 priority patent/US10900166B2/en
Priority to US17/133,467 priority patent/US20210148041A1/en

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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
    • D06P5/131—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
    • D06P5/13—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
    • 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
    • D06P5/135—Fugitive dyeing or stripping dyes with combined acids or bases + oxidants + reductants means
    • 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
    • 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
    • D06P5/15—Locally discharging the dyes
    • D06P5/156—Locally discharging the dyes with combined A+B+C means

Definitions

  • the present invention generally relates to a process for local surface treatment of textile material with a chemical composition, more specifically to the local treatment of a textile material with a nitrate salt and an acid catalyst in order to obtain a color change or a vintage look of the textile material at desired regions.
  • Fabric such as denim
  • denim fabrics are ring dyed to enable the formation of a worn look when the colour from the most outer part of the yarn is physically or chemically removed.
  • Common dyes for the denim textile are sulphur dyes, reactive dyes, direct dyes, VAT dyes, basic dyes, pigment dyes, or natural dyes.
  • a combination of different dyes is possible and can emerge as top or bottom indigo combination dye, coatings, or bottoms.
  • Indigo and sulphur dyes are most common on our fabric type. They emerge as solid dyed, top or bottom indigo combination dyed. Reactive dyes are used very often because of their wide colour offering and range together with their high fastness which is not always an advantage.
  • Direct dyes can also be used and are not so fast on cotton as reactive. This often is desired to achieve a distressed washed out look.
  • VAT dyes - such as indigo - are used on cotton and blends with other man made fibers. Pigment dyes are often used in conjunction with a cationiser. Surface dyeing so compliments the indigo abrasion concept. Has limitations on darker shades since often a reactive bottom is used. Natural dyes are also possible depending on the desired effect.
  • wet processes 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 worn look.
  • an enzyme wash in combination with agitation elements 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.
  • US 5 350 423 A discloses a process for pre-treating cotton denim to enhance abrasion and shade reduction by embrittling the fibers with an acid and heat-activated finishing, thus increasing susceptibility/amenability of the indigo dye to a subsequent bleaching method (e.g. chlorine bleaching) and thereby reducing stonewashing time and expense.
  • a subsequent bleaching method e.g. chlorine bleaching
  • EP 1 486 607 A1 discloses a process for an indigo-dyed cloth in which a sole nitrogen based oxidizing agent is applied. In order to obtain the desired vintage look the pretreated cloth is subjected to a dramatic heating step higher 170 °C.
  • JP 2004 068179 A discloses a process for an indigo dyed cloth in which an acid compound is applied to a fabric by immersion and subjected to a heating step at very high baking temperature (180 °C) for the embrittlement of the cellulose backbone by acid hydrolysis and eventually physical removal of indigo dye.
  • JP H1 1 200261 A discloses the use of aqueous nitric acid to be applied onto indigo-dyed denim and achromatic (white) cloth by immersion and subsequent basic rinsing in order to achieve light-brown cotton goods after nitrification of the cellulose backbone. In this application the cloth is immersed completely into the solution and no local bleaching is possible.
  • [001 1] According the invention there is provided 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 compound in presence of an acid catalyst or treatment conditions which induce acid formation.
  • One embodiment of the invention relates to a method for changing the color of a dyed textile material to obtain a vintage and/or worn appearance comprising the steps of: a. contacting said textile material with at least one nitrate salt,
  • step b) maintaining step b) until the desired color change is achieved.
  • a further embodiment of the invention relates to the 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
  • a further embodiment of the invention relates to the method as described above, wherein the nitrate salt is Mg(NO 3 ) 2 , KNO , LiNOs, NaNOs, 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 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
  • One embodiment of the invention relates to a method for changing the color of a dyed textile material to obtain a vintage and/or worn appearance comprising the steps of:
  • nitrate salt Mg(NO 3 ) 2 , KNO 3 , LiNO 3 , NaNOs, Ai(NO 3 ) 3 , Ca(NO 3 ) , Fe(NO 3 ) 3 ,
  • step b) maintaining step b) until the desired color change is achieved.
  • a further embodiment of the invention relates to the method as described above, wherein the acid catalyst is an organic or inorganic acid, preferably selected from the group consisting of methanesulfonic acid, citric acid, tartaric acid, oxalic acid, toluenesulfonic acid, succinic acid, maleic acid, malic acid, sulfuric acid, hydrochloric acid, phosphoric acid, salicylic acid and mixtures thereof and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
  • the acid catalyst is an organic or inorganic acid, preferably selected from the group consisting of methanesulfonic acid, citric acid, tartaric acid, oxalic acid, toluenesulfonic acid, succinic acid, maleic acid, malic acid, sulfuric acid, hydrochloric acid, phosphoric acid, salicylic acid and mixtures thereof and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
  • 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 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, pentapotassium triphosphate.
  • 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.
  • a further embodiment of the invention relates to the method as described above, wherein the textile material is treated with an aqueous solution comprising at least one nitrate salt which is activated by an acid catalyst , wherein the treatment is carried out until the desired color change is achieved.
  • a further embodiment of the invention relates to the method as described above, wherein said aqueous solution comprises Mg(NO3)2, a different nitrate salt (e.g. AI(NO3)3) and an acid catalyst, e.g. tartaric acid.
  • a further embodiment of the invention relates to the method as described above, wherein said aqueous solution comprises AI(NO3)3 and toluenesulfonic acid.
  • a further embodiment of the invention relates to the method as described above, wherein the fabric is not immerced into the aqueous solution.
  • a further embodiment of the invention relates to the method as described above, wherein the treatment 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 method is carried out in the presence of a sulfate and/or chloride compound.
  • One embodiment of the invention relates to the use of an aqueous composition comprising at least one nitrate salt and optionally at least one acid catalyst and optionally an auxiliary chemical agent for the treatment of textile material in order to obtain a worn appearance and/or vintage look.
  • a further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 10 - 75 vol% nitrate salt, optionally about 0.01 - 5 vol% of a different nitrate salt, and about 0.5 - 50.0 vol% acid catalyst, and optionally about 0.01 - 0.05 vol% of at least one chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
  • a further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 20 - 50 vol% nitrate salt, optionally about 0.05 - 3 vol% of a different nitrate salt, and about 1.0 - 35.0 vol% acid catalyst, and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
  • a further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 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, and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
  • a further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 20 - 30 vol% Mg(NO3)2, about 0.05 - 2 vol% of another nitrate salt, about 1.0 - 30.0 vol% tartaric acid and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
  • a further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 5 - 20 vol% AI(NO3)3, about 5 vol% butyl diglycol, mixing with a solution of about 10 - 35 vol% toluenesulfonic acid, and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
  • a further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 10 vol% AI(NO3)3, about 5 vol% butyl diglycol, mixing with a solution of about 30 vol% toluenesulfonic acid, and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
  • a further embodiment of the invention relates to the method as described above, wherein optionally an auxiliary agent is used.
  • One embodiment of the invention relates to a method to increase the color value of 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.
  • One embodiment of the invention relates to a method to increase the color value of 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.
  • One embodiment of the invention relates to a method to increase the color value of treated fabric by applying a solution comprising of an aluminum based nitrate salt, optionally a wetting agent, and toluenesulfonic acid to the fabric.
  • a further embodiment of the invention relates to the use as described above, wherein the auxiliary agent 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 a buffer solution derived from the salt of an acid and the corresponding acid.
  • the auxiliary agent 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 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 fabric is dyed by commonly used dyes for the textiles.
  • a further embodiment of the invention relates to the method as described above, wherein the dye is selected from the group consisting of sulphur dye, reactive dye, direct dye, VAT dye, basic dye, pigment dye, or natural dyes, or a mixture thereof.
  • a further embodiment of the invention relates to the method as described above, wherein the dye is a solid dye of a top or bottom indigo combination dye.
  • a further embodiment of the invention relates to the method as described above, wherein the ⁇ _ 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 acid catalyst is provided as a buffered substance.
  • a further embodiment of the invention relates to the method as described above, wherein the pH of the aqueous solution is higher than 2.
  • the present invention provides a method for obtaining a worn and/or vintage appearance of a fabric in which the shortcomings of the prior art are avoided.
  • the present invention relates to a method of providing a worn or vintage appearance of a fabric, wherein said fabric is subjected to acid treatment in the presence of a nitrate salt.
  • 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, acetat type), and in special cases also fibers based on proteins (e.g. soja, casein, fibroin, sericin, etc.), starch and glucose (e.g.
  • 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
  • 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, polyphenylensulfide, aramide, etc.
  • polymerization e.g. polyacrylonitrile
  • 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 aliphatic, aromatic, heterocyclic or a biochemical organic compound selected from the group consisting of alkanes, alkenes, alkynes, cyclic compounds, as well as allyl-, 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, chaicogens, 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 allyl-, alkyl-, arylcompounds, alcohols, aldehydes, esters, ethers, ketones, carbohydrates
  • the nitrogen compound is a nitrate salt which is selected from the group consisting of Mg(N03)2, KNO3, LJNO3, AI(N03)3,
  • 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, Bransted-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 carboxyiic acids, amino acids, halogenated carboxyiic acids and vinylogous carboxyiic 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, penta potassium 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-A/JV-diacetic 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
  • a buffer solution might be appropriate. Suitable buffer solutions are well known to a person skilled in the art.
  • 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 MgS0 4 , Ce(SO 4 ) 2 , VOS0 4 , FeSO 4 , Fe 2 (S0 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 2 , CoCI , NiCI 2 or AICI3.
  • the textile material is treated with
  • the textile material is treated with
  • 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 salt in a
  • 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(NO3) 2 , UNO3, AI(NO3)3, Ca(NO3) 2 , Fe(N03)3, Cu(NO 3 ) 2 , KNO3, NaNOs, (NH 4 ) 2 Ce(N0 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%, 6.76 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 voi%, 12.0 vol%, 13.0 vol%, 1.0 vol%, 1.25 vol%,
  • 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, FeCb, CuCb, FeCb, AICI 3 , LiNOa, CaCb, NaCI, KCI, LiCI, SrCb, MgCb, (NH ) 2 SO 4 , CuSO 4 , Li 2 SO 4 , NH 4 AI(SO 4 ) 2 , KAI(SO ) 2 , ZnSO 4 , NaH 2 PO 4 , Na 2 HPO 4 , KH 2 PO , K 2 HPO 4 , Zn 3 (PO ) 2 , Ca(H 2 PO 4 ) 2 , CaHPO 4 , Na 2 H 2 P 2 O 7 , Na 3 HP 2 O 7
  • 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%, 6.76 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 (CH 3 SO 3 H), 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,/ ⁇ Adiacetic 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,
  • aqueous solution comprises Mg( 03)2, optionally a different nitrate salt, 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 a different nitrate salt, and optionally about 0.01 - 0.05 chelating agent.
  • About 1.0 - 10.0 vol% tartaric acid is 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 , Ce(SO 4 )2, VOS0 4 , FeSO 4 , Fe 2 (SO 4 ) 3 , ZnCb, FeC , CuCb, FeCb, AlCb, UNO3, 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 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 (CH3SO3H), citric acid, tartaric acid, oxalic acid, HCI, maleic acid, H 2 SO 4 , lactic acid, or malonic acid or mixtures thereof.
  • CH3SO3H methanesulfonic acid
  • 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(S0 ) 2 , VOS0 4 , FeS0 4 , Fe 2 (SO 4 ) 3! ZnCb, FeC , CuCb, FeCI 2 , AlCb, CaCb, NaCI, KCI, LiCI, SrC , MgCb, (NH 4 ) 2 S0 4 , CuSO 4 , Li 2 S0 4l NH 4 AI(SO 4 ) 2 ,
  • methanesulfonic acid toluenesulfonic acid, citric acid, tartaric acid, oxalic acid, HCI, maleic acid, H 2 S0 4 , lactic acid, succinic acid or malonic acid, and optionally comprising at least one further auxiliary chemical and/or thickening agent.
  • 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.
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Mg(NO3) 2 , about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% K(NO3) 2 , about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Li(NO3) 2 , about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Na(NO3) 2 , about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Ca(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Fe(NO:3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Cu(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Zn(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
  • a further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Co(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
  • 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 the 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 compounds under given conditions.
  • the treatment may optionally be carrying out at a temperature of about 10 - 90 °C, or of about 10 - 70 °C, or of about 10 - 60 °C, or of about 10 - 40°C, or of about 20 - 80 °C, or of about 20 - 60 °C, or of about 20 - 35 °C.
  • 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,AAdiacetic 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
  • 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 salt 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 salt 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
  • a denim fabric was subjected to a singeing treatment, a skewing treatment, a preshrinking treatment and a desizing treatment. Then, an aqueous solution
  • a denim fabric was subjected to a singeing treatment, a skewing treatment, a preshrinking treatment and a desizing treatment. Then, an aqueous solution
  • a nitrate salt comprising a nitrate salt 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.
  • 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 salt is applied by immersing or only to the surface (e.g. kiss roll, knife application, foaming, etc.). The effect is generated during a subsequent heat 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 salt is applied by immersion or only to the surface (e.g. kiss roll, knife application, foaming, etc.). The effect is generated during a subsequent heat 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 heat 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 heat treatment.
  • 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 is applied to the garment and dried. Subsequently a solution containing an acid 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 is applied to the garment and dried. Subsequently a solution containing a nitrate 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 and subsequently agitated with a denim garment in a tumbler.
  • a denim garment is wetted and placed together with a powder containing nitrate and acid (if needed together with a filler material like sand, perlite, etc.) in a bag and agitated until the effect is created.
  • a solution containing nitrate salt and an acid catalyst acid is applied to a fabric or denim garment and subjected to microwave irradiation.
  • the power of irradiation varies from 100 W to 1000 W, depending on the desired effect.
  • the time of irradiation varies from 10 second to 1200 seconds, also depending on the desired effect.
  • a solution containing nitrate salt and an acid catalyst is applied to a fabric or denim garment and subjected to microwave irradiation.
  • Examples according to [00106] to [00125] 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 of aqueous solutions which are applied to denim fabrics.
  • Table 8 depicts examples of microwave irradiation as respective

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Abstract

The present invention generally relates to a method for changing the color of a textile material to obtain a vintage and/or worn appearance comprising the steps of contacting said fabric textile material with a nitrate salt, activating the nitrate salt by the addition of an acid catalyst until the desired color change is achieved.

Description

TREATMENT OF TEXTILE MATERIAL
Description
Field of the Invention
[0001] The present invention generally relates to a process for local surface treatment of textile material with a chemical composition, more specifically to the local treatment of a textile material with a nitrate salt and an acid catalyst in order to obtain a color change or a vintage look of the textile material at desired regions.
Background Art
[0002] Fabric, such as denim, can be processed to simulate a worn look. Typically denim fabrics are ring dyed to enable the formation of a worn look when the colour from the most outer part of the yarn is physically or chemically removed. Common dyes for the denim textile are sulphur dyes, reactive dyes, direct dyes, VAT dyes, basic dyes, pigment dyes, or natural dyes. A combination of different dyes is possible and can emerge as top or bottom indigo combination dye, coatings, or bottoms. Indigo and sulphur dyes are most common on our fabric type. They emerge as solid dyed, top or bottom indigo combination dyed. Reactive dyes are used very often because of their wide colour offering and range together with their high fastness which is not always an advantage. Direct dyes can also be used and are not so fast on cotton as reactive. This often is desired to achieve a distressed washed out look. VAT dyes - such as indigo - are used on cotton and blends with other man made fibers. Pigment dyes are often used in conjunction with a cationiser. Surface dyeing so compliments the indigo abrasion concept. Has limitations on darker shades since often a reactive bottom is used. Natural dyes are also possible depending on the desired effect. Conventionally, wet processes, 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 worn look. Specifically, an enzyme wash in combination with agitation elements, 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. In an exemplary embodiment, the faded areas of the denim fabric can correspond to where stones or rocks contact the fabric during the enzyme washing process.
[0003] However, traditional stonewash and/or enzyme processes have numerous drawbacks. For example, each manufacturing cycle requires extensive time to create the stonewashed look in which a significant amount of water is used during the process. In addition, the handling and disposal of the enzymes and wastewater can require substantial attention regarding environmental concerns.
[0004] US 5 350 423 A discloses a process for pre-treating cotton denim to enhance abrasion and shade reduction by embrittling the fibers with an acid and heat-activated finishing, thus increasing susceptibility/amenability of the indigo dye to a subsequent bleaching method (e.g. chlorine bleaching) and thereby reducing stonewashing time and expense.
[0005] EP 1 486 607 A1 discloses a process for an indigo-dyed cloth in which a sole nitrogen based oxidizing agent is applied. In order to obtain the desired vintage look the pretreated cloth is subjected to a dramatic heating step higher 170 °C.
[0006] JP 2004 068179 A discloses a process for an indigo dyed cloth in which an acid compound is applied to a fabric by immersion and subjected to a heating step at very high baking temperature (180 °C) for the embrittlement of the cellulose backbone by acid hydrolysis and eventually physical removal of indigo dye.
[0007] JP H1 1 200261 A discloses the use of aqueous nitric acid to be applied onto indigo-dyed denim and achromatic (white) cloth by immersion and subsequent basic rinsing in order to achieve light-brown cotton goods after nitrification of the cellulose backbone. In this application the cloth is immersed completely into the solution and no local bleaching is possible.
[0008] Therefore there is still the need for an improved method at lower temperature (e.g. by catalysis) and a technical as well as chemical solution for rendering local surface-treatment possible in order to impart a fabric a local vintage look.
Summary of invention
[0009] It is the objective of the present invention to provide for localized bleaching of dyed goods by using nitric compounds for chemically bleaching dyestuff on fabrics.
[0010] The object is solved by the subject of the present invention.
[001 1] According the invention there is provided 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 compound in presence of an acid catalyst or treatment conditions which induce acid formation.
[0012] One embodiment of the invention relates to a method for changing the color of a dyed textile material to obtain a vintage and/or worn appearance comprising the steps of: a. contacting said textile material with at least one nitrate salt,
b. activating said nitrate salt by the addition of an acid catalyst, and
c. maintaining step b) until the desired color change is achieved.
[0013] A further embodiment of the invention relates to the method as described above, wherein the nitrate salt is an organic or inorganic nitrate salt.
[0014] 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
Mg(NO3)2, KNO3, L1NO3, AI(NO3)3, Ca(NO3)2, Fe(NO3)3, Cu(NO3)2, Co(NO3)2,
(NH4)2Ce(NO3)6, NaNOs, RbNO3, CsNOs, Sr(NO3)2, Ba(NO3)2, Sc(NO3)3, Ti(NO3)4,
Zr(NO3)4, VO(NO3)3, Cr(NO3)3, Mn(NO3)2, Co(NO3)2, Co(NO3)3, Ni(NO3)2, Pd(NO3)2,
AgNO3, Cd(NO3)2, Hg2(NO3)2, Hg(NO3)2, [B(NO3)4]-, Ga(NO3)3, TI(NO3)3, Pb(NO3)2,
Bi(NO3)3, FNO3, CINOs, Xe(NO3)2, Ce(NO3)3, Ce(NO3)4, Gd(NO3)3.
[0015] A further embodiment of the invention relates to the method as described above, wherein the nitrate salt is Mg(NO3)2, KNO , LiNOs, NaNOs, AI(NO3)3, Ca(NO3)2,
Fe(NO3)3, Cu(NO3)2, Zn(NO3)2, Co(NO3)2, or (NH4)2Ce(NO3)6.
[0016] 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.
[0017] A further embodiment of the invention relates to the method as described above, wherein nitrate salt is applied on local parts of the fabric.
[0018] 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
whereupon figurative patterns are obtained.
[0019] One embodiment of the invention relates to a method for changing the color of a dyed textile material to obtain a vintage and/or worn appearance comprising the steps of:
a. contacting said textile material with at least one nitrate salt, wherein the nitrate salt is Mg(NO3)2, KNO3, LiNO3, NaNOs, Ai(NO3)3, Ca(NO3) , Fe(NO3)3,
Cu(NOs)2, Co(NOs)2, or (NH4)2Ce(NO3)6,
b. activating said nitrate salt by a heating step, and
c. maintaining step b) until the desired color change is achieved.
[0020] A further embodiment of the invention relates to the method as described above, wherein the acid catalyst is an organic or inorganic acid, preferably selected from the group consisting of methanesulfonic acid, citric acid, tartaric acid, oxalic acid, toluenesulfonic acid, succinic acid, maleic acid, malic acid, sulfuric acid, hydrochloric acid, phosphoric acid, salicylic acid and mixtures thereof and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
[0021] 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.
[0022] 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
magnesium sulfate, iron sulfate, iron sulfate, cerium sulfate, vanadium sulfate, copper sulfate, lithium sulfate, aluminum sulfate, potassium aluminum sulfate, ammonium aluminum sulfate, sodium sulfate, sodium hydrogen sulfate, zinc sulfate and
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, pentapotassium triphosphate.
[0023] A further embodiment of the invention relates to the method as described above, wherein the acid catalyst is capsuled.
[0024] 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.
[0025] A further embodiment of the invention relates to the method as described above, wherein the textile material is treated with an aqueous solution comprising at least one nitrate salt which is activated by an acid catalyst , wherein the treatment is carried out until the desired color change is achieved.
[0026] A further embodiment of the invention relates to the method as described above, wherein said aqueous solution comprises Mg(NO3)2, a different nitrate salt (e.g. AI(NO3)3) and an acid catalyst, e.g. tartaric acid. [0027] A further embodiment of the invention relates to the method as described above, wherein said aqueous solution comprises AI(NO3)3 and toluenesulfonic acid.
[0028] A further embodiment of the invention relates to the method as described above, wherein the fabric is not immerced into the aqueous solution.
[0029] A further embodiment of the invention relates to the method as described above, wherein the treatment 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.
[0030] A further embodiment of the invention relates to the method as described above, wherein the method is carried out in the presence of a sulfate and/or chloride compound.
[0031] One embodiment of the invention relates to the use of an aqueous composition comprising at least one nitrate salt and optionally at least one acid catalyst and optionally an auxiliary chemical agent for the treatment of textile material in order to obtain a worn appearance and/or vintage look.
[0032] A further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 10 - 75 vol% nitrate salt, optionally about 0.01 - 5 vol% of a different nitrate salt, and about 0.5 - 50.0 vol% acid catalyst, and optionally about 0.01 - 0.05 vol% of at least one chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
[0033] A further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 20 - 50 vol% nitrate salt, optionally about 0.05 - 3 vol% of a different nitrate salt, and about 1.0 - 35.0 vol% acid catalyst, and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
[0034] A further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 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, and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
[0035] A further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 20 - 30 vol% Mg(NO3)2, about 0.05 - 2 vol% of another nitrate salt, about 1.0 - 30.0 vol% tartaric acid and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
[0036] A further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 5 - 20 vol% AI(NO3)3, about 5 vol% butyl diglycol, mixing with a solution of about 10 - 35 vol% toluenesulfonic acid, and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
[0037] A further embodiment of the invention relates to the use as described above, wherein the aqueous solution comprises about 10 vol% AI(NO3)3, about 5 vol% butyl diglycol, mixing with a solution of about 30 vol% toluenesulfonic acid, and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
[0038] A further embodiment of the invention relates to the method as described above, wherein optionally an auxiliary agent is used.
[0039] One embodiment of the invention relates to a method to increase the color value of 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.
[0040] One embodiment of the invention relates to a method to increase the color value of 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.
[0041] One embodiment of the invention relates to a method to increase the color value of treated fabric by applying a solution comprising of an aluminum based nitrate salt, optionally a wetting agent, and toluenesulfonic acid to the fabric.
[0042] A further embodiment of the invention relates to the use as described above, wherein the auxiliary agent 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 a buffer solution derived from the salt of an acid and the corresponding acid.
[0043] A further embodiment of the invention relates to the method as described above, wherein the fabric is dyed by commonly used dyes for the textiles. [0044] A further embodiment of the invention relates to the method as described above, wherein the dye is selected from the group consisting of sulphur dye, reactive dye, direct dye, VAT dye, basic dye, pigment dye, or natural dyes, or a mixture thereof.
[0045] A further embodiment of the invention relates to the method as described above, wherein the dye is a solid dye of a top or bottom indigo combination dye.
[0046] A further embodiment of the invention relates to the method as described above, wherein the ΔΙ_ value between the untreated and treated part is greater than 2. L stands for the lightness in the CIE 1976 Lab color space.
[0047] A further embodiment of the invention relates to the method as described above, wherein the acid catalyst is provided as a buffered substance.
[0048] A further embodiment of the invention relates to the method as described above, wherein the pH of the aqueous solution is higher than 2.
Description of embodiments
[0049] In order to obtain a worn or vintage look of fabrics currently large amounts of chemicals and water are required which are harmful to the environment.
[0050] Therefore the present invention provides a method for obtaining a worn and/or vintage appearance of a fabric in which the shortcomings of the prior art are avoided.
[0051] The present invention relates to a method of providing a worn or vintage appearance of a fabric, wherein said fabric is subjected to acid treatment in the presence of a nitrate salt.
[0052] In the present invention the term "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.).
[0053] In one embodiment of the invention the textile material is finished colored denim. In one further embodiment of the invention 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.
[0054] The textile material may be dyed or coated with a dye, preferably with a natural or synthesized dye. In one embodiment of the invention the fabrics are dyed with an indigo dye which may be a natural or synthesized indigo dye or sulphur black dye. In another embodiment of the invention 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.
[0055] 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, acetat 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,
polytetrafluorethylene, polyethylene, polypropylene, polyvinylchloride, etc.) and fibers produced by polyaddition procedure (e.g. polyurethane, etc.), but not limited to.
[0056] By the inventive combination of an aqueous nitrate salt treatment in the presence of an acid catalyst the additional activating step by heating above 100 °C is needless.
[0057] The nitrogen compound may be an organic nitro- or nitrate-compound like aliphatic, aromatic, heterocyclic or a biochemical organic compound selected from the group consisting of alkanes, alkenes, alkynes, cyclic compounds, as well as allyl-, 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, chaicogens, halogens, noble gases, as well as from the group of transition metals, Lanthanides and Actinides.
[0058] In one embodiment of the invention the nitrogen compound is a nitrate salt which is selected from the group consisting of Mg(N03)2, KNO3, LJNO3, AI(N03)3,
Ca(N03)2, Fe(NO3)3, Cu(N03)2, Zn(N03)2, Co(N03)2, (NH4)2Ce(NO3)6, NaNOs, RbNO3, CsNOs, Be(N03)2, Sr(NO3)2> Ba(N03)2, Sc(N03)3, Ti(NO3)4, Zr(N03)4, VO(N03)3,
Cr(N03)3, Mn(N03)2, Co(N03)3, Ni(N03)2, Pd(N03)2, AgNO3, Cd(N03)2, Hg2(N03)2, Hg(N03)2, [Β(Ν03)4]-, Ga(NO3)3, TI(NO3)3, Pb(N03)2, Bi(N03)3, FNO3, CINO3,
Xe(N03)2, Ce(NO3)3, Ce(N03)4, UO2(NO3)2, Gd(NO3)3, as well as their salts with nitrite. [0059] In one embodiment of the invention the nitrate salt is selected from the group consisting of Mg(N03)2, UNO3, AI(NO3)3, Fe(N03)3, Zn(N03)2, Ce(N03)3, Ce(N03)4, as well as their respective salts with nitrite.
[0060] 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.
[0061] Appropriate 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, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, propylene glycol phenyl ether, tripropylene glycol monobutyl ether and polyethylene glycol ethers, hexyl carbitol ether, phenols, alkylphenols, fatty acids, terpene alcohols, terpene oils, copolymers of vinylpyrrolidone, polyglycols and polypropylene glycol. The solvent may further include additives such as dispersants, wetting agents, anti-foaming agents, softeners, plastics, thickeners, etc.
[0062] The acid may be an Arrhenius acid, Bransted-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 carboxyiic acids, amino acids, halogenated carboxyiic acids and vinylogous carboxyiic acid or salts thereof. In one embodiment of the invention the acid may be selected from the group consisting of sulfuric acid, hydrochloric acid, fluorosulfuric acid, phosphoric acid, fluoroantimonic acid, fluoroboric acid,
hexafluorophosphoric acid, chromic acid, boric acid, methanesulfonic acid,
ethanesulfonic acid, amidosulfonic acid, sulfamidic acid, sulfanilic acid,
benzenesulfonic acid, toluenesulfonic acids, trifluoromethanesulfonic acid, polystyrene sulfonic acid, acetic acid, citric acid, formic acid, gluconic acid, glycolic acid, lactic acid, tartaric acid, oxalic acid, maleic acid, pyruvic acid, benzoic acid, gallic acid, barbituric acid, dihydroxybenzoic acid, cinnamic acids, aminobutyric acid, fumaric acid, malic acid, succinic acid, malonic acid, glutaminic acid, nitrosalicylic acid, nitrobenzoic acids, nitrobenzenesulfonic acid, levolinic acid, pimelic acid, salicylic acid, sulfosalicylic acid, adipic acid, caprylic acid, nicotinic acids, uric acid, phthalic acid, chloroacetic acid, fluoroacetic acid, trifluoroacetic acid, chloroacetic acid, dichloroacetic 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.
[0063] 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
hydrochloride, or aspartic acid hydrochloride.
[0064] 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, penta potassium 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 Λ/,/V-di acetic acid tetra sodium salt, alanine-A/JV-diacetic 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.
[0065] 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.
[0066] 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.
[0067] 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. In one embodiment of the invention 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. In another embodiment of the invention 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.
[0068] 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.
[0069] In one embodiment of the invention 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.
[0070] Additionally 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. [0071] In one embodiment of the invention addition of a buffer solution might be appropriate. Suitable buffer solutions are well known to a person skilled in the art.
[0072] In one embodiment of the invention 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 MgS04, Ce(SO4)2, VOS04, FeSO4, Fe2(S04)3, CuSO4,
KAI(S04)2, AI2(SO4)3, ZnSO4, NaHSO4, KHSO4, Li2SO4, CaSO4. The phosphate may be selected from the group of calcium, sodium, potassium and ammonium phosphates such as NaH2PO4, Na2HPO4, KH2PO4, K2HPO4, Ca(H2PO4)2, CaHPO4, Na2H2P2O7, Na3HP2O7, NasPsOio, K5P3O10, (NH4)H2PO4, (NH4)2HPO4. The chloride may be selected from heavy metal chloride such as for example from ZnCI2, FeC , FeCI2, CuCI2, MnCI2, CoCI , NiCI2 or AICI3.
[0073] In one embodiment of the invention the textile material is treated with
Mg(NO3)2 in the presence of methanesulfonic acid for about 30 min.
[0074] In one embodiment of the invention the textile material is treated with
Mg(N03)2 in the presence of tartaric acid and another nitrogen compound for about 20 min at a temperature of about 60 °C.
[0075] In one embodiment of the invention 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%. In one embodiment of the invention the aqueous solution comprises at least one nitrate salt in a
concentration of about 1 vol%, 2.5 vol%, 5 vol%, 7.5 vol%, 10 vol%, 15 vol%, 18 vol%, 20 vol%, 25 vol%, 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%.
[0076] In a further embodiment of the invention 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(NO3)2, UNO3, AI(NO3)3, Ca(NO3)2, Fe(N03)3, Cu(NO3)2, KNO3, NaNOs, (NH4)2Ce(N03)6, Co(NO3)2, or Fe(NO3)2, or hydrates thereof. Optionally, the aqueous solution may also comprise auxiliary agents.
[0077] In a further embodiment of the invention 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%, 6.76 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 voi%, 12.0 vol%, 13.0 vol%, 14.0 vol%, 15.0 vol%, 17.5 vol%, 20.0 vol%, 22.5 vol%, or 25.0 vol%.
[0078] In a further embodiment of the invention 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 MgSO4, Ce(SO4)2, VOSO4, FeSO4, Fe2(SO4)3, ZnCb, FeCb, CuCb, FeCb, AICI3, LiNOa, CaCb, NaCI, KCI, LiCI, SrCb, MgCb, (NH )2SO4, CuSO4, Li2SO4, NH4AI(SO4)2, KAI(SO )2, ZnSO4, NaH2PO4, Na2HPO4, KH2PO , K2HPO4, Zn3(PO )2, Ca(H2PO4)2, CaHPO4, Na2H2P2O7, Na3HP2O7, NasPsOio, K5P3Oio, (NH4)H2PO , (NH4)2HPO4 or hydrates thereof.
Optionally, the aqueous solution may also comprise auxiliary agents.
[0079] In a further embodiment of the invention 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%, 6.76 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%, 14.0 vol%, 15.0 vol%, 16.0 vol%, 17.0 vol% 18.0 vol%, 19.0 vol%, 20.0 vol%, 22.5 vol%, 25.0 vol%, 27.5 vol%, 30.0 vol%, 32.5 vol%, 35.0 vol%, 37.5 vol%, 40.0 vol%, 42.5 vol%, 45.0 vol%, 47.5 vol%, or 50.0 vol%.
[0080] In a further embodiment of the invention 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, H2SO4, lactic acid, succinic acid or malonic acid. Optionally, the aqueous solution may also comprise auxiliary agents.
[0081 ] In a further embodiment of the invention the aqueous solution comprises at least one nitrate salt, at least one acid in respective concentrations as stated above and optionally auxiliary agents. [0082] In a further embodiment of the invention 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%. Preferably, 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.
[0083] In a further embodiment of the invention 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%. Preferably, 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.
[0084] In a further embodiment of the invention 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%. Preferably, 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,/\Adiacetic 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, 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. [0085] In a further embodiment of the invention the aqueous solution comprises Mg( 03)2, optionally a different nitrate salt, and optionally a complexing agent. Tartaric acid is added to create the used/vintage look.
[0086] In a further embodiment of the invention the aqueous solution comprises about 26 vol% Mg(NO3)2, about 0.05 - 0.1 vol% of a different nitrate salt, and optionally about 0.01 - 0.05 chelating agent. About 1.0 - 10.0 vol% tartaric acid is 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.
[0087] 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.
[0088] 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 , Ce(SO4)2, VOS04, FeSO4, Fe2(SO4)3, ZnCb, FeC , CuCb, FeCb, AlCb, UNO3, CaCb, NaCI, KCI, LiCI, SrCb, MgCb, (NH4)2SO4, CuSO4, Li2SO4, NH4AI(SO4)2, KAI(SO4)2, Zn3(PO4)2,
NaH2PO4, Na2HPO4, KH2PO4, K2HPO4, Ca(H2PO4)2, CaHPO4, Na2H2P2O7, Na3HP2O7, NasPsOio, K5P3O10, (NH4)H2PO4, (NH4)2HPO4, or hydrates thereof.
[0089] 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 (CH3SO3H), citric acid, tartaric acid, oxalic acid, HCI, maleic acid, H2SO4, lactic acid, or malonic acid or mixtures thereof.
[0090] 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 MgSO4, Ce(S0 )2, VOS04, FeS04, Fe2(SO4)3! ZnCb, FeC , CuCb, FeCI2, AlCb, CaCb, NaCI, KCI, LiCI, SrC , MgCb, (NH4)2S04, CuSO4, Li2S04l NH4AI(SO4)2,
KAI(S04)2, Zn(N03)2, NaH2PO4, Na2HP04, KH2P04, K2HP04, Ca(H2P04)2, CaHP04, Na2H2P207, Na3HP207, NasPsOio, K5P3O10, (NH4)H2P04, (NH4)2HPO4 or hydrates thereof, or wherein the acid catalyst is selected from the group consisting of
methanesulfonic acid, toluenesulfonic acid, citric acid, tartaric acid, oxalic acid, HCI, maleic acid, H2S04, lactic acid, succinic acid or malonic acid, and optionally comprising at least one further auxiliary chemical and/or thickening agent.
[0091] 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.
[0092] A further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Mg(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
[0093] A further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% K(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
[0094] A further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Li(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
[0095] A further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Na(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
[0096] A further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Ca(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
[0097] A further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Fe(NO:3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
[0098] A further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Cu(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
[0099] A further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Zn(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
[00100] A further embodiment of the invention relates to the use of an aqueous solution comprising about 10 - 30 vol% Co(NO3)2, about 5 - 10 vol% potassium and sodium phosphate buffer salts and optionally a thickener for about 12 cP (20 °C) and about 0.05 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.
[00101] In a further embodiment the colour value changes and can be measured in a ΔΙ_ 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.
[00102] In a further embodiment isatin, anthranilic acid (2-aminobenzoic acid) and carbamic acid are formed due to the general oxidation reaction of indigo. 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 the 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.
[00103] In a further embodiment the anhydroglucose units of the denim material may be esterified on positions 2, 3 and/or 6 by action of the nitrate compounds under given conditions.
[00104] As stated above for activation no heating step is required for the bleaching process. According to the inventive process bleaching occurs after catalytic activation of the nitrate salt by the acid catalyst. However, applying a moderate heating step by a type of advection, conduction, convection or radiation, or a combination , may improve the intensity of the effect on various fabric and dyeing types and increase the speed of effect generation. Therefore the treatment may optionally be carrying out at a temperature of about 10 - 90 °C, or of about 10 - 70 °C, or of about 10 - 60 °C, or of about 10 - 40°C, or of about 20 - 80 °C, or of about 20 - 60 °C, or of about 20 - 35 °C.
[00105] Additionally further textile auxiliary chemicals may be added in any
combination and concentration in solid or liquid form to improve the usability and performance of the product according to what is required: 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. These 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,
Azorubin, Betanin, Brown FK, Brown HT, Brilliant blue, Brilliant black, Canthaxanthin, Carotin, Annatto (Norbixin), Capsanthin, Lycopin, 8'-Apo- -caroten-8'-al, Ethyl-8'-apo- -caroten-8'-oat, Chinolin yellow, Chlorophyll, Cochenille red A, Curcumin, Iron oxide, Erythrosin, Yellow orange, Gold, Green S, Indigotin, Cochenille, Lactoflavin, Litholrubin BK, Lutein, Patent Blue V, Riboflavin, Silver, Tartrazin, Titanium dioxide, Zeaxanthin, as well as duramine (e.g. Red), chromene (e.g. Red, Blue, Yellow), Evron Red may also be used. Other 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,AAdiacetic 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.
methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, ethylhydroxyethyl cellulose), alginates (i.e. sodium-, potassium-, ammonium-, propylenglycol alginate), gum arabic, carrageen, agar-agar, Ceratonia silique, guar gum, Traganth, gellan, pectin, gelatin. 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.). [Examples
The Examples which follow are set forth to aid in the understanding of the invention but are not intended to, and should not be construed to limit the scope of the invention in any way. The Examples do not include detailed descriptions of conventional methods. Such methods are well known to those of ordinary skill in the art.
[00106] 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 salt was applied to the surface.
[00107] 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 salt was applied to the surface by printing.
[00108] 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 containing solution is applied by spray to the garment.
[00109] 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 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.
[001 10] 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 salt 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.
[001 1 1] The color changing effect in such pretreated denim fabrics is then generated with or without heat treatment (including microwave irradiation, IR irradiation, etc.) depending on the composition of the solution.
[001 12] 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 salt is applied by immersing or only to the surface (e.g. kiss roll, knife application, foaming, etc.). The effect is generated during a subsequent heat treatment.
[001 13] 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 salt is applied by immersion or only to the surface (e.g. kiss roll, knife application, foaming, etc.). The effect is generated during a subsequent heat treatment.
[001 14] 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 heat treatment.
[001 15] 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 heat treatment.
[001 16] 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.
[001 17] 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.
[001 18] 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.
[001 19] 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 is applied to the garment and dried. Subsequently a solution containing an acid is applied by brush or sponge on specific areas of the garment.
[00120] 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 is applied to the garment and dried. Subsequently a solution containing a nitrate is applied by brush or sponge on specific areas of the garment.
[00121] Pumice stones are soaked in a solution containing an acid and a nitrate and subsequently agitated with a denim garment in a tumbler. [00122] A denim garment is wetted and placed together with a powder containing nitrate and acid (if needed together with a filler material like sand, perlite, etc.) in a bag and agitated until the effect is created.
[00123] The color changing effect in such pretreated denim fabrics is then generated with or without applying any heat treatment.
[00124] A solution containing nitrate salt and an acid catalyst acid is applied to a fabric or denim garment and subjected to microwave irradiation. The power of irradiation varies from 100 W to 1000 W, depending on the desired effect. The time of irradiation varies from 10 second to 1200 seconds, also depending on the desired effect.
[00125] A solution containing nitrate salt and an acid catalyst is applied to a fabric or denim garment and subjected to microwave irradiation.
[00126] Examples according to [00106] to [00125] 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.
[00127] Examples according to [00106] to [00125] are subsequently washed with methods known to the skilled person of the art, e.g. chlorine treatment, hydrogen peroxide treatment, potassium peroxide treatment, ozone treatment, enzyme
(cellulose, laccase, peroxidase, etc.) treatment, stonewashing, glucose treatment, organo peroxide treatment, softening, tinting (adjusting the colour tone with dyestuffs), etc.
[00128] Examples according to [00106] to [00125] are previously washed with methods known to the skilled person of the art, e.g. chlorine treatment, hydrogen peroxide treatment, potassium peroxide treatment, ozone treatment, enzyme
(cellulose, laccase, peroxidase, etc.) treatment, stonewashing, glucose treatment, organo peroxide treatment, scraping, lasering, ice-blasting, carbon dioxide blasting, sand blasting, etc.
[00129] Tables 1 to 7 depict compositions of aqueous solutions which are applied to denim fabrics.
[00130] Table 8 depicts examples of microwave irradiation as respective
heating/activation step. CS003P 23
Table 1
# Nitrate Salt [%] Acid Catalyst [%] Acid [%] Time [h]
1 Mg(N03)2-6H20 51 .0 MgSO.i 5.7 methanesulfonic acid 10.0 0.5
2 Mg(N03)2-6H20 51 .0 Ce(S04)2 1 .0 methanesulfonic acid 10.0 0.5
3 Mg(N03)2-6H20 51 .0 VOSO4 4.2 methanesulfonic acid 10.0 0.5
4 Mg(N03)2-6H20 51 .0 FeSO.i 1 .6 methanesulfonic acid 10.0 0.5
5 Mg(N03)2-6H20 51 .0 Fe2(S04)3 6.5 methanesulfonic acid 10.0 0.5
6 Mg(N03)2-6H20 52.0 citric acid 30.0 4
7 Mg(N03)2-6H20 34.8 tartaric acid 40.0 2
8 Mg(N03)2-6H20 55.1 oxalic acid 5.0 0.5
9 Mg(N03)2-6H20 51 .0 methanesulfonic acid 10.0 0.5
10 Mg(N03)2-6H20 51 .0 nitric acid 6.5 0.5
1 1 Mg(N03)2-6H20 51 .0 methanesulfonic acid 10.0 0.5
12 Mg(N03)2-6H20 51 .0 HCI 25% 10.0 0.5
13 Mg(N03)2-6H20 51 .0 ZnC 3.3 methanesulfonic acid 10.0 0.5
14 Mg(N03)2-6H20 51 .0 FeCI3 90% 9.7 methanesulfonic acid 10.0 0.5
15 Mg(N03)2-6H20 51 .0 CuCb 4.1 methanesulfonic acid 10.0 0.5
16 Mg(N03)2-6H20 51 .0 FeCb 4.8 methanesulfonic acid 10.0 0.5
17 Mg(N03)2-6H20 51 .0 AICI3 3.2 methanesulfonic acid 10.0 0.5
Mg(NO3)2-6H2O 40.0
18 maleic acid 16.0 1
LiNOs 2.0
CS003P 24
# Nitrate Salt [%] Acid Catalyst Acid [%] Time [h]
Figure imgf000025_0001
Mg(N03)2-6H20 51 .0
20 HCI 25% 15.0 0.5
LiN03 2.6
Mg(N03)2-6H20 30.0
21 tartaric acid 30.0 3
LiN03 1.5
Mg(N03)2-6H20 60.0
22 H2S04 98% 1 .0 0.5
LiN03 3.0
23 LiNOs 27.9 methanesulfonic acid 10.0 0.5
24 AI(N03) 3 50.5 methanesulfonic acid 10.0 0.5
25 Ca(N03)2 47.7 methanesulfonic acid 10.0 0.5
26 Fe(N03)3-9H20 54.0 methanesulfonic acid 10.0 0.5
27 Cu(N03)2 48.0 methanesulfonic acid 10.0 0.5
28 Zn(N03)2 60.0 methanesulfonic acid 10.0 0.5
29 KN03 40.0 methanesulfonic acid 10.0 0.5
30 LiNOs 13.9 methanesulfonic acid 10.0 0.5
31 KN03 20.0 methanesulfonic acid 10.0 0.5
32 Fe(N03)3-9H20 40.0 methanesulfonic acid 10.0 0.5
33 (NH4)2Ce(N03)6 36.0 methanesulfonic acid 10.0 0.5
34 Co(N03)2-6H20 58.0 methanesulfonic acid 10.0 0.5
35 AI(N03)3-9H20 30.0 citric acid 25.0 4
CS003P 25
# Nitrate Salt [%] Acid Catalyst [%] Acid [%] Time [h]
36 Mg(N03)2-6H20 63.0 methanesuifonic acid 10.0 0.3
Table 2
±L Mg(N03)2 + Nitrate Salt Acid Acid Additive Thickener Temp T tr
■6H2O [%] [%] Catalyst [%] [%] [%] [%] [°C] [
37 25 AI(N03)3-9H20 5 xanthan gum 0.3 50
38 25 AI(N03)3-9H20 4 xanthan gum 0.3 50
39 25 AI(N03)3-9H20 3 xanthan gum 0.3 50
40 25 AI(N03)3-9H20 2 xanthan gum 0.3 50
41 25 AI(N03)3-9H20 1 xanthan gum 0.3 50
42 25 ΑΙ(Ν03)3·9Η20 0.1 tartaric acid 1 60
43 25 ΑΙ(Ν03)3·9Η20 45 80
44 ΑΙ(Ν03)3·9Η20 40 80
45 ΑΙ(Ν03)3·9Η20 35 80
46 ΑΙ(Ν03)3·9Η20 30 80
47 ΑΙ(Ν03)3·9Η20 25 80
48 ΑΙ(Ν03)3·9Η20 20 80
49 ΑΙ(Ν03)3·9Η20 18 80
50 70 CaC 2 20
51 70 ZnCb 2 20
52 70 NaCI 2 20
CS003P 26
Mg(N03)2 + Nitrate Salt Acid Acid Additive Thickener Temp T ff
■6H20 [%] [%] Catalyst [%] [%] [%] [%] [°C] [
53 70 KCI 2 20
54 70 LiCI 2 20
55 70 SrCb 2 20
56 70 MgCI2 2 20
57 70 (NH4)2S04 2 20
58 70 CuS04 2 20
59 70 Li2S04 2 20
60 70 NH4AI(S04)2 2 20
61 70 KAI(S04)2 2 20
62 70 FeS04 2 20
63 Ce(S04)2 2 20
64 20 AI(N03)39H20 4 Zn(N03)2-6H20 0.05 xanthan gum 0.15 60
65 25 Fe(N03)2-6H20 1 tartaric acid 4 80
66 30 Fe(N03)2-6H20 0.01 tartaric acid 1 80
67 LiN03 30 80
68 35 CaCb 2 citric acid 10 60
69 35 ZnCb 2 citric acid 10 60
70 35 NaCI 2 citric acid 10 60
71 35 KCI 2 citric acid 10 60
72 35 LiCI 2 citric acid 10 60
73 35 SrCb 2 citric acid 10 60
CS003P 27
4£ g(N03)2 + Nitrate Salt Acid Acid Additive Thickener Temp T
W
■6H20 [%] [%] Catalyst [%] [%] [%] [%] [°C] [
74 35 MgC 2 citric acid 10 60
75 35 (NH4)2S04 2 citric acid 10 60
76 35 CuSO 2 citric acid 10 60
77 35 SJ2SO4 2 citric acid 10 60
78 35 NH4AI(S04)2 2 citric acid 10 60
79 35 KAI(S04)2 2 citric acid 10 60
80 35 FeS04 2 citric acid 10 60
81 35 Ce(S04)2 2 citric acid 10 60
82 35 CaCb 2 tartaric acid 4 60
83 35 ZnCb 2 tartaric acid 4 60
84 35 NaCI 2 tartaric acid 4 60
85 35 KCI 2 tartaric acid 4 60
86 35 LiCI 2 tartaric acid 4 60
87 35 SrCb 2 tartaric acid 4 60
88 35 MgCb 2 tartaric acid 4 60
89 35 (NH. 2SO4 2 tartaric acid 4 60
90 35 CuS04 2 tartaric acid 4 60
91 35 Li2S04 2 tartaric acid 4 60
92 35 NH.,AI(S04)2 2 tartaric acid 4 60
93 35 KAI(S04)2 2 tartaric acid 4 60
94 35 FeS0 2 tartaric acid 4 60
CS003P 28
# Mg(N03)2 + Nitrate Salt Acid Acid Additive Thickener Temp T
■6H2O [%] [%] Catalyst [%] [%] [%] [%] [°C] [
95 35 Ce(S04)2 2 tartaric acid 4 60
96 25 tartaric acid 5 Zn(N03)2-6H20 60
Table 3
Mg(N03)2 Temp Ti
# + Nitrate Salt [%] Acid [%] Addition [%] Thickener [%]
*6H20 [%] [°C] [
97 26.6 Zn(N03)2 *6H20 0.05 tartaric acid 2 60
98 26.6 Zn(N03)2 *6H20 0.05 malonic acid 2 60
99 26.6 Zn(N03)2 *6H20 0.05 citric acid 2 60
100 26.6 Zn(N03)2 *6H20 0.05 maleic acid 2 60
101 26.6 Zn(N03)2 *6H20 0.05 methanesulfonic acid 5 60
102 26.6 Zn(N03)2 *6H20 0.05 methanesulfonic acid 10 60
103 26.6 Zn(N03)2 *6H20 0.05 tartaric acid 2 DMSO 1 60
104 26.6 Zn(N03)2 *6H20 0.05 tartaric acid 2 LiN03 1 60
105 26.6 Zn(N03)2 *6H20 0.05 tartaric acid 2 triethanolamine 5 60
CS003P Table 4
# g(N03)2*6H20 [%] Acid Catalyst [%] Acid Temp [°C] Time [min]
KAI(S04)2-12H20 5
106 35 tartaric acid 60 20
LiCI 2.5
KAI(S04)2-12H20 5
107 35 tartaric acid 60 20
LiCI 1
KAI(SC¼)2-12H20 5
108 35 tartaric acid 60 20
LiCI 0.5
KAI(S04)2-12H20 5
109 35 tartaric acid 60 20
LiCI 0.1
1 10 35 KAI(S04)2-12H20 5 malonic acid 60 20
1 1 1 35 KAI(S04)2-12H20 5 citric acid 60 20
1 12 35 KAI(S04)2-12H20 5 maleic acid 60 20
1 13 35 KAI(S04)2-12H20 5 lactic acid 60 20
1 14 35 KAI(S04)2-12H20 5 oxalic acid 60 20
CS003P 30
Table 5
# Mg(N03)2-eH20 [%] Acid Catalyst [%] Acid [%] Addititive [%] Temp [°C] Time [min]
1 15 35 KAI(SC¼)2-12H20 5 acetic acid 2 60 20
1 16 35 KAI(S04)2-12H20 5 phosphoric acid 1 60 20
1 17 70 KAI(S04)2-12H20 5 hydrochloric acid 3.6 60 20
1 18 35 KAI(S04)2-12H20 5 sulphuric acid 4.5 60 20
1 19 35 KAI(S04)2-12H20 5 salpetric acid 1 .5 60 20
Dispersoko
120 35 KAI(S04)2-12H20 5 tartaric acid 2 0.01 60 20
ICP 100 CO
Dispersoko
121 35 KAI(S04)2-12H20 5 tartaric acid 2 0.01 60 20
ICP 100 PL
polysorbate
122 35 KA!(S04)2-12H20 5 tartaric acid 2 0.1 60 20
20
123 35 KAI(S04)2-12H20 5 tartaric acid 2 Nofome AF 0.1 60 20
Table 6
# g(N03)2- Temp Time
Nitrate Salt [%] Acid Catalyst Acid [%] Additive [%]
6H20 [%] [°C] [min]
tartaric 2 Setamol Disperse
124 35 KAI(S04)2-12H20 0.1 60 20 acid WS
CS003P 31
#
Figure imgf000032_0001
tartaric
125 26.6 Zn(N03)2-6H20 0.05 2 Methyl red 0.01 60 20 acid
tartaric
126 26.6 Zn(N03)2-6H20 0.05 2 Chromene Red 0.005 60 20 acid
tartaric
127 26.6 Zn(N03)2-6H20 0.05 2 Chromene Red 0.01 60 20 acid
tartaric
128 26.6 Zn(N03)2-6H20 0.05 2 Chromene Red 0.015 60 20 acid
tartaric
129 26.6 Zn(N03)2-6H20 0.05 2 Chromene Red 0.02 60 20 acid
tartaric
130 26.6 Zn(N03)2-6H20 0.05 2 Chromene Red 0.025 60 20 acid
tartaric
131 35 KAI(SC¼)2-12H20 5 2 Methyl red 0.01 60 20 acid
tartaric
132 35 KAI(S04)2-12H20 5 2 Chromene Red 0.005 60 20 acid
tartaric
133 35 KAI(S04)2-12H20 5 2 Chromene Red 0.01 60 20 acid
CS003P 32
Table 7
g(N03)2 Acid Catalyst/ Temp Ti
[%] Acid Additive [%] Thickener [%]
■6H2O [%] Nitrate Salt [°C] [ tartaric
134 KAI(S04)2-12H20 Chromene Red 0.015 60
acid
tartaric
135 KAI(S04)2-12H20 Chromene Red 0.02 60
acid
tartaric
136 KAI(S04)2-12H20 Chromene Red 0.025 60
acid
monosodium
137 35 60
phosphate
monosodium
138 35 60
phosphate
monopotassium
139 35 60
phosphate
monopotassium
140 35 60
phosphate
141 35 60
disodium
142 35 60
pyrophosphate
disodium
143 25 60
pyrophosphate
Mg(N03)2 Acid Catalyst/ Temp
Thickener [%] •6H2O [%] Nitrate Salt [°C]
144 20 60
145 15 60
146 35 45
147 20 45 tartaric
148 35 1.5 60 acid
tartaric
149 26.6 Zn(N03)2-6H20 Trilon M 0.01 60 acid
tartaric
150 26.6 Zn(N03)2-6H20 Dissolvine GL 38 0.01 60 acid
Table 8
# Time [sec] Power
151 10 1000
152 20 1000
153 30 1000
154 20 800
155 30 800
156 40 800
157 30 600
158 40 600
159 60 400
160 80 400
161 60 500
162 90 500
163 60 300
164 90 300
165 90 200
166 120 200

Claims

Claims
1. A method for changing the color of a dyed textile material to obtain a vintage
and/or worn appearance comprising the steps of:
a. contacting said textile material with at least one nitrate salt,
b. activating said nitrate salt by the addition of an acid catalyst, and
c. maintaining step b) until the desired color change is achieved.
2. The method according to claim 1 , wherein the nitrate salt is an organic or inorganic nitrate salt.
3. The method according to claim 2, wherein the inorganic nitrate salt is selected from the group consisting of Mg(N03)2, KNO3, UNO3, AI(NO3)3, Ca(NO3)2, Fe(NO3)3, Cu(NO3)2, Co(NO3)2, (NH4)2Ce(NO3)6, NaNO3, RbNO3, CsNO3, Sr(NO3)2,
Ba(NO3)2, Sc(NO3)3, Ti(NO3)4, Zr(NO3)4, VO(NO3)3, Cr(NO3)3, Mn(NO3)2, Co(NO3)2, Co(NO3)3, Ni(NO3)2, Pd(NO3)2, AgNO3, Cd(NO3)2, Hg2(NO3)2, Hg(NO3)2,
[B(NO3)4]-, Ga(NO3)3, TI(NO3)3, Pb(NO3)2, Bi(NO3)3, FNO3, CINO3, Xe(NO3)2, Ce(NO3)3, Ce(NO3)4, Gd(NO3)3.
4. The method according to claim 3, wherein the nitrate salt is Mg(NO3)2, KNO3,
LiNOs, NaNOs, AI(NO3)3, Ca(NO3)2, Fe(NO3)3, Cu(NO3)2, Zn(NO3)2, Co(NO3)2, or (NH4)2Ce(NO3)6.
5. The method according to any of claims 1 to 4, wherein the nitrate salt is applied in solution, wet or dry form.
6. The method according to any one of claims 1 to 5, wherein the acid catalyst is
selected from the group consisting of organic or inorganic compounds, i.e. organic or inorganic acids, organic or inorganic chlorides, sulfates, phosphates, borates, fluorides, acid forming esters, amino acid hydrochlorides, and Lewis acid chlorides.
7. The method according to claim 6, wherein the acid catalyst is an organic or
inorganic acid.
8. The method according to claim 7, wherein the acid catalyst is selected from the group consisting of methanesulfonic acid, citric acid, tartaric acid, oxalic acid, toluenesulfonic acid, succinic acid, maleic acid, malic acid, sulfuric acid,
hydrochloric acid, phosphoric acid, and salicylic acid, or mixtures thereof.
9. The method according to claim 6, wherein the Lewis acid chloride is ferric chloride, zinc chloride, lithium chloride, copper chloride, magnesium chloride or aluminum chloride and a sulfate as magnesium sulfate, iron sulfate, iron sulfate, cerium sulfate, vanadium sulfate, copper sulfate, lithium sulfate, aluminum sulfate, potassium aluminum sulfate, ammonium aluminum sulfate, sodium sulfate, sodium hydrogen sulfate, zinc sulfate and 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.
10. The method according to any one of claims 6 to 9, wherein the acid catalyst is
capsuled.
1 1. The method according to any one of claims 1 to 10, 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 salt.
12. The method according to claim 1 , wherein the textile material is treated with an aqueous solution comprising at least one nitrate salt which is activated by an acid catalyst, wherein the treatment is carried out until the desired color change is achieved.
13. The method according to claim 12, wherein said aqueous solution comprises about 10 - 75 vol% nitrate salt, optionally 0.01 - 5 vol% of a different nitrate salt , and 0.5 - 50 vol% acid catalyst.
14. The method according to claim 12, wherein said aqueous solution comprises about 15 - 50 vol% AI(N03)3 and about 0.5 - 10 vol% toluenesulfonic acid.
15. The method according to any of claims 12 to 14, wherein the treatment 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.
16. The method according to any of claims 1 to 15, wherein an auxiliary agent is
comprised.
17. The method according to any one of claims 1 to 16, in which commonly used dyes for the textile are sulphur dye, reactive dye, direct dye, VAT dye, basic dye, pigment dye, or natural dyes. A combination of different dyes is also possible and can emerge as solid dye, top or bottom indigo combination dye.
18. The method according to any one of claims 1 to 17, wherein the acid catalyst is provided as a buffered agent.
19. The method according to any one of claims 12 to 18, wherein the pH of the solution is higher than 2.
20. Use of an aqueous composition comprising at least one nitrate salt, optionally a different nitrate salt, and at least one acid catalyst, and optionally an auxiliary and/or chelating agent, for the treatment of textile material in order to obtain a worn appearance and/or vintage look.
21. The use according to claim 20, wherein the aqueous solution comprises about 10 - 75 vol% nitrate salt, optionally about 0.01 - 5 vol% of a different nitrate salt, and about 0.5 - 50.0 vol% acid catalyst, and optionally about 0.01 - 0.05 vol% of at least one chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
22. The use according to claim 20 or 21 , wherein the aqueous solution comprises
about 20 - 30 vol% nitrate salt, optionally about 0.05 - 3 vol% of a different nitrate salt, and about 1.0 - 30.0 vol% acid catalyst, and optionally about 0.01 - 0.05 vol% chelating agent and optionally about 0.01 - 15 vol% of at least one auxiliary agent.
23. The use according to any one of claims 20 to 22, wherein said auxiliary agent is selected from the group consisting of a softener, brightening agent, plastic, 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.
24. A method according to claim 1 , where the ΔΙ_ value between the untreated and treated part is greater than 2. L stands for the lightness in the CIE 1976 Lab color space.
PCT/EP2016/080370 2015-12-10 2016-12-09 Treatment of textile material WO2017097952A1 (en)

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US5350423A (en) * 1992-09-23 1994-09-27 Burlington Industries Inc. Fabric finishing procedure
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CN112888819A (en) * 2019-05-08 2021-06-01 尚科纺织企业工业及贸易公司 Method for changing the color of textiles, fabrics and garments

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