WO2024044164A1 - Launderable activated cotton garment - Google Patents

Launderable activated cotton garment Download PDF

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Publication number
WO2024044164A1
WO2024044164A1 PCT/US2023/030789 US2023030789W WO2024044164A1 WO 2024044164 A1 WO2024044164 A1 WO 2024044164A1 US 2023030789 W US2023030789 W US 2023030789W WO 2024044164 A1 WO2024044164 A1 WO 2024044164A1
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WO
WIPO (PCT)
Prior art keywords
garment
cotton
wax
dye
lock
Prior art date
Application number
PCT/US2023/030789
Other languages
French (fr)
Inventor
Graham Ralph Stewart
Original Assignee
Energy Ogre Llc
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Filing date
Publication date
Application filed by Energy Ogre Llc filed Critical Energy Ogre Llc
Publication of WO2024044164A1 publication Critical patent/WO2024044164A1/en

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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/76Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/15Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using organic agents
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/40Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using enzymes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/50Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/17Natural resins, resinous alcohols, resinous acids, or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58Material containing hydroxyl groups
    • D06P3/60Natural or regenerated cellulose
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58Material containing hydroxyl groups
    • D06P3/60Natural or regenerated cellulose
    • D06P3/6025Natural or regenerated cellulose using vat or sulfur dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58Material containing hydroxyl groups
    • D06P3/60Natural or regenerated cellulose
    • D06P3/66Natural or regenerated cellulose using reactive dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02After-treatment
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10Repellency against liquids
    • D06M2200/12Hydrophobic properties
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D06P1/228Indigo
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/30General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using sulfur dyes

Definitions

  • the present disclosure is directed to a process for increasing the strength and decreasing the wettability of cotton garments.
  • Cotton is a natural fiber with a negative environmental impact when processed.
  • the fiber is bleached, finished with strong alkali to prepare for a dying process, and dyed.
  • the strong alkali has to be neutralized at each stage of production in particular to mitigate the damaging effluent that would otherwise be released into the worlds aqueous eco systems.
  • a substantial amount of water waste is generated by repeatedly washing off the alkali involved in wet processing.
  • Cotton is at the top end of this estimate, requiring more water to process than polyester, viscose rayon, and wool. Thus, it is likely that the production and dying of cotton fabric is a significant contributor.
  • An embodiment described in examples herein provides a method for making water- resistant cotton garments.
  • the method includes treating cotton fabric with soda ash at a temperature of less than about 150 °F (about 66 °C) and a pH of about 9.5 and bleaching the cotton fabric with hydrogen peroxide at a temperature of less than about 150 °F (about 66 °C).
  • the hydrogen peroxide is neutralized, and the pH is lowered with an organic acid to between about 6 and about 7.
  • a garment is made from the cotton fabric and a wax lock is applied to the garment.
  • the garment is dyed at a temperature of less than about 150 °F (about 66 °C), and dried.
  • Another embodiment described in examples herein provides a cotton garment formed from an activated cotton material, including a layer of natural wax locked to the surface of cotton fibers by a wax lock.
  • Figure 1 is a process flow diagram of a method for making a treated cotton garment.
  • Figure 2 is a process flow diagram of a dying process that uses a reduction dye (RD) to make the treated cotton garment.
  • RD reduction dye
  • Kiering The industry standard technique for treating cotton for dying is termed Kiering. Kiering is generally performed on cotton fabric or yam to prepare it for dyeing. It uses a scouring process in which hot alkali (NaOH) solutions are used to saponify the natural wax coating on the cotton fibers, removing the wax. This increases the absorbancy (hydrophilicity) of the cotton fabric, making the fabric easier to dye.
  • NaOH hot alkali
  • the cotton is bleached to remove color bodies, forming a white material.
  • the bleaching can be performed by the use of hydrogen peroxide or other bleaches, such as hypochlorite bleach, among others.
  • the treated cotton can then be dyed, for example, as yarns, fabric, or garments, depending on the products.
  • the cotton articles are passed through, or soaked in, baths that include chemicals that help the dye to adhere to the cotton, for example, by forming hydroxyl groups at the surface of the cotton.
  • the cotton is then passed through, or soaked in, a bath containing the dye. This is often followed by multiple rinses to remove any excess dye that does not adhere to the cloth.
  • the treating and dying process is performed on a cotton yarn
  • the yam is then formed into a fabric, for example, by knitting or weaving.
  • the currently used techniques for treating cotton form an absorbent fabric with a color selected by the techniques used.
  • the alkali treatment reduced the strength of the cotton fibers, for example, by as much as 50 % or more, from the raw cotton.
  • a process is provided herein for producing a cotton product, termed an activated cotton, which leaves the natural wax in place on the cotton fibers, lowers water usage, and improves the properties of the cotton.
  • the natural wax coating on the cotton fibers imparts high performance properties to yarns, fabrics, and garments, for example, increasing the cooling properties of the fabric by allowing water vapor to pass through the fabric without being adsorbed.
  • the process includes the addition of a compound termed a wax lock.
  • the wax coating on natural cotton is generally removed during Keiring. Further, even if left on by a milder process, home laundering will remove the natural wax in a few cycles. To overcome this, the activated cotton is treated with the wax lock to fix the wax in place on the fabric.
  • the wax lock includes a silicone compound that interacts with the natural wax to prevent surfactants from removing the wax.
  • the wax lock is a cross-linking agent, such as a synthetic acrylic oligomer, which is applied before the final drying process and activated during drying.
  • a natural product that includes cross-linking material, along with a natural wax, can also be used. The cross-linking agent forms cross-links that hold the natural wax in place on the fibers.
  • the bleaching is performed using hydrogen peroxide.
  • a peroxide activator, triacetin is used along with a sequestering (or chelating) agent to protect the cotton fiber and the natural wax.
  • the triacetin gradually lowers the pH, creating conditions for the peroxide to be a highly effective bleaching agent to prepare the cotton for dying. This allows the elimination of the strong caustic alkali used in used in traditional bleaching and dye preparation methods. This also creates conditions for an enzyme bleach catalyst to be effective.
  • arylesterase is used as the oxidation catalyst.
  • the arylesterase is effective at low concentrations (high dilutions), such as about 0.5 grams per liter (g/L) about 0.2 g/L, or less.
  • high dilutions such as about 0.5 grams per liter (g/L) about 0.2 g/L, or less.
  • the use of the arylesterase allows the hydrogen peroxide reaction to occur at lower temperatures and in a shorter time, which lowers both the time and energy for the reaction, increasing the economic yield.
  • Figure l is a process flow diagram of a method for making a treated cotton garment.
  • An example of the treatment process used for the garment is described in the examples section below. It should be noted that the individual steps may be rearranged, eliminated, or modified. For example, in some embodiments, the soda ash pretreatment may be eliminated. It should also be noted that no surfactants or detergents are used in the process to avoid removing the natural wax coating, eliminating the potential negative environmental problems associated with surfactants or detergents.
  • the method 100 includes five basic processes, a pretreatment process 102 used to clean the cotton fabric and bleach it to remove color bodies and prepare the fabric for dying.
  • a garment production process 104 is used to prepare a garment from a pretreated fabric.
  • a treatment process 106 is used to prepare the garment for dying and to apply the wax lock to the fabric.
  • a dying process 108 is used to impart color to the garment.
  • a drying process 110 is then used to fix the wax lock on the garment, protecting the natural wax coating on the cotton fibers, and allowing multiple home launderings without removing the wax coating.
  • the pretreatment process 102 begins at block 112 with a soda ash pretreatment.
  • soda ash NaiCOi
  • CaOH caustic soda
  • the use of NaOH sets the pH at 12.5, which damages the cotton fibers and removes the natural wax by saponification.
  • the soda ash sets the pH of the treatment, for example, to about 10, or about 9.5.
  • the lower pH prevents, or decreases, the likelihood of saponification of the wax coating. Further, this is performed at a lower temperature than previous pretreatment procedures, for example, about 150 °F (66 °C).
  • a bleach activator for example, glyceryl triacetate (triacetin)
  • triacetin glyceryl triacetate
  • the triacetin is available from Cekal Specialties of Mt. Holly, NC, USA, under the tradename CEKASSIST BIO.
  • a sequestering agent such as ethylenediaminetetraacetic acid (EDTA)
  • EDTA ethylenediaminetetraacetic acid
  • the sequestering agent is CEKAQUEST PB from Cekal Specialties, which is also helping stabilize the hydrogen peroxide bleach. The decreasing concentration of the divalent metal ions will further stabilize the hydrogen peroxide during the bleaching procedure.
  • a bleaching procedure is performed using a 50 % solution of hydrogen peroxide.
  • an arylesterase catalyst is added to speed the reaction between the peroxide and the color bodies, as described herein.
  • the arylesterase catalyst is produced by microorganisms, for example, in a commercial production process. Any number of arylesterase catalysts can be used in the current procedures.
  • the arylesterase catalyst is obtained from Cekal Specialties under the tradename CEKAZYME BB.
  • the arylesterase catalyst is obtained from Cekal Specialties under the tradename CEKAZYME BB.
  • a catalase enzyme Any number of catalase enzymes may be used in the current procedures.
  • the catalase is CEKAZYME EPK200 from Cekal Specialties.
  • a test strip is used to confirm that the peroxide is eliminated. If not, in some embodiments, a water wash is used to rinse any remaining peroxide from the cotton. Generally, the peroxide is completely reacted, which allows a processor to go directly to the dyeing process. This avoids the washes that are needed to remove the peroxide, for example, saving around 10,000 liters of water per 1,000 kg of textile substrate.
  • the pH is lowered to a pH of less than about 8, less than about 7, or between 6.5 and 7. In some embodiments, this is performed by the addition of an organic acid, such as citric acid, acetic acid, or others. Tn some embodiments, the pH is checked to confirm that it is between 6.5 and 7. If not, more acid may be added, and the pH retested.
  • an organic acid such as citric acid, acetic acid, or others.
  • a surface tension test may be used to confirm that the pretreatment process 102 did not damage or remove the natural wax coating.
  • the surface tension test is performed by placing a drop of water on the surface of the fabric and noting if the water beads or is absorbed.
  • a goniometer is used to determine the surface tension of the surface, which may be used to determine the efficacy of the treatment.
  • the fabric from the pretreatment process 102 is then used to make a garment in the garment production process 104.
  • the fabric is cut into the appropriate shaped pieces, and sewn into the final garment.
  • the pieces are generally larger than the final size expected for the garment, as the garment accounts for shrinkage during the dying, finishing, and drying stages.
  • the treatment process 106 is used to prepare the garment for dying and to apply the wax lock if performance is desired.
  • the treatment process 106 begins at block 120, with the treatment of the garment with sodium sulfate.
  • NazCCh sodium sulfate
  • NazCCh sodium sulfate
  • the pH may be checked, and more Na2CC>3 added if needed to adjust the pH to 9.5.
  • the use of the weak alkali helps retain and protect the cotton wax and the cotton cellulose. It is used in place of the caustic soda (NaOH) used in the standard Kiering procedure, which would set the pH at 12.5, damaging the cotton and removing the natural wax via saponification.
  • the wax lock is applied, for example, by adding the wax lock material to the solution containing the garment.
  • the wax lock locks the natural wax to the cotton fibers, slowing its removal by laundering.
  • the wax lock may include silicone compounds, acrylic oligomers, or combinations. Other materials may be used, such as other types of oligomers or monomers.
  • the wax lock is hydrophobic, further protecting the natural was from being removed by laundering.
  • the silicone wax lock compound used in some embodiments is available from Apexical Specialty Chemicals of Spartanburg, SC, USA, as Apexosil 2137.
  • a small amount of acrylic monomers or oligomers may be included, such as about 1 wt.
  • the wax lock is a blend that includes an acrylic oligomer, such as available from Cekal Specialties as CEKAPEL NFWR.
  • the acrylic polymer blend includes 20-30 wt. % of a liquid, crosslinking acrylic polymer.
  • the blend also includes 5- 10 wt. % of dipropylene glycol. The dipropylene glycol lowers the viscosity of the polymer blend, improving the uptake into the cotton.
  • the wax lock compound is a blend that includes natural plant material isolated from plant wastes, for example, the by-products that accumulate during the processing of cereal grains in the food industry.
  • a crosslinker may be included in the blend to assist in locking the natural wax and the natural plant material to the fibers of the cotton.
  • the natural plant material is available from Rudolf GmbH of Geresreid, DE, as RUCO®-DRY BIO CGR.
  • the crosslinker is available from Rudolf as RUCO®-LINK XHC.
  • Other products from Rudolf can be used as the wax lock in embodiments.
  • RUCO®-DRY BIO NPE is a combined natural plant product and cross-linking agent that can be used as the wax lock.
  • the dying process 108 is described with respect to blocks 126 to 132. It can be noted that the generic procedure of Figure 1 will work with all dyes. However, specific information on the use of pre-reduced dyes, such as reduction dyes, including indigo, sulfur dyes, pre-reduced indigo, and pre-reduced sulfur dyes, is described further with respect to Figure 2.
  • reduction dyes including indigo, sulfur dyes, pre-reduced indigo, and pre-reduced sulfur dyes
  • the dying compound is added to the solution containing the garment.
  • the dye is a reactive dye, although any number of other types of dyes may be used, including direct dyes, sulfur dyes, azoic dyes, or vat dyes, among others described herein.
  • the dye liquor is heated to a maximum temperature of about 140 °F (about 60 °C) at a rate of about 2 °F/min (about 1.1 °C/min.).
  • the dye is allowed to stay in contact with the cotton for a sufficient period of time for absorbance, for example, 30 min., 45 min., 60 min., or longer.
  • the dye and salts are rinsed from the garment.
  • the pH is lowered to less than 8, or less than 7, or about 6.5. This is performed by the addition of an organic acid, such as citric acid, acetic acid, or the like.
  • a water rinse is performed to remove the acid and any remaining dyes or salts from the garment.
  • the pH of the rinse solution containing the garment is checked to confirm that it is between 6.5 and 7. If not, more acid may be added, and the pH retested.
  • the garment is dried to fix the wax lock compound. In various embodiments, this is performed at a temperature of less than about 400 °F (about 204 °C), or less than about 390 °F (about 199 °C), or less than about 350 °F (about 177 °C), or less than about 310 °F (about 154 °C), or between about 300 °F (about 149 °) and about 390 °F (about 199 °C), for example, in a tumble dryer or on a frame or moving line at a speed of about 25 to about 30 yds. /min (or about 23 to about 27 meters/min).
  • FIG. 2 is a process flow diagram of a dying process 200 that uses a reduction dye.
  • a reduction dye is a dye that is insoluble in water until it is reduced.
  • the RD is an indigo dye, a sulfur dye, a pre-reduced indigo dye, a pre-reduced sulfur dye, or other pre-reduced dye.
  • the pre-reduced dye is not fully reduced, for example, only being reduced by about 60 %.
  • the dying process 200 begins with the treatment of the garment with sodium sulfate at block 118, for example, using about 30 g/1 to about 50 g/1.
  • Na2COs sodium sulfate
  • the pH may be checked, and more Na2COs added if needed to adjust the pH to 9.5.
  • the garment is treated with the wax lock compound, as described herein.
  • the RD is added to the solution.
  • a reducing agent is added at block 204 to fully reduce the dye for solubilization.
  • the reducing agent may be a catalase, such as CEKAZYME EPK200 from Cekal added at about 4 g/1 to about 6 g/1, depending on whether the reduction dye is pre-reduced before use.
  • the reducing agent is sodium borohydride, hydrogen sulfide, or sodium hydrosulfite, among others.
  • a mordant or dye fixative agent, is added to assist in adhering the dye to the cloth.
  • the mordant is Ah(SO4)3, FeSCL, CuSCU, ZnSCh, or MnSCL, among others.
  • the mordant is selected based on the efficacy and the potential effects on the color. Further, the mordant may increase the efficacy of the reducing agent, for example, if a catalase is used, by increasing the ORP of the catalase solution.
  • the mordant can be added at about 10 g/1 to about 20 g/1.
  • the dye liquor and reducing agent are heated to a maximum temperature of about 140 °F (about 60 °C) at a rate of about 2 °F/min (about 1.1 °C/min.).
  • the dye is allowed to stay in contact with the cotton for a sufficient period of time for absorbance, for example, 30 min., 45 min., 60 min., or longer.
  • the dye, mordant, and salts are rinsed from the solution.
  • an oxidizer is added to the water solution to oxidize the reduced dye.
  • the oxidizer is hydrogen peroxide, air, oxygen, a water solution of ozone, and the like.
  • hydrogen peroxide is added at between about 1 g/1 and about 5 g/1.
  • the dye is allowed to oxidize in air for about 20 to about 30 minutes. The amount of oxidation controls the color, with higher levels of oxidation correlated to darker colors.
  • the pH is lowered to less than 8, or less than 7, or about 6.5. This is performed by the addition of an organic acid, such as citric acid, acetic acid, or the like.
  • a water rinse is performed to remove the acid and any remaining dyes or salts. In some embodiments, the pH is checked to confirm that it is between 6.5 and 7. If not, more acid may be added, and the pH retested.
  • any number of other dyes may be used in embodiments described herein, including, including vat dyes, sulfur dyes, pre-reduced versions of vat and sulfur dyes, and other dyes that are insoluble and are applied to substrates via redox methods.
  • Other dyes include azo dyes, such as direct dyes, metal complex dyes, reactive dyes, substantive dyes, and aniline dyes, such as natural and synthetic indigo dye, among others.
  • cotton fabric can be made into garments, and the wax lock can be applied during the dying process, for example, before the dye is added.
  • a cotton fabric prepared using this technique with a silicone softener as the wax lock compound retained the natural wax through greater than 25 laundering cycles using a cool wash cycle, 1 g/L Tide laundry detergent, and a cool dry cycle. This was tested by performed a surface tension test after each laundering cycle by applying a water droplet and determining that it beaded on the cotton fabric.
  • the natural wax lock products from Rudolph, Ruco-Dry Bio CGR and Ruco-Dry Bio NPE are highly effective.
  • the burst strength of the cotton fabric was compared to a sample of cotton fabric that was treated by the normal caustic wash.
  • the test performed to determine the strength was the Mullen diaphragm burst test, following ASTM D3787.
  • the strength retained by the cotton fibers depended on the initial lengths of the cotton fibers, e.g., the quality of the cotton.
  • a sample of fabric made using a high-quality cotton and treated using the procedure described with respect to Figure 1 provided an average burst strength of up to 210 psi (about 1448 kPa), versus a sample of the same fabric treated with the standard Kiering procedure, which had an average burst strength of about 110 psi (about 758 kPa).
  • An embodiment described in examples herein provides a method for making water- resistant cotton garments.
  • the method includes treating cotton fabric with soda ash at a temperature of less than about 150 °F (about 66 °C) and a pH of about 9.5 and bleaching the cotton fabric with hydrogen peroxide at a temperature of less than about 150 °F (about 66 °C).
  • the hydrogen peroxide is neutralized, and the pH is lowered with an organic acid to between about 6 and about 7.
  • a garment is made from the cotton fabric and a wax lock is applied to the garment.
  • the garment is dyed at a temperature of less than about 150 °F (about 66 °C), and dried.
  • making the garment includes cutting pieces from the cotton fabric and sewing the pieces together to form the garment.
  • the method includes adding a bleach activator with the soda ash.
  • the method includes adding a sequestering agent with the soda ash.
  • the method includes adding an arylesterase catalyst with the hydrogen peroxide.
  • neutralizing includes adding an enzyme to degrade the hydrogen peroxide.
  • the organic acid includes citric acid.
  • applying the wax lock to the garment includes treating the garment with sodium sulfate, treating the cotton with soda ash to raise the pH to about 9.5, and applying the wax lock to the garment.
  • the dying includes treating the garment with a dye solution, rinsing the garment, neutralizing the dye solution to a pH of about 6.5, and rinsing the garment.
  • the dye solution includes a prereduced dye.
  • the method includes adding a reducing agent to the dye solution.
  • the method includes adding a mordant to the dye solution.
  • the method includes treating the garment with an oxidant.
  • the method includes treating the garment with the wax lock.
  • the method includes drying the garment at between about 300 °F (about 149 °C) and about 390 °F (about 199 °C).
  • the wax lock includes a silicone compound.
  • wax lock includes an acrylic compound.
  • Another embodiment described in examples herein provides a cotton garment formed from an activated cotton material, including a layer of natural wax locked to a surface of cotton fibers by a wax lock.
  • the cotton garment includes a dye.
  • the cotton garment includes a prereduced dye.
  • the pre-reduced dye includes indigo.
  • the wax lock includes a silicone compound.
  • the wax lock includes an acrylic oligomer. [0079] In an aspect, combinable with any other aspect, the wax lock includes a natural plant material.
  • the wax lock includes a natural plant material combined with a cross-linking agent.

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Abstract

A method for making water-resistant cotton garments and the water-resistant cotton garments are provided. An exemplary method includes treating cotton fabric with soda ash at a temperature of less than about 150 °F (about 66 ºC) and a pH of about 9.5 and bleaching the cotton fabric with hydrogen peroxide at a temperature of less than about 150 °F (about 66 ºC). The hydrogen peroxide is neutralized, and the pH is lowered with an organic acid to between about 6 and about 7. A garment is made from the cotton fabric and a wax lock is applied to the garment. The garment is dyed at a temperature of less than about 150 °F (about 66 ºC), and dried.

Description

LAUNDERABLE ACTIVATED COTTON GARMENT
Cross-Reference to Related Application
[0001] This application is a PCT Application which claims the benefit of US Provisional Application No. 63/373,101 filed August 22, 2022, the disclosure of which is incorporated herein.
Technical Field
[0002] The present disclosure is directed to a process for increasing the strength and decreasing the wettability of cotton garments.
Background
[0003] Cotton is a natural fiber with a negative environmental impact when processed. Currently, the fiber is bleached, finished with strong alkali to prepare for a dying process, and dyed. The strong alkali has to be neutralized at each stage of production in particular to mitigate the damaging effluent that would otherwise be released into the worlds aqueous eco systems. [0004] A substantial amount of water waste is generated by repeatedly washing off the alkali involved in wet processing. For example, a report in the Planet Tracker, “Will Fashion Dye Another Day” (December 2020), notes “textile production requires an estimated 430 liters or 114 US gallons to produce 1 kg of textile fabric.” The report continues, stating that an estimated 8,000 toxic chemicals, used globally, are used to turn raw materials into textiles. Many of these chemicals are released into freshwater sources as waste streams. For example, “the dyeing and treatment of textiles is estimated to cause 20% of global industrial water pollution.”
[0005] Cotton is at the top end of this estimate, requiring more water to process than polyester, viscose rayon, and wool. Thus, it is likely that the production and dying of cotton fabric is a significant contributor.
[0006] Further, the current processing techniques used for cotton are energy intensive, requiring multiple drying cycles. Reducing the heat used in dyeing and shortening the dye cycles will lower the energy demand.
Summary [0007] An embodiment described in examples herein provides a method for making water- resistant cotton garments. The method includes treating cotton fabric with soda ash at a temperature of less than about 150 °F (about 66 °C) and a pH of about 9.5 and bleaching the cotton fabric with hydrogen peroxide at a temperature of less than about 150 °F (about 66 °C). The hydrogen peroxide is neutralized, and the pH is lowered with an organic acid to between about 6 and about 7. A garment is made from the cotton fabric and a wax lock is applied to the garment. The garment is dyed at a temperature of less than about 150 °F (about 66 °C), and dried.
[0008] Another embodiment described in examples herein provides a cotton garment formed from an activated cotton material, including a layer of natural wax locked to the surface of cotton fibers by a wax lock.
Brief Description of Drawings
[0009] Figure 1 is a process flow diagram of a method for making a treated cotton garment. [0010] Figure 2 is a process flow diagram of a dying process that uses a reduction dye (RD) to make the treated cotton garment.
Detailed Description
[0011] The industry standard technique for treating cotton for dying is termed Kiering. Kiering is generally performed on cotton fabric or yam to prepare it for dyeing. It uses a scouring process in which hot alkali (NaOH) solutions are used to saponify the natural wax coating on the cotton fibers, removing the wax. This increases the absorbancy (hydrophilicity) of the cotton fabric, making the fabric easier to dye.
[0012] However, multiple rinses of water are required to remove the alkali solutions. Further, the alkali softens the fabric by partially breaking down the fibers, leading to a lower strength product. The highly corrosive NaOH is also hazardous to operators if not properly handled in processing textiles. In addition, if the effluent created is not properly neutralized and disposed of it can be very damaging to water systems and the associated environment.
[0013] After the scouring, the cotton is bleached to remove color bodies, forming a white material. The bleaching can be performed by the use of hydrogen peroxide or other bleaches, such as hypochlorite bleach, among others. [0014] The treated cotton can then be dyed, for example, as yarns, fabric, or garments, depending on the products. In the dying process, the cotton articles are passed through, or soaked in, baths that include chemicals that help the dye to adhere to the cotton, for example, by forming hydroxyl groups at the surface of the cotton. The cotton is then passed through, or soaked in, a bath containing the dye. This is often followed by multiple rinses to remove any excess dye that does not adhere to the cloth.
[0015] If the treating and dying process is performed on a cotton yarn, the yam is then formed into a fabric, for example, by knitting or weaving. The currently used techniques for treating cotton form an absorbent fabric with a color selected by the techniques used. However, the alkali treatment reduced the strength of the cotton fibers, for example, by as much as 50 % or more, from the raw cotton.
[0016] A process is provided herein for producing a cotton product, termed an activated cotton, which leaves the natural wax in place on the cotton fibers, lowers water usage, and improves the properties of the cotton. The natural wax coating on the cotton fibers imparts high performance properties to yarns, fabrics, and garments, for example, increasing the cooling properties of the fabric by allowing water vapor to pass through the fabric without being adsorbed. To implement this, the process includes the addition of a compound termed a wax lock.
[0017] As described, the wax coating on natural cotton is generally removed during Keiring. Further, even if left on by a milder process, home laundering will remove the natural wax in a few cycles. To overcome this, the activated cotton is treated with the wax lock to fix the wax in place on the fabric. In some embodiments, the wax lock includes a silicone compound that interacts with the natural wax to prevent surfactants from removing the wax. In other embodiments, the wax lock is a cross-linking agent, such as a synthetic acrylic oligomer, which is applied before the final drying process and activated during drying. A natural product that includes cross-linking material, along with a natural wax, can also be used. The cross-linking agent forms cross-links that hold the natural wax in place on the fibers. This retains the natural hydrophobicity of the cotton fabric and enables it to maintain the hydrophobicity during numerous home laundering cycles, for example, greater than 20 cycles, greater than 25 cycles, greater than 30 cycles, or longer. [0018] In the process, the bleaching is performed using hydrogen peroxide. A peroxide activator, triacetin, is used along with a sequestering (or chelating) agent to protect the cotton fiber and the natural wax. The triacetin gradually lowers the pH, creating conditions for the peroxide to be a highly effective bleaching agent to prepare the cotton for dying. This allows the elimination of the strong caustic alkali used in used in traditional bleaching and dye preparation methods. This also creates conditions for an enzyme bleach catalyst to be effective.
[0019] In various embodiments, arylesterase is used as the oxidation catalyst. The arylesterase is effective at low concentrations (high dilutions), such as about 0.5 grams per liter (g/L) about 0.2 g/L, or less. The use of the arylesterase allows the hydrogen peroxide reaction to occur at lower temperatures and in a shorter time, which lowers both the time and energy for the reaction, increasing the economic yield.
[0020] The process changes and combinations described herein shorten the process further and increase water savings. This provides a more stable, repeatable, and ecologically favorable process. Further, the natural wax coating on the cotton will withstand 30 or more home laundering cycles with a surfactant, such as laundry detergent.
[0021] Figure l is a process flow diagram of a method for making a treated cotton garment. An example of the treatment process used for the garment is described in the examples section below. It should be noted that the individual steps may be rearranged, eliminated, or modified. For example, in some embodiments, the soda ash pretreatment may be eliminated. It should also be noted that no surfactants or detergents are used in the process to avoid removing the natural wax coating, eliminating the potential negative environmental problems associated with surfactants or detergents.
[0022] The method 100 includes five basic processes, a pretreatment process 102 used to clean the cotton fabric and bleach it to remove color bodies and prepare the fabric for dying. A garment production process 104 is used to prepare a garment from a pretreated fabric. A treatment process 106 is used to prepare the garment for dying and to apply the wax lock to the fabric. A dying process 108 is used to impart color to the garment. A drying process 110 is then used to fix the wax lock on the garment, protecting the natural wax coating on the cotton fibers, and allowing multiple home launderings without removing the wax coating.
[0023] The pretreatment process 102 begins at block 112 with a soda ash pretreatment. The use of soda ash, NaiCOi, is in place of caustic soda (NaOH) used in the standard Kiering process The use of NaOH sets the pH at 12.5, which damages the cotton fibers and removes the natural wax by saponification. The soda ash sets the pH of the treatment, for example, to about 10, or about 9.5. The lower pH prevents, or decreases, the likelihood of saponification of the wax coating. Further, this is performed at a lower temperature than previous pretreatment procedures, for example, about 150 °F (66 °C).
[0024] During the soda ash pretreatment at block 112, a bleach activator, for example, glyceryl triacetate (triacetin), is added for activation of hydrogen peroxide in the subsequent bleaching procedure. The triacetin is available from Cekal Specialties of Mt. Holly, NC, USA, under the tradename CEKASSIST BIO. Further, a sequestering agent, such as ethylenediaminetetraacetic acid (EDTA), is used to lower the concentration of divalent metal ions, such as magnesium (II) and calcium (II). In an embodiment, the sequestering agent is CEKAQUEST PB from Cekal Specialties, which is also helping stabilize the hydrogen peroxide bleach. The decreasing concentration of the divalent metal ions will further stabilize the hydrogen peroxide during the bleaching procedure.
[0025] At block 114, a bleaching procedure is performed using a 50 % solution of hydrogen peroxide. During the bleaching procedure, an arylesterase catalyst is added to speed the reaction between the peroxide and the color bodies, as described herein. Generally, the arylesterase catalyst is produced by microorganisms, for example, in a commercial production process. Any number of arylesterase catalysts can be used in the current procedures. In an embodiment, the arylesterase catalyst is obtained from Cekal Specialties under the tradename CEKAZYME BB. [0026] At block 116, should there be any peroxide bleach remaining, it is neutralized by the addition of a catalase enzyme. Any number of catalase enzymes may be used in the current procedures. In an embodiment, the catalase is CEKAZYME EPK200 from Cekal Specialties. In some embodiments, a test strip is used to confirm that the peroxide is eliminated. If not, in some embodiments, a water wash is used to rinse any remaining peroxide from the cotton. Generally, the peroxide is completely reacted, which allows a processor to go directly to the dyeing process. This avoids the washes that are needed to remove the peroxide, for example, saving around 10,000 liters of water per 1,000 kg of textile substrate.
[0027] At block 118, the pH is lowered to a pH of less than about 8, less than about 7, or between 6.5 and 7. In some embodiments, this is performed by the addition of an organic acid, such as citric acid, acetic acid, or others. Tn some embodiments, the pH is checked to confirm that it is between 6.5 and 7. If not, more acid may be added, and the pH retested.
[0028] A surface tension test may be used to confirm that the pretreatment process 102 did not damage or remove the natural wax coating. In some embodiments, the surface tension test is performed by placing a drop of water on the surface of the fabric and noting if the water beads or is absorbed. In other embodiments, a goniometer is used to determine the surface tension of the surface, which may be used to determine the efficacy of the treatment.
[0029] The fabric from the pretreatment process 102 is then used to make a garment in the garment production process 104. For example, the fabric is cut into the appropriate shaped pieces, and sewn into the final garment. The pieces are generally larger than the final size expected for the garment, as the garment accounts for shrinkage during the dying, finishing, and drying stages.
[0030] After preparation of the garment, the treatment process 106 is used to prepare the garment for dying and to apply the wax lock if performance is desired. The treatment process 106 begins at block 120, with the treatment of the garment with sodium sulfate. At block 122, NazCCh (soda ash) is added to raise the pH to about 9.5, or about 10. The pH may be checked, and more Na2CC>3 added if needed to adjust the pH to 9.5. The use of the weak alkali helps retain and protect the cotton wax and the cotton cellulose. It is used in place of the caustic soda (NaOH) used in the standard Kiering procedure, which would set the pH at 12.5, damaging the cotton and removing the natural wax via saponification.
[0031] At block 124, the wax lock is applied, for example, by adding the wax lock material to the solution containing the garment. As described herein, the wax lock locks the natural wax to the cotton fibers, slowing its removal by laundering. The wax lock may include silicone compounds, acrylic oligomers, or combinations. Other materials may be used, such as other types of oligomers or monomers. Generally, the wax lock is hydrophobic, further protecting the natural was from being removed by laundering. The silicone wax lock compound used in some embodiments is available from Apexical Specialty Chemicals of Spartanburg, SC, USA, as Apexosil 2137. In some embodiments, a small amount of acrylic monomers or oligomers may be included, such as about 1 wt. %, about 2 wt. %, about 5 wt. %, about 10 wt. %, about 20 wt. %, or higher. [0032] Tn some embodiments, the wax lock is a blend that includes an acrylic oligomer, such as available from Cekal Specialties as CEKAPEL NFWR. In this example, the acrylic polymer blend includes 20-30 wt. % of a liquid, crosslinking acrylic polymer. The blend also includes 5- 10 wt. % of dipropylene glycol. The dipropylene glycol lowers the viscosity of the polymer blend, improving the uptake into the cotton.
[0033] Similar materials are available from other suppliers. These include blends in the Hycar line from Lubrizol, Corp, of Wickliffe, OH, USA. Other materials are available from Apexical Specialty Chemicals, Huntsman Chemicals of Charlotte, NC, USA, and Chemours of Wilmington, DE, USA.
[0034] In some embodiments, the wax lock compound is a blend that includes natural plant material isolated from plant wastes, for example, the by-products that accumulate during the processing of cereal grains in the food industry. A crosslinker may be included in the blend to assist in locking the natural wax and the natural plant material to the fibers of the cotton. The natural plant material is available from Rudolf GmbH of Geresreid, DE, as RUCO®-DRY BIO CGR. The crosslinker is available from Rudolf as RUCO®-LINK XHC. Other products from Rudolf can be used as the wax lock in embodiments. For example, RUCO®-DRY BIO NPE is a combined natural plant product and cross-linking agent that can be used as the wax lock.
[0035] The dying process 108 is described with respect to blocks 126 to 132. It can be noted that the generic procedure of Figure 1 will work with all dyes. However, specific information on the use of pre-reduced dyes, such as reduction dyes, including indigo, sulfur dyes, pre-reduced indigo, and pre-reduced sulfur dyes, is described further with respect to Figure 2.
[0036] At block 126, the dying compound is added to the solution containing the garment. In some embodiments, the dye is a reactive dye, although any number of other types of dyes may be used, including direct dyes, sulfur dyes, azoic dyes, or vat dyes, among others described herein. The dye liquor is heated to a maximum temperature of about 140 °F (about 60 °C) at a rate of about 2 °F/min (about 1.1 °C/min.). The dye is allowed to stay in contact with the cotton for a sufficient period of time for absorbance, for example, 30 min., 45 min., 60 min., or longer.
[0037] At block 128, the dye and salts are rinsed from the garment. At block 130, the pH is lowered to less than 8, or less than 7, or about 6.5. This is performed by the addition of an organic acid, such as citric acid, acetic acid, or the like. At block 132, a water rinse is performed to remove the acid and any remaining dyes or salts from the garment. In some embodiments, the pH of the rinse solution containing the garment is checked to confirm that it is between 6.5 and 7. If not, more acid may be added, and the pH retested.
[0038] In the drying process 110, the garment is dried to fix the wax lock compound. In various embodiments, this is performed at a temperature of less than about 400 °F (about 204 °C), or less than about 390 °F (about 199 °C), or less than about 350 °F (about 177 °C), or less than about 310 °F (about 154 °C), or between about 300 °F (about 149 °) and about 390 °F (about 199 °C), for example, in a tumble dryer or on a frame or moving line at a speed of about 25 to about 30 yds. /min (or about 23 to about 27 meters/min).
[0039] Figure 2 is a process flow diagram of a dying process 200 that uses a reduction dye. Like numbered items, including the pretreatment process 102, garment production process 104, treatment process 106, and drying process 110, are as described with respect to Figure 1. As used herein, a reduction dye (RD) is a dye that is insoluble in water until it is reduced. In various embodiments, the RD is an indigo dye, a sulfur dye, a pre-reduced indigo dye, a pre-reduced sulfur dye, or other pre-reduced dye. The pre-reduced dye is not fully reduced, for example, only being reduced by about 60 %.
[0040] As for the treatment process 106 of Figure 1, the dying process 200 begins with the treatment of the garment with sodium sulfate at block 118, for example, using about 30 g/1 to about 50 g/1. At block 120, Na2COs (soda ash) is added to raise the pH to about 9.5, or about 10, for example, using about 6 g/1 to about 10 g/1. The pH may be checked, and more Na2COs added if needed to adjust the pH to 9.5. At block 122, the garment is treated with the wax lock compound, as described herein.
[0041] At block 202, the RD is added to the solution. As the dye is not soluble until it is reduced, a reducing agent is added at block 204 to fully reduce the dye for solubilization. In some embodiments, the reducing agent may be a catalase, such as CEKAZYME EPK200 from Cekal added at about 4 g/1 to about 6 g/1, depending on whether the reduction dye is pre-reduced before use. In other embodiments, the reducing agent is sodium borohydride, hydrogen sulfide, or sodium hydrosulfite, among others.
[0042] At block 206, a mordant, or dye fixative agent, is added to assist in adhering the dye to the cloth. In some embodiments, the mordant is Ah(SO4)3, FeSCL, CuSCU, ZnSCh, or MnSCL, among others. The mordant is selected based on the efficacy and the potential effects on the color. Further, the mordant may increase the efficacy of the reducing agent, for example, if a catalase is used, by increasing the ORP of the catalase solution. The mordant can be added at about 10 g/1 to about 20 g/1.
[0043] The dye liquor and reducing agent are heated to a maximum temperature of about 140 °F (about 60 °C) at a rate of about 2 °F/min (about 1.1 °C/min.). The dye is allowed to stay in contact with the cotton for a sufficient period of time for absorbance, for example, 30 min., 45 min., 60 min., or longer.
[0044] At block 126, the dye, mordant, and salts are rinsed from the solution. At block 208, an oxidizer is added to the water solution to oxidize the reduced dye. In various embodiments, the oxidizer is hydrogen peroxide, air, oxygen, a water solution of ozone, and the like. In some embodiments, hydrogen peroxide is added at between about 1 g/1 and about 5 g/1. In other embodiments, the dye is allowed to oxidize in air for about 20 to about 30 minutes. The amount of oxidation controls the color, with higher levels of oxidation correlated to darker colors.
[0045] At block 128, the pH is lowered to less than 8, or less than 7, or about 6.5. This is performed by the addition of an organic acid, such as citric acid, acetic acid, or the like. At block 130, a water rinse is performed to remove the acid and any remaining dyes or salts. In some embodiments, the pH is checked to confirm that it is between 6.5 and 7. If not, more acid may be added, and the pH retested.
[0046] It can be noted that all of the enzymes described herein are available from other suppliers. For example, AB Enzymes of Darmstadt, DE, produces analogous arylesterase catalysts and catalase enzymes that may be used in the processes described herein.
[0047] Further, any number of other dyes may be used in embodiments described herein, including, including vat dyes, sulfur dyes, pre-reduced versions of vat and sulfur dyes, and other dyes that are insoluble and are applied to substrates via redox methods. Other dyes than can be used include azo dyes, such as direct dyes, metal complex dyes, reactive dyes, substantive dyes, and aniline dyes, such as natural and synthetic indigo dye, among others.
[0048] EXAMPLES
[0049] The treatment process described herein, for example, with respect to Figure 1, was tested on cotton fabric using the parameters described in Table 1. The dye used in the process described in Table 1 can be used pre-reduced dyes, such as pre-reduced indigo and pre-reduced sulfur dyes, as shown in Table 2. [0050] TABLE 1 : Parameters for treating process applied to cotton fabric
Figure imgf000011_0001
[0051] TABLE 2: Parameters for dying cotton fabric using a pre-reduced dye
Figure imgf000012_0001
[0052] As described herein, after the pretreatment, cotton fabric can be made into garments, and the wax lock can be applied during the dying process, for example, before the dye is added. A cotton fabric prepared using this technique with a silicone softener as the wax lock compound retained the natural wax through greater than 25 laundering cycles using a cool wash cycle, 1 g/L Tide laundry detergent, and a cool dry cycle. This was tested by performed a surface tension test after each laundering cycle by applying a water droplet and determining that it beaded on the cotton fabric. As described herein, the natural wax lock products from Rudolph, Ruco-Dry Bio CGR and Ruco-Dry Bio NPE, are highly effective.
[0053] The burst strength of the cotton fabric was compared to a sample of cotton fabric that was treated by the normal caustic wash. The test performed to determine the strength was the Mullen diaphragm burst test, following ASTM D3787. The strength retained by the cotton fibers depended on the initial lengths of the cotton fibers, e.g., the quality of the cotton. A sample of fabric made using a high-quality cotton and treated using the procedure described with respect to Figure 1 provided an average burst strength of up to 210 psi (about 1448 kPa), versus a sample of the same fabric treated with the standard Kiering procedure, which had an average burst strength of about 110 psi (about 758 kPa). [0054] A sample of fabric prepared from a lower quality cotton, e g., with shorter fiber lengths, still maintained a significant strength advantage when treated with the procedure of Figure 1 versus the normal Kiering procedure. The fabric prepared from the lower quality cotton that was treated with the standard Kiering procedure had an average burst strength of about 93.9 psi (647 kPa). A sample of the same fabric treated with the procedure of Figure 1 had an average burst strength of about 109.8 psi (757 kPa).
[0055] Embodiments
[0056] An embodiment described in examples herein provides a method for making water- resistant cotton garments. The method includes treating cotton fabric with soda ash at a temperature of less than about 150 °F (about 66 °C) and a pH of about 9.5 and bleaching the cotton fabric with hydrogen peroxide at a temperature of less than about 150 °F (about 66 °C). The hydrogen peroxide is neutralized, and the pH is lowered with an organic acid to between about 6 and about 7. A garment is made from the cotton fabric and a wax lock is applied to the garment. The garment is dyed at a temperature of less than about 150 °F (about 66 °C), and dried.
[0057] In an aspect, combinable with any other aspect, making the garment includes cutting pieces from the cotton fabric and sewing the pieces together to form the garment.
[0058] In an aspect, combinable with any other aspect, the method includes adding a bleach activator with the soda ash.
[0059] In an aspect, combinable with any other aspect, the method includes adding a sequestering agent with the soda ash.
[0060] In an aspect, combinable with any other aspect, the method includes adding an arylesterase catalyst with the hydrogen peroxide.
[0061] In an aspect, combinable with any other aspect, neutralizing includes adding an enzyme to degrade the hydrogen peroxide.
[0062] In an aspect, combinable with any other aspect, the organic acid includes citric acid.
[0063] In an aspect, combinable with any other aspect, applying the wax lock to the garment includes treating the garment with sodium sulfate, treating the cotton with soda ash to raise the pH to about 9.5, and applying the wax lock to the garment. [0064] In an aspect, combinable with any other aspect, the dying includes treating the garment with a dye solution, rinsing the garment, neutralizing the dye solution to a pH of about 6.5, and rinsing the garment.
[0065] In an aspect, combinable with any other aspect, the dye solution includes a prereduced dye.
[0066] In an aspect, combinable with any other aspect, the method includes adding a reducing agent to the dye solution.
[0067] In an aspect, combinable with any other aspect, the method includes adding a mordant to the dye solution.
[0068] In an aspect, combinable with any other aspect, the method includes treating the garment with an oxidant.
[0069] In an aspect, combinable with any other aspect, the method includes treating the garment with the wax lock.
[0070] In an aspect, combinable with any other aspect, the method includes drying the garment at between about 300 °F (about 149 °C) and about 390 °F (about 199 °C).
[0071] In an aspect, combinable with any other aspect, the wax lock includes a silicone compound.
[0072] In an aspect, combinable with any other aspect, wax lock includes an acrylic compound.
[0073] Another embodiment described in examples herein provides a cotton garment formed from an activated cotton material, including a layer of natural wax locked to a surface of cotton fibers by a wax lock.
[0074] In an aspect, combinable with any other aspect, the cotton garment includes a dye.
[0075] In an aspect, combinable with any other aspect, the cotton garment includes a prereduced dye.
[0076] In an aspect, combinable with any other aspect, the pre-reduced dye includes indigo.
[0077] In an aspect, combinable with any other aspect, the wax lock includes a silicone compound.
[0078] In an aspect, combinable with any other aspect, the wax lock includes an acrylic oligomer. [0079] In an aspect, combinable with any other aspect, the wax lock includes a natural plant material.
[0080] In an aspect, combinable with any other aspect, the wax lock includes a natural plant material combined with a cross-linking agent.
[0081] Other implementations are also within the scope of the following claims.

Claims

Claims What is claimed is:
1. A method for making water-resistant cotton garments, comprising: treating cotton fabric with soda ash at a temperature of less than about 150 °F (about 66 °C) and a pH of about 9.5; bleaching the cotton fabric with hydrogen peroxide at a temperature of less than about 150 °F (about 66 °C); neutralizing the hydrogen peroxide; lowering the pH with an organic acid to between about 6 and about 7; making a garment from the cotton fabric; applying a wax lock to the garment; dying the garment at a temperature of less than about 150 °F (about 66 °C); and drying the garment.
2. The method of claim 1, wherein making the garment comprises: cutting pieces from the cotton fabric; and sewing the pieces together to form the garment.
3. The method of claim 1, comprising adding a bleach activator with the soda ash.
4. The method of claim 1, comprising adding a sequestering agent with the soda ash.
5. The method of claim 1, comprising adding an arylesterase catalyst with the hydrogen peroxide.
6. The method of claim 1, wherein neutralizing comprises adding an enzyme to degrade the hydrogen peroxide.
7. The method of claim 1, wherein the organic acid comprises citric acid.
8. The method of claim 1 , wherein applying the wax lock to the garment, comprises: treating the garment with sodium sulfate; treating the cotton with soda ash to raise the pH to about 9.5; and applying the wax lock to the garment.
9. The method of claim 1, wherein the dying comprises: treating the garment with a dye solution; rinsing the garment; neutralizing the dye solution to a pH of about 6.5; and rinsing the garment.
10. The method of claim 9, wherein the dye solution comprises a pre-reduced dye.
11. The method of claim 10, comprising adding a reducing agent to the dye solution.
12. The method of claim 10, comprising adding a mordant to the dye solution.
13. The method of claim 10, comprising treating the garment with an oxidant.
14. The method of claim 1, comprising treating the garment with the wax lock.
15. The method of claim 14, comprising drying the garment at between about 300 °F (about
149 °C) and about 390 °F (about 199 °C).
16. The method of claim 14, wherein the wax lock comprises a silicone compound.
17. The method of claim 14, wherein the wax lock comprises an acrylic compound.
18. A cotton garment formed from an activated cotton material, comprising a layer of natural wax locked to a surface of cotton fibers by a wax lock.
19. The cotton garment of claim 18, comprising a dye.
20. The cotton garment of claim 18, comprising a pre-reduced dye.
21. The cotton garment of claim 20, wherein the pre-reduced dye comprises indigo.
22. The cotton garment of claim 18, wherein the wax lock comprises a silicone compound.
23. The cotton garment of claim 18, wherein the wax lock comprises an acrylic oligomer.
24. The cotton garment of claim 18, wherein the wax lock comprises a natural plant material.
25. The cotton garment of claim 18, wherein the wax lock comprises a natural plant material combined with a cross-linking agent.
PCT/US2023/030789 2022-08-22 2023-08-22 Launderable activated cotton garment WO2024044164A1 (en)

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US202263373101P 2022-08-22 2022-08-22
US63/373,101 2022-08-22

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050097685A1 (en) * 2003-10-21 2005-05-12 Dystar Textilfarben Gmbh & Co. Deutschland Kg Continuous dyeing of fabrics comprising cellulosic fibers
US20140335294A1 (en) * 2011-12-23 2014-11-13 Eun Hyo Cho Fiber product provided with water repellant coating layer and method for manufacturing the fiber product
US20150299948A1 (en) * 2012-09-07 2015-10-22 Lubrizol Advanced Materials, Inc. Fabric pretreatment for digital printing
US20220235518A1 (en) * 2021-01-25 2022-07-28 Energy Ogre Llc Launderable activated cotton
US20220389650A1 (en) * 2021-01-25 2022-12-08 Energy Ogre Llc Launderable activated cotton

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050097685A1 (en) * 2003-10-21 2005-05-12 Dystar Textilfarben Gmbh & Co. Deutschland Kg Continuous dyeing of fabrics comprising cellulosic fibers
US20140335294A1 (en) * 2011-12-23 2014-11-13 Eun Hyo Cho Fiber product provided with water repellant coating layer and method for manufacturing the fiber product
US20150299948A1 (en) * 2012-09-07 2015-10-22 Lubrizol Advanced Materials, Inc. Fabric pretreatment for digital printing
US20220235518A1 (en) * 2021-01-25 2022-07-28 Energy Ogre Llc Launderable activated cotton
US20220389650A1 (en) * 2021-01-25 2022-12-08 Energy Ogre Llc Launderable activated cotton
US20230018084A1 (en) * 2021-01-25 2023-01-19 Energy Ogre Llc Launderable activated cotton

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