WO1995013415A1 - Decoloration de tissus et de vetements au moyen d'un agent de traitement liquide contenant de l'ozone - Google Patents

Decoloration de tissus et de vetements au moyen d'un agent de traitement liquide contenant de l'ozone Download PDF

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Publication number
WO1995013415A1
WO1995013415A1 PCT/US1994/012506 US9412506W WO9513415A1 WO 1995013415 A1 WO1995013415 A1 WO 1995013415A1 US 9412506 W US9412506 W US 9412506W WO 9513415 A1 WO9513415 A1 WO 9513415A1
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WIPO (PCT)
Prior art keywords
fabric
treating agent
ozone
liquid treating
decolorizing
Prior art date
Application number
PCT/US1994/012506
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English (en)
Inventor
Robert Dale Hei
Helmut K. Maier
Lynne Ann Olson
Jay Thomas Kummet
David Jay Falbaum
Original Assignee
Ecolab Inc.
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 Ecolab Inc. filed Critical Ecolab Inc.
Priority to AU81299/94A priority Critical patent/AU8129994A/en
Publication of WO1995013415A1 publication Critical patent/WO1995013415A1/fr

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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
    • D06P5/15—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
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B11/00—Treatment of selected parts of textile materials, e.g. partial dyeing
    • D06B11/0093—Treatments carried out during or after a regular application of treating materials, in order to get differentiated effects on the textile material
    • D06B11/0096—Treatments carried out during or after a regular application of treating materials, in order to get differentiated effects on the textile material to get a faded look
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/50—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs by irradiation or ozonisation

Definitions

  • the invention relates to an ozone-containing composition.
  • the invention also relates to a method for decolorizing a fabric.
  • the invention relates to a decolorized fabric.
  • Garments made from cellulosic or cellulosic-blend fabric such as cotton and denim are stiff in texture due to the presence of sizing compositions used to facilitate or aid manufacturing, handling and assembling of the garments and typically have an unused, dark, dyed appearance.
  • the garments particularly blue jeans, can develop in the fabric panels and on the seams localized areas of color variations in the form of lightening or fading, in the depth or density of color.
  • a general fading of the garments can often appear in conjunction with the production of a "fuzzy" surface, some "pucker", in seams and some wrinkling in the fabric panels.
  • the clothing while wet is tumbled with the pumice for a sufficient period such that the pumice abrades the fabric to produce in the fabric panels localized abraded areas of lighter color and similar lightened areas in the seams.
  • the pumice softens the fabric and produces a fuzzy surface similar to that produced by the extended wear of a garment.
  • these processes cause substantial mechanical deterioration or degradation of the fabric, as demonstrated by measurable tensile strength loss.
  • the stone-pumice process is troubled with considerable processing equipment wear and deterioration from mechanical stone abrasion. Wastewater problems with the process are also an issue, since a large quantity of denim- dye and pumice grit are generated. Both of these by-products tend to lead to expensive, labor intensive garment finishing and water treatment steps in the process.
  • processing rates are detrimentally affected by the stones since a portion of the processing equipment volume (often up to 50%) is taken up by the stone volume.
  • Patent 4,740,213 or prepare a bleaching composition comprising a partially saturated carrier and a powdered or granulated oxidizing agent
  • a powdered or granulated oxidizing agent Dickson et al., U.S. Patent 4,900,323, and Olson et al., U.S. Patent No. 4,997,450.
  • Tumbling dry or dampened garments with stones, pellets, or powders containing such oxidizing systems gives a stone-washed or frosted look, depending on the type and concentration of oxidizing agent, physical form of the contacting solid, and the balance of water between the garments and bleach carrier within the tumbling apparatus.
  • Ozone has been used in the bleaching, or whitening, of non-dyed cellulosic materials such as paper and fabric.
  • Ozone (0 3 ) is composed entirely of oxygen atoms which is a high energy form of oxygen and is unstable at room, or higher temperatures, and decomposes to form oxygen (0 2 ) .
  • U.S. Patent No. 5,118,322 asinger et al.
  • U.S. Patent No. 4,283,251 (Singh)
  • Japanese Patent No. 4,100,987 discloses a process of exposing a dyed fabric to a wet atmosphere of ozone.
  • the invention provides a method of decolorizing a colored or dyed fabric using a liquid treating agent containing ozone and a decolorized fabric resulting from the decolorizing.
  • a method for decolorizing dyed fabric comprising the step of contacting a dyed fabric with a liquid treating agent containing an aqueous liquid medium, having a pH sufficiently low to retard ozone decomposition in the liquid treating agent, and an active ozone composition sufficient to decolorize the fabric.
  • the invention also provides a method of obtaining a "fuzzy", "used” or “pre-worn” fabric surface similar to that produced by pumice stones or extended wear of a garment, and even more similar to the look known in the industry as "frosted", currently a look only achieved by the dry bleach technology.
  • the visual appearance of the surface fuzziness or napping is variable with reaction time, pH, temperature and processing equipment loading; i.e. the ratio of visual fuzz development to decolorization of the fabric base can be controlled by processing conditions.
  • the extent of nap development (surface change) is variable with reaction time, pH, temperature and processing equipment loading; i.e., a variety of "looks" with potential consumer appeal can be obtained in combination with fabric decolorization.
  • a method for decolorizing a fabric comprising the steps of injecting a gas containing ozone at a flow rate at about 20 to 225 standard cubic feet per hour into an aqueous liquid medium having a pH of up to about 13 flowing at a rate of about 1 to 50 gal/min, mixing the gas containing ozone with the aqueous liquid medium to produce a liquid treating agent and contacting the fabric with the liquid treating agent for about 15 to 45 minutes during the contacting step.
  • the temperature of the liquid treating agent is maintained at a temperature in the range of 1 to 70°C.
  • the invention is directed to a decolorized and/or abraded fabric resulting from the method of the invention.
  • the invention also provides a liquid treating agent for decolorizing fabric which comprises an aqueous liquid medium having a pH of up to about 13, an active ozone composition sufficient to decolorize and abrade the fabric and pumice.
  • the composition can further include an ozone potentiator, a buffer, a mineral acid, an inorganic base and mixtures thereof.
  • the invention teaches how to produce a "pre-worn, or frosted, or used" garment look using room temperature, or cooler, aqueous solutions of dissolved ozone at a variety of pH's. Additionally, the invention provides for, and demonstrates, the unexpected minimization, or elimination, of other aforementioned processing problems; such as: waste water issues, dye redeposition and pocket whiteness, fabric strength loss, and no loss in equipment processing volume. Also, a modifiable degree of apparent "fuzziness" or "pre- worness" which allows for a variety of customized garment looks; can be controlled by reaction conditions such as time, pH, temperature and processing load.
  • FIGURE 1 is a schematic diagram of a preferred embodiment of apparatus that can be used to carry out the invention.
  • a method for decolorizing a dyed or colored fabric comprising the step of contacting the fabric with an ozonated liquid treating agent in an amount sufficient to decolorize and/or give a "fuzzy", "pre-worn” or “frosted” appearance to the fabric.
  • Ozone cannot be easily stored or shipped. Therefore, the ozone that is utilized in the invention is typically generated on- site and dissolved into an aqueous medium at the use locus just prior to use. Within particular limits, shortening the distance between the points of ozone generation and use reduces the ozone decomposition loss in the aqueous medium.
  • the half-life of ozone in neutral solutions is on the order of 3 to 10 minutes and decreases as the pH increases.
  • Weak concentrations of ozone can be generated using ultra-violet radiation, but generally, production of the ozone is by using electrical corona discharge.
  • the process of the invention involves a source of oxygen (0 2 ), generally atmospheric oxygen (air), or oxygen enriched air.
  • the source of 0 2 is passed between electrodes across which a high voltage alternating potential is maintained.
  • the electrodes are powered from a step transformer using service current.
  • the potential is established across the electrodes which are configured to prevent arcing.
  • As oxygen molecules enter the area of the potential a corona is created having a proportion of free atomic oxygen ions from disassociated 0 2 .
  • the high energy atomic ions (0) when combined with oxygen (0 2 ) form a mixture of oxygen and ozone.
  • These ozone generators are available commercially.
  • the gas containing ozone used in the invention for decolorization does not have to be pure ozone gas, and can be ozone enriched air.
  • the gas containing ozone is generally contacted with an aqueous solution through bubbling, injection or other gas dispersion techniques to introduce a concentration of ozone into the aqueous medium.
  • the contact between the gas containing ozone and the aqueous medium is engineered to maximize the absorption of ozone when compared to the rate of decomposition of ozone in the aqueous medium.
  • the rate of dissolution of the ozone in the aqueous medium of the invention can be improved by introducing the gas containing ozone into the aqueous medium with the smallest practical diameter bubble formation to promote the mass transfer of ozone into the aqueous medium.
  • Surface active agents which lower the interfacial tension between the gas containing ozone phase and aqueous liquid phase of the treating agent, can be used to enhance the gas containing ozone dissolution into the aqueous medium. Rapid dissolution of the ozone can reduce the tendency of the ozone to bubble out of the liquid treating agent.
  • total ozone relates to the amount of ozone generated in the gas phase.
  • Measured ozone is the apparent concentration of ozone (as 0 3 in aqueous solution).
  • the difference between total ozone and measured ozone relates to an amount of ozone off-gassed from solution, or apparently converted in the liquid treating agent by reaction with inorganic species in the aqueous medium to form oxidized radicals and anions, e.g., hydroxyl radicals and anions, ozonide radical ion, super oxide radical ion, etc.
  • oxidized radicals and anions e.g., hydroxyl radicals and anions, ozonide radical ion, super oxide radical ion, etc.
  • Such oxidized materials like ozone, can be a source of oxidizing potential.
  • the decolorizing power of the liquid treating agent of the invention relates to the presence of free solubilized "measured” ozone species and the presence of species that can act as oxidizing agents created in-situ from the reaction of the ozone.
  • active ozone refers to the total concentration of oxidizing species produced by introducing ozone into the aqueous medium of the invention.
  • initial ozone means the measured concentration of ozone immediately after introduction of ozone into the aqueous solution. The difference between initial ozone and measured ozone can be related to the timing of the measurement. Measured ozone is the concentration of ozone in solution measured at any time after the initial ozone value is found.
  • the ozone reacts with the dye(s) or dye residues in the fabric resulting from the dyeing or coloring of the fabric in the manufacturing thereof. Additionally, under a variety of controllable conditions, various chemical and mechanical mechanisms apparently give rise to fabric surface changes which can produce a variety of "used”, “fuzzy”, or "pre-worn” appearances.
  • the concentration of the ozone is preferably maintained as high as practical to obtain the most active decolorizing action. Accordingly, a concentration as high as about 40 parts by weight of ozone per million parts of the liquid treating agent, depending on pH and temperature, is a desirable goal. Due to the decomposition of ozone and the limited solubility of ozone in water, the concentration of the oxidizing species commonly will fall between about 0.1 and 30 parts of measured ozone per million parts of the liquid treating agent, and usually from about 1 to about 10 parts per million of measured ozone in the liquid treating agent.
  • the decolorization capacity of the liquid treating agent increases substantially.
  • the measurement of potential or electro-motive force can be used to characterize the decolorizing capacity of the liquid treating agent of the invention.
  • Reference electrodes that can be used to measure the potential of the liquid treating agent include standard reference hydrogen electrodes (having a potential of 0.0 V) and standard Ag/AgCl electrodes; also a reference electrode known as a Calomel electrode can be used.
  • the hydrogen electrode relies on the H 2 H + +e" half-reaction.
  • the standard Ag/AgCl electrode contains 1.0M KCl, relies on the AgCl+e" Ag 0 +Cl " half-reaction, and has a reference potential of 0.2223 volt at 25°C.
  • the Calomel electrode consists of mercury in the bottom of a vessel with a paste of mercurous chloride over it in contact with a solution of KCI saturated with mercurous chloride.
  • the Calomel half reaction is J sHg 2 Cl 2 +e " Hg 0 +Cl " .
  • the normal Calomel contains a 1M solution of potassium chloride and has a reference potential of 0.2830 volt at 25°C with reference to the standard hydrogen electrode.
  • the measurements of the potential of the liquid treating agent of the invention can be obtained using a procedure set forth in Inorganic Chemistry an Advanced Textbook, Thirald Moeller, J. A. Wiley & Sons, N.Y. (1952), a standard inorganic chemistry reference text disclosing oxidization-reduction measurements.
  • the liquid treating agent comprises an aqueous liquid medium preferably having a pH low enough to retard ozone decomposition in the liquid treating agent.
  • the pH can be adjusted with standard acids and bases, with the mineral acids of phosphoric, hydrochloric, nitric or sulfuric being preferred; and the inorganic bases of metal hydroxides, carbonates, bicarbonates, phosphates or silicates being preferred.
  • the pH is generally maintained at less than about 11, preferably less than about 9; however, aqueous ozone stabilizers like: 1) inorganic carbonates or bicarbonates, and 2) short-chain alcohols like tert-butanol, and 3) polysaccharides like dextrans, dextrins, and amylose (as outlined in DEPS 41 00 782) can be used. Especially at the more alkaline pH's between 7 and 10.
  • the liquid treating agent can further comprise an ozone potentiator, a buffer, a surfactant, a pH adjuster and mixtures thereof.
  • ozone potentiator can be used to initiate, propagate, or inhibit the secondary side-reactions of ozone in forming the aforementioned radicals and ions in basic solutions; as outlined in "Ozone in Water Treatment, Application and Engineering, ed., Bruno Langlais, David Reckhow, Deborah Brink, Lewis Publishers (1991), Chapt. 2, pp. 16-31.
  • the potentiators modify the aqueous ozone half-life.
  • inorganic potentiators are preferred due to the tendency of organic materials to be oxidized by the ozone; however, some short chain organic alcohols such as tert-butanol, isopropanol, etc., can be used.
  • Inorganic ozone potentiators can include an acid or salt of an inorganic carbonate or bicarbonate, hydrogen peroxide and inorganic phosphates, borates or silicates.
  • a pH buffer system can aid in maintaining a pH at an optimal pH for the liquid treating agent.
  • buffers can include: inorganic carbonates, bicarbonates, silicates, phosphates, borates, and organic short-chain acids like citric, formic, and acetic.
  • pH controlling agents such as buffers, which will provide an environment of the proper pH can be used in the treating agents of the invention.
  • the total concentration of additive (pH adjuster, buffer, potentiator, stabilizer) used in the liquid treating agent can range from about 10 ppm to about 100,000 ppm (10.0 wt-%).
  • the use concentrations typically fall between 50 and 3000 ppm, and preferably 300 to 1000 ppm of the liquid treating agent.
  • the ozone decolorizing systems can be formulated to contain effective amounts of synthetic organic surfactants and/or wetting agents.
  • the surfactants must be selected so as to be stable and chemically-compatible in the presence of ozone and alkaline builder salts. These surfactants can typically be used at concentrations above about 5 ppm.
  • One class of preferred surfactants is the anionic synthetic detergents. This class of synthetic detergents can be broadly described as the water-soluble salts, particularly the alkali metal (sodium, potassium, etc.) salts, or organic sulfuric reaction products having in the molecular structure an alkyl radical containing from about eight to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
  • Preferred anionic organic surfactants contain carboxylates, sulfates, phosphates (and phosphonates) or sulfonate groups.
  • Preferred sulfates and sulfonates include alkali metal (sodium, potassium, lithium) primary or secondary alkane sulfonates, alkali metal alkyl sulfates, and mixtures thereof, wherein the alkyl group is of straight or branched chain configuration and contains about nine to about 18 carbon atoms.
  • Specific compounds preferred from the standpoints of superior performance characteristics and ready availability include the following: sodium decyl sulfonate, sodium dodecyl sulfonate, sodium tridecyl sulfonate, sodium tetradecyl sulfonate, sodium hexadecyl sulfonate, sodium octadecyl sulfonate, sodium hexadecyl sulfate, sodium tetradecyl sulfonate, sodium dodecyl diphenyloxide disulfonate, and sodium n-decyl diphenyloxide disulfonate.
  • Carboxylate surfactants can also be used in the materials of the invention.
  • Soaps represent the most common of commercial carboxylates. Additional carboxylate materials include alphasulfocarboxylic acid esters, polyalkoxycarboxylates and acyl sarcocinates .
  • the mono and diesters and orthophosphoric acid and their salts can be useful surfactants.
  • Quaternary ammonium salt surfactants are also useful in the compositions of the invention.
  • the quaternary ammonium ion is a stronger hydrophile than primary, secondary or tertiary amino groups, and is more stable to ozonolysis.
  • Preferred quaternary surfactants include substantially those stable in contact with ozone include C 6 _ 24 alkyl trimethyl ammonium chloride, C 8 _ 10 dialkyl dimethyl ammonium chloride, C 6 _ 24 alkyl-di ethyl benzyl ammonium chloride, C 6 _ 24 alkyl-dimethyl amine oxides, C 6 _ 24 dialkyl-methyl amine oxides, C 6 _ 24 trialkyl amine oxides, etc.
  • Nonionic synthetic surfactants may also be employed, either alone or in combination with anionic and cationic types.
  • This class of synthetic detergents may be broadly defined as compounds produced by the condensation of alkylene oxide or polyglycoside groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water soluble or dispersible compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • nonionic synthetic detergents For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name "Neodol". These compounds are formed by condensing ethylene oxide with a hydrophobic fatty alcohol base. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the products is retained up to the point where the polyoxyethylene content is about 50 percent of the total weight of the condensation product.
  • Another example of nonionic detergents with noted stability during the cleaning procedure are the class of materials on the market under the tradename of APG- polyclycosides. These nonionic surfactants are based on glucose and fatty alcohols.
  • nonionic synthetic detergents include the polyalkylene oxide condensates of alkyl phenols, the products derived from the condensation of ethylene oxide or propylene oxide with the reaction product of propylene oxide and ethylene diamine, the condensation product of aliphatic fatty alcohols with ethylene oxide as well as amine oxides and phosphines oxides.
  • the temperature of the aqueous medium can be maintained up to about 70°C.
  • the temperature of the aqueous medium is maintained at about 5 to 50°C. More preferably, the temperature of the aqueous medium is maintained at about 10 to 40°C.
  • fabrics which can be subjected to the process of the invention are dyed fabrics or, alternatively, finished garments or items made from previously cut and assembled dyed fabric, for example, trousers, jackets, shirts, wallets, purses, knapsacks, etc.
  • Fabric or garments treated in accordance with the invention can be made up of: flax, jute, hemp, ramie, sisal, wool, cashmere, angora, silk, rayon, acetate, triacetate, nylon, polyester, acrylic, modacrylic, olefin, spandex, aramid, novoloid, rubber (synthetic), saran, vinyon, cellulosic materials such as cotton or cotton/synthetic such as nylon, rayon, or polyester fiber blends or mixtures thereof;
  • the process of the invention is not limited to a certain weight of fabric and may be applied to denim weight weaves as easily as to fine pin-point cotton weaves.
  • the process of the invention may be used to significantly decolorize fabrics or garments dyed with dye, or colored pigments, that is ozone-reactive.
  • the process may also be used to treat new fabrics or garments, as well as with already used, stained, or bleached fabric or garments.
  • Fabrics or garments dyed with cellulosic substantive dyes, such as vat dyes, which are common in the garment industry, are preferably treated in accordance with this invention. Dyes are absorbed into the fabric fibers and physically trapped or chemically bound. The chemical nature of the fiber governs the chemistry of the appropriate coloring material.
  • Dyes are classified by tradename and chemical structures in reference manuals known as the Colour Index. (Colour Index, The Society of Dyers and Colourists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, England, BPl, 2JB, England; and. The American Association of Textile Chemists and Colorists, P.O. Box 12215, Research Triange Park, North Carolina, 27702).
  • cellulosic fibers can be dyed with vat dyes such as; C.I. vat blue 5, C.I. vat black 1, C.I. Natural blue 1 or CI vat blue 1 (natural or synthetic indigo), direct dyes such as; C.I. direct blue 80, C.I.
  • Most protein fibers are dyed with dyes of the acid or basic chemical classification for example C.I. acid yellow 178, C.I., basic green 1-3. Acrylic, modacrylic and nylon can also be dyed with this class of colorant.
  • Synthetic fibers are typically dyed with what is known in the industry as the disperse class of dyes such as; C.I. disperse blue 16- 19.
  • textiles can be colored with pigments.
  • colored particles are attached to the fiber with a binder.
  • the binder must be compatible with the fabric to make the textile colorfast.
  • pigments are: C.I. pigment blue 1, C.I. pigment green 3.
  • the liquid treating agent additionally comprises a solid fabric-abrading material, preferably pumice stones, ceramic pellets, rubberballs and sand, used in conjunction with the ozonated liquid to enhance the process. This allows for an even more rapid, and greater degree, of the decolorization and/or
  • the pumice stones have a particle size of about 1 to 10 inches. Smaller pumice particles are generated by the abrasive nature of the process.
  • the clothing item is tumbled with the pumice and ozonated liquid for a sufficient period of time such that the pumice abrades the fabric, and the ozonated liquid decolorizes the piece, to produce in the fabric panels, localized abraded areas of lighter color and similar lightened areas in the seams. Additionally, the pumice and ozonated liquid soften the fabric and produce a fuzzy surface similar to that produce by the extended wear of the fabric.
  • the amount of pumice that can be used in the stone washing is about 5 to 50% of the machine volume, preferably about 10 to 30% being used.
  • the fabrics can be pre- or post-processed using conventional laundering methods such as desizing using enzymes, cleansing of the fabrics with surfactant washes, high temperature or chemical swelling, decolorization using a cellulose enzyme or pumice, etc.
  • conventional laundering methods such as desizing using enzymes, cleansing of the fabrics with surfactant washes, high temperature or chemical swelling, decolorization using a cellulose enzyme or pumice, etc.
  • the decolorizing process found most advantageous to follow using a conventional industrial wheel washing machine was to pre-wash the fabric with surfactants, de-size with enzymes using a multiple rinse, then decolorize with the liquid treating agent, post-wash with surfactants, and, machine dry. These steps can be done in a batch-type style or in a step-wise continuous process.
  • Textile fabrics can be exposed to the liquid treating agent via mechanical apparatus other than the conventional commercial or industrial washing equipment.
  • the liquid treating agent could be sprayed or padded onto the fabric.
  • Padding is a process whereby fabric is passed through a trough which contains chemicals, and is then squeezed between heavy rollers to remove excess liquor. This process is commonly used for dyeing and finishing of fabrics. A Dictionary of Textile Terms. Dan River Inc., Ill West 40th Street, New York, N.Y. 10018.
  • Fabric surface preparation is an important factor when working toward a desired "look".
  • Mechanical action (abrasion level) can be altered by methods as simple as altering fabric loading, water levels, and drum rotation in standard industrial laundering equipment.
  • the textile surface can be chemically and/or mechanically altered by methods other than enzyme or pvunice stone treatment before or after exposure to the liquid treating agent. Examples include, but are not limited to; sand blasting, tumbling with sand, with molded objects comprised of cement, ceramic, or elastomers, and/or tumbling with chemically reactive material in liquid, powder or pellet form.
  • a desizing step may be undertaken before decolorization to remove starch and starch-based materials from the fabric through application of a desizing agent such as an enzymatic desizing agent or an alkaline desizing agent.
  • a desizing agent such as an enzymatic desizing agent or an alkaline desizing agent.
  • desizing can also increase the absorbency, and as a result, enhance the susceptibility of the fabric to the decolorizing process.
  • the dyed fabric may also be pretreated before decolorization with any number of other chemical or physical elements to create a variety of effects during the subsequent decolorization process of this invention including cellulose enzymes, pumice, blocking agents, fabric softeners, and fabric swelling pretreatment agents such as a solution of NaOH, phosphoric acid or zinc chloride.
  • the fabric can be either pre- or post-processed with either a cellulase enzyme or pumice, or mixtures thereof, in a separate step then treating the fabric with the liquid treating agent of this invention. This additional decolorization and/or abrasion step will usually result in an increased decolorization and worn look of the fabric compared to treating the fabric with the liquid treating agent alone.
  • FIGURE 1 is a schematic diagram of an aqueous ozonating system designated generally by 100 that can be used to practice a preferred embodiment of the invention.
  • the system 100 comprises an ozone generator 101, a gas inlet means 103, a mixing means 104, a pump means 106, a filter 112, and a utilization point 105 which is typically a closed system commonly referred to as a wash wheel.
  • the utilization point 105 has a liquid inlet port 113 and a liquid outlet port 114.
  • Such commercial washing machines come in a variety of configurations with common sizes being rated in the industry as 35, 400, 600, etc., pound machines.
  • the liquid outlet port 114 is in fluid communication with the pump means 106.
  • An aqueous sampling port 111 can be used for solution monitoring.
  • a filter 112 is in fluid communication between the liquid outlet means 114 and the pump means 106.
  • the pump means 106 is in fluid communication with the gas inlet means 103 and the liquid outlet means 114.
  • An ozone generator 101 is in gaseous communication with the gas inlet means 103 by a hose 102.
  • the aqueous ozonating system 100 is completed with the gas inlet means 103 being in fluid communication with the liquid inlet port 113 of the utilization point 105.
  • a mixing means 104 such as a mixing loop, static mixer, contact tower, or other gas/liquid mixing device is in fluid communication between the gas inlet means 103 and the liquid inlet port 113.
  • the liquid treating agent comprises an aqueous liquid medium having a pH of less than about 10 and of an active ozone composition sufficient to decolorize the fabric.
  • the liquid treating agent is prepared by injecting a gas containing ozone, which is produced in the ozone generator 101, through a hose 102 into the in-line gas-mixing eductor 103 which, in turn, introduces and mixes the gas containing ozone into the aqueous medium.
  • the gas containing ozone is injected into the aqueous medium at a rate of about 10 to 225 SCFH. More preferably, the gas containing ozone is injected into the aqueous medium at a flow rate at about 20 to 80 SCFH.
  • the aqueous medium is pumped at a rate such that about 5 to 100% of the aqueous medium in the washing machine 105 is recirculated through the aqueous ozonating system 100 every minute. More preferably, the aqueous liquid medium is pumped through the system 100, at a rate so that about 10 to 30% of the aqueous medium in the washing machine 105 is being recirculated throughout the system 100 every minute.
  • the temperature of the aqueous liquid medium is preferably maintained at a temperature of about 1 to 60°C, more preferably 10 to 40°C.
  • the temperature of the aqueous medium is important because it determines the solubility of the ozone in the aqueous medium. The lower the temperature, the more soluble the ozone is in the aqueous medium, and therefore, produces a more potent decolorizing liquid treating agent.
  • the mixing loop 104 which can be variable lengths of coiled tubing between the gas-mixing eductor 103 and the washing machine 105 allows for different ozone-aqueous medium contact times and, thus, variable degrees of mixing. Otherwise, a contact tower, educator, static mixer, or any other gas/liquid mixer can be utilized.
  • the aqueous medium can be buffered, unbuffered, or contain an ozone potentiator.
  • the pH is adjusted prior to the injection of the ozone gas into the aqueous medium by the injection of pH adjuster into an addition port (not shown in Figure 1) on the wash wheel 105 to lower the pH to less than 13, preferably about less than 9.
  • the pH adjustment is primarily for ozone stabilization, and therefore, should be accomplished prior to the addition of the ozone into the aqueous medium.
  • ozone potentiators can be added by the same port.
  • the liquid treating agent can be pumped directly to the washing machine 105, or it can be pumped to a holding tank (not shown in FIGURE 1) where the liquid treating agent can be bled off and sprayed onto the surfaces of the fabric to be decolorized.
  • the circulating pump 106, or additional pumps (not shown in Figure 1), can be used to deliver the liquid treating agent through a tube (not shown in Figure 1) and directly onto the fabric to be decolorized.
  • the fabric to be decolorized is contacted in the washing machine 105 with the liquid treating agent for a time of about 5 to 60 minutes. More preferably, the fabric to be decolorized is contacted with the liquid treating agent for a period of about 15 to 45 minutes.
  • the ozone concentration level of the liquid treating agent can be controlled by controlling the gas containing ozone flow rate, the aqueous medium pumping rate, temperature, pH, decolorization time, potentiator level, or the amperage applied to the 0 3 generator 101. These parameters can be scaled to greater or lesser values depending upon the size of the processing equipment such as the washing machine 105, the size or weight of the fabric to be decolorized, the types of dyes or pigments employed, and the degree of color loss desired.
  • Constant monitoring of the oxidizing power and pH of the liquid treating agent can be performed using a conventional oxidation-reduction potential (ORP) probe 108 and pH probe 109, respectfully. This continued monitoring of the oxidation power and pH allows for regular monitoring and control of the ozone generating equipment 101. Circulation of the liquid treating agent over these probes can be done using a circulation pump 110 on the wash wheel 105. Additional ORP and pH monitoring can be done at any point in the aqueous ozone system 100.
  • ORP oxidation-reduction potential
  • the total load volume in the washing machine 105 is the total load volume in the washing machine 105.
  • the total volume of fabric and liquid treating agent can range from about 10 to 120% of the total manufacturer's load (usually weight rating) of the washing machine 105, preferably 40 to 100%.
  • the decolorized fabric can then be washed with surfactants, rinsed and dried. After washing the decolorized fabric, the extent of the decolorization and/or abrasion of the fabric can be evaluated by visual inspection, reflectance measurements, tensile strength, and weight loss.
  • Reflectance measurements are an industry standard instrumental measurement of the fraction of the incident light that is reflected by the surface of the fabric. Reflectance measurements can be done on a Hunter Ultra-Scan Sphere Spectrocolorimeter (Hunter lab) . Decolorization of the fabric surface is related to an increase in the lightness L-value (a measurement of the lightness that varies from 100 for perfect white to 0 for black, approximately as the eye would evaluate it) and the color loss delta-E (a measure of the color difference value derived from the opponent-color scales (L-lightness) , a (yellowness), b (blueness)), and approximate the NBS unit of color difference. Both values have been found to be reproducible and numerically representative of the results from visual inspection.
  • L-value a measurement of the lightness that varies from 100 for perfect white to 0 for black, approximately as the eye would evaluate it
  • the color loss delta-E a measure of the color difference value derived from the opponent-color scales (L-lightness) , a (y
  • a new, desized fabric might have an L-value around 19 +/- 1.
  • the L-value might increase to about 20, with a delta E typically less than 2 (the delta E is a measurement of the color loss in the decolorization experiment relative to the control desized fabric).
  • contacting the fabric with a liquid treating agent can increase the L-value to greater than 26, and sometimes greater than 29, and the delta E value to greater than 6, and sometimes greater than 12.
  • increases in L-value or delta E of over one unit are significant for demonstrating visibly detectable color loss, and a change above 6 units indicates extensive decolorization.
  • TS measurements were done following the standard ASTM:D1682 (breaking load and elongation of textile fabrics). Grab Method. Typically, it was found that there were no appreciable changes in TS relative to the control-air studies, and usually better than a commercial enzyme process.
  • the percent weight loss of the decolorized jeans are calculated relative to a similar standard reproducible size swatch cut from the air exposed jeans. Weights were obtained after the swatches were dried at 70°C for 24 hours and cooled to room temperature in a desiccator. A value of 10% weight loss or more is considered to represent a significant difference of the fabric weights after exposure to ozone compared to after exposure to air.
  • Fabric Decolorization Examples Table 1 illustrates the effect and scope, of decolorizing denim fabrics according to this invention by using the liquid treating agents at a variety of temperatures.
  • the data exemplifies using liquid treating agents to decolorize dyed fabric at temperatures where ozone is soluble (Tests 980-2, 957-9, 960-2 and 986-8 on lines 3, 4, 7, and 8 respectively).
  • the data also shows the lack of decolorization under temperature conditions where ozone is marginally, or not at all, soluble (Test 995-7, 998-000 and 989-991 on lines 5, 6, and 9, respectively).
  • the decolorization is demonstrated by a rise in the lightness value L from about 20 (negligible decolorization) for an aerated solution (air only) to about 26-30 (moderate-to- extensive decolorizations) for the ozonated liquid treating agents.
  • the fabric surface appearance was found to change with temperature, i.e., the garments which were decolorized (lines 3-4, 7-8) also appear to be "fuzzier", "abraded” or "worn”. This is in contrast to the higher temperature studies (lines 5-6, 9) which were not significantly decolorized or have a worn appearance, as compared to the air studies.
  • the results establish the ability of the invention to use aqueous ozone solutions in contrast to gas phase ozone, pumice stone, or enzyme for fabric and garment decolorization processes.
  • the data also establish the value of the ozonated liquid treating agent of the invention in making the garment pockets (or any white area) whiter.
  • the data also exemplifies the decolorizing effect in relationship to oxidization-reduction potential (ORP) .
  • ORP oxidization-reduction potential
  • the data demonstrates the ability to decolorize garments, using an ozone solution at a variety of temperatures where ozone is soluble, with an ORP reading of greater than about 400 mv (for pH's between about 3 and 8, since the ORP value is pH sensitive) is obtained (lines 3-5, 7-8), for a solution without garments, dye(s) or other ozone reactable components, present. Conversely, little color loss, or abrasion effects, are found below this value as evidenced by the ORP's of the air runs (lines 3-9), or the high temperature runs (lines 6, 9). These examples teach the application of using ORP values to evaluate the decolorization potential of an ozonated solution. TABLE 1 THE EFFECT OF TEMPERATURE ON DENIM DECOLORIZATION USING
  • Final L is the reflectometry lightness value (100 for white, 0 for black) taken after the ozonation, or air, study.
  • Delta E is the color difference reflectometry value derived from the opponent-color scales (L,A,B) and approximates the NBS Unit of Color Difference; and calculated relative to the control value.
  • ORP oxidation reduction potential
  • the tabulated values for the control study is an average of data for all the fabrics before any processing (air or ozone) but after desizing.
  • the slightly blue control pocket is designated 1002 as a relative pocket whiteness.
  • a Z Pocket Whiteness value greater than 1002 indicates the pockets being whiter, after processing, than the control study designated at 1002.
  • Table 2 establishes the effect, and scope, of decolorizing denim fabrics using liquid treating agents of the invention at a variety of pHs.
  • the data demonstrates the ability to decolorize the dyed fabrics using liquid treating agents (vs. the air studies) at pH's of between about 1-10. Again, significant increases in lightness (L) and color difference (delta- E) are shown for the dyed garments; with the effect being most pronounced when the liquid treating agents are at lower pHs (Tests 992-4, 968-70, 957-9, 971-3, 960-2, 983-5 on lines 3-5, 7-9) and dropping off at pHs above about 10 (Tests 951-3 and 954-6, lines 6, 10) .
  • the pocket whitenesses are also enhanced by these pH conditions.
  • Final L is the reflectometry lightness value (10C for white, 0 for black) taken after the ozonation, or air, study.
  • Delta E is the color difference reflectometry value derived from the opponent-color scales (L,A,B), and approximates the NBS Unit of Color Difference, and calculated relative to the control value.
  • ORP oxidation-reduction potential
  • the control study is an average of data for all the fabrics before any processing (air or ozone) ; but 5 after desizing.
  • the slightly blue control pocket is designated at 1002 as a relative pocket whiteness .
  • a Z Pocket Whiteness value greater than 1002 indicates the pockets being whiter, after processing, than the control study designated at 1002.
  • Table 3 illustrates some other fabric decolorization systems which give rise to active oxidation-reduction potentials (ORP's) greater than 400 mv.
  • ORP's active oxidation-reduction potentials
  • the data demonstrates the use of various acids (H 3 P0 4/ H 2 S0 4 , H 3 BO 3 ) , alkalines (NaOH, Na 4 Si0 4 , Na 2 C0 3 , NaHC0 3 ) , buffers (H 3 BO 3 , NaHC0 3 , Na 5 P 3 O 10 , Na 2 C0 3 ) , and surfactant systems (alkyl glycosides, alcohol ethoxylates, alkylphenol ethoxylates, alkane sulfonates and sulfates, amine oxides, and alkyl diphenoxide derivatives) for generating the required ORP for decolorization.
  • surfactant systems alkyl glycosides, alcohol ethoxylates, alkylphenol ethoxylates
  • ORP oxidation-reduction potential
  • APGTM 325 CS an alkyl glycoside; Henkel Corp. (225 ppm use level).
  • NeodolTM 91-8 an alcohol ethoxylate; Shell Chem. Co. (744 ppm use level).
  • IgepalTM CO710 a nonylphenol ethoxylate; Rhone-Poulenc (25.1 ppm use level).
  • Hostap rTM SAS an alkane sulfonate, sodium salt; Hoechst AG (744 ppm use level) .
  • APGTM 600 CSUP an alkyl glycoside; Henkel Corp. (744 ppm use level).
  • BarloxTM 12 an alkyl dimethyl amine oxide; Lonza, Inc. (100 ppm use level).
  • StepanolTM WA-100 sodium lauryl sulfate; (Stepan Co.) (228 ppm use level).
  • Table 4 is a kinetic study of decolorizing denim fabrics using the liquid treating agents of the invention.
  • the data illustrate an increase in decolorization with time (vs. the air studies) .
  • the results show for typical commercial fabric processing times (15-45 minutes) , that the liquid treating agents can be employed for dye removal and fabric decolorization. Additionally, it was shown that the visually perceived degree of "fuzziness” or "wear” increased with increasing reaction time.
  • Final L is the reflectometry lightness value (100 for white, 0 for black) taken after the ozonation, or air, study.
  • Delta E is the color difference reflectometry value derived from the opponent-color scales (L,A,B), and approximates the NBS Unit of Color Difference, and calculated relative to the control value.
  • control study is an average of data for all the fabrics before any processing (air or ozone); but after desizing.
  • a Z Pocket Whiteness value greater than 100. ⁇ _ indicates the pockets being whiter, after processing, than the control study designated at 100Z.
  • Table 5 shows the effect of combining, simultaneously, the ozonated liquid treating agents with current commercial processes like pumice stone washing.
  • the results show the ozone decolorization is enhanced by the co-application (or pre/post- applications) of other decolorization methods (Compare Runs Nos. 1 and 3, 2 and 4) .
  • Delta E is the color difference reflectometry value derived fror_ the opponent-color scales (L,A,B) and approximates the NBS Unit of Color Difference, and is relative to the garments before processing.
  • Table 6 illustrates the results of ASTM Grab-Break test, and % weight loss for: a control study (line 1) , a commercial enzyme study (line 2) , and various examples of the invention (Tests 957-90, 960-20, 951-30 and 954- 60, lines 3-10) .
  • the tests show for the examples, within the accuracy of the measurement, there is no significant loss in fabric strength as measured by Tensile Strength (TS) measurements (cf., the starting control study line 1, and the ozone studies Tests 957- 90, 960-20, 951-30 and 954-60 on lines 3, 5, 7, 9 respectively.
  • TS Tensile Strength
  • Weight Loss Difference is the percent difference between weight loss in the ozone (test O's) and air (test A's) studies.
  • control study is an average of data for all the fabrics before any processing (air or ozone); but after desizing; i.e., a base starting value.
  • Table 7 demonstrates the results of effluent water measurements taken from the decolorization process of the invention, control-air studies, and a commercial enzyme process.
  • the experiments show that the process of the invention, in contrast to the commercial enzyme process, allows for effective control, and minimization, of waste ⁇ water related issues such as: chemical oxygen demand (COD), biological oxygen demand (BOD), total solids by evaporation (TSEV), total suspended solids (TSS), and total dissolved solids (TDS).
  • COD chemical oxygen demand
  • BOD biological oxygen demand
  • TSEV total solids by evaporation
  • TDS total suspended solids
  • TDS total dissolved solids

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  • Textile Engineering (AREA)
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Abstract

Un agent de traitement liquide, contenant de l'ozone, peut être utilisé pour décolorer un tissu. Les caractéristiques de décoloration peuvent être optimalisées par des additifs. L'ozone peut être mélangé à un milieu aqueux apte à décolorer efficacement les tissus.
PCT/US1994/012506 1993-11-10 1994-11-01 Decoloration de tissus et de vetements au moyen d'un agent de traitement liquide contenant de l'ozone WO1995013415A1 (fr)

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AU81299/94A AU8129994A (en) 1993-11-10 1994-11-01 Decolorizing fabrics and garments with a liquid treating agent containing ozone

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US15044193A 1993-11-10 1993-11-10
US08/150,441 1993-11-10

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19546075A1 (de) * 1995-06-22 1997-01-02 Juergen Bernloehr Verfahren und Einrichtung zum Entfärben von Gewebe bzw. Bekleidung, insbesondere Jeansbekleidung
FR2739041A1 (fr) * 1995-09-22 1997-03-28 Ecolab Inc Procede de nettoyage et d'assainissement de surfaces solides ou d'installations industrielles
EP1264026A1 (fr) * 1999-11-10 2002-12-11 Eric Wasinger Appareil destine au traitement de vetements teints et de matieres textiles par des gaz oxydants
US7141075B1 (en) * 2004-09-26 2006-11-28 Fiberzone Technologies Inc. Process for selective decolorizing fabric
WO2007043905A1 (fr) * 2005-10-07 2007-04-19 Lavandaria Pizarro, Sa. Procede de vieillissement pour tissus utilisant des agents decolorants reducteurs ou oxydants appliques par pulverisation
US7550013B1 (en) * 2004-09-26 2009-06-23 Fiberzone Inc Process for selective decolorizing fabric
WO2014113238A2 (fr) * 2013-01-21 2014-07-24 Youn Kevin Jin Procédé de décoloration de tissu denim utilisant de l'ozone
WO2017066000A1 (fr) * 2015-10-14 2017-04-20 Guardian Manufacturing, Inc. Élimination de couleur de l'eau avec de l'ozone dans un procédé de blanchiment de textiles
WO2018065388A1 (fr) * 2016-10-03 2018-04-12 Acticell Gmbh Procédé respectueux de l'environnement pour le blanchiment local et reproductible d'un tissu avec de l'ozone
US10227720B2 (en) 2014-04-24 2019-03-12 Guardian Manufacturing, Inc. Ozone process for color removal
EP3477001A1 (fr) * 2017-10-31 2019-05-01 Fast Retailing Co., Ltd. Procédé d'endommagement destiné à un produit textile
EP3770322A1 (fr) * 2019-07-24 2021-01-27 Zhejiang Jingxing Paper Joint Stock Co., Ltd. Procédé pour améliorer la douceur de fibres de pâte à haut rendement
CN114507964A (zh) * 2021-12-30 2022-05-17 广东前进牛仔布有限公司 一种牛仔面料环保褪色处理工艺及后整理线

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1361314A (fr) * 1962-07-09 1964-05-22 Air Liquide Procédé de décoloration de fibres textiles
EP0307564A2 (fr) * 1987-09-15 1989-03-22 Ecolab Inc. Méthodes pour introduire des variations de densité de couleur dans des matériaux cellulosiques teints
JPH03146094A (ja) * 1989-11-02 1991-06-21 Masayoshi Kodesen 洗濯方法、ストーンウォッシュ方法及びオゾン水製造装置
EP0554648A1 (fr) * 1990-07-31 1993-08-11 Eric Wasinger Décolaration de vêtements par action d'ozone

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
FR1361314A (fr) * 1962-07-09 1964-05-22 Air Liquide Procédé de décoloration de fibres textiles
EP0307564A2 (fr) * 1987-09-15 1989-03-22 Ecolab Inc. Méthodes pour introduire des variations de densité de couleur dans des matériaux cellulosiques teints
JPH03146094A (ja) * 1989-11-02 1991-06-21 Masayoshi Kodesen 洗濯方法、ストーンウォッシュ方法及びオゾン水製造装置
EP0554648A1 (fr) * 1990-07-31 1993-08-11 Eric Wasinger Décolaration de vêtements par action d'ozone

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* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 115, no. 22, 2 December 1991, Columbus, Ohio, US; abstract no. 234611, page 128; *

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19546075A1 (de) * 1995-06-22 1997-01-02 Juergen Bernloehr Verfahren und Einrichtung zum Entfärben von Gewebe bzw. Bekleidung, insbesondere Jeansbekleidung
FR2739041A1 (fr) * 1995-09-22 1997-03-28 Ecolab Inc Procede de nettoyage et d'assainissement de surfaces solides ou d'installations industrielles
NL1004029C2 (nl) * 1995-09-22 1998-12-29 Ecolab Inc Gepotentieerde waterige reinigings- en ontsmettingssamenstelling met ozon voor het verwijderen van een besmettende verontreiniging van een oppervlak.
EP1264026A1 (fr) * 1999-11-10 2002-12-11 Eric Wasinger Appareil destine au traitement de vetements teints et de matieres textiles par des gaz oxydants
EP1264026A4 (fr) * 1999-11-10 2003-03-05 Eric Wasinger Appareil destine au traitement de vetements teints et de matieres textiles par des gaz oxydants
US7141075B1 (en) * 2004-09-26 2006-11-28 Fiberzone Technologies Inc. Process for selective decolorizing fabric
US7550013B1 (en) * 2004-09-26 2009-06-23 Fiberzone Inc Process for selective decolorizing fabric
WO2007043905A1 (fr) * 2005-10-07 2007-04-19 Lavandaria Pizarro, Sa. Procede de vieillissement pour tissus utilisant des agents decolorants reducteurs ou oxydants appliques par pulverisation
WO2014113238A2 (fr) * 2013-01-21 2014-07-24 Youn Kevin Jin Procédé de décoloration de tissu denim utilisant de l'ozone
WO2014113238A3 (fr) * 2013-01-21 2014-10-23 Youn Kevin Jin Procédé de décoloration de tissu denim utilisant de l'ozone
US10227720B2 (en) 2014-04-24 2019-03-12 Guardian Manufacturing, Inc. Ozone process for color removal
WO2017066000A1 (fr) * 2015-10-14 2017-04-20 Guardian Manufacturing, Inc. Élimination de couleur de l'eau avec de l'ozone dans un procédé de blanchiment de textiles
WO2018065388A1 (fr) * 2016-10-03 2018-04-12 Acticell Gmbh Procédé respectueux de l'environnement pour le blanchiment local et reproductible d'un tissu avec de l'ozone
CN110073054A (zh) * 2016-10-03 2019-07-30 阿克蒂切有限责任公司 用臭氧对织物进行局部和可再现漂白的环境友好方法
CN110073054B (zh) * 2016-10-03 2023-05-30 阿克蒂切有限责任公司 用臭氧对织物进行局部和可再现漂白的环境友好方法
EP3477001A1 (fr) * 2017-10-31 2019-05-01 Fast Retailing Co., Ltd. Procédé d'endommagement destiné à un produit textile
CN109722837A (zh) * 2017-10-31 2019-05-07 株式会社迅销 纺织品的损伤方法
US10400388B2 (en) 2017-10-31 2019-09-03 Fast Retailing Co., Ltd. Damage process for a textile product
CN109722837B (zh) * 2017-10-31 2021-05-25 株式会社迅销 纺织品的损伤方法
EP3770322A1 (fr) * 2019-07-24 2021-01-27 Zhejiang Jingxing Paper Joint Stock Co., Ltd. Procédé pour améliorer la douceur de fibres de pâte à haut rendement
CN114507964A (zh) * 2021-12-30 2022-05-17 广东前进牛仔布有限公司 一种牛仔面料环保褪色处理工艺及后整理线
CN114507964B (zh) * 2021-12-30 2024-06-11 广东前进牛仔布有限公司 一种牛仔面料环保褪色处理工艺及后整理线

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