US20140304922A1 - Fabric having ultraviolet radiation protection - Google Patents

Fabric having ultraviolet radiation protection Download PDF

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Publication number
US20140304922A1
US20140304922A1 US14/246,285 US201414246285A US2014304922A1 US 20140304922 A1 US20140304922 A1 US 20140304922A1 US 201414246285 A US201414246285 A US 201414246285A US 2014304922 A1 US2014304922 A1 US 2014304922A1
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United States
Prior art keywords
cotton
solution
fabric
ultraviolet radiation
mmol
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US14/246,285
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Robert B Kramer
Ronald Kramer
Nicholas Marshall
Jason Rosenberg
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Individual
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Individual
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Priority claimed from US13/317,152 external-priority patent/US8277518B1/en
Application filed by Individual filed Critical Individual
Priority to US14/246,285 priority Critical patent/US20140304922A1/en
Publication of US20140304922A1 publication Critical patent/US20140304922A1/en
Abandoned legal-status Critical Current

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    • 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
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • 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
    • D06M11/36Treating 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 oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38Oxides or hydroxides of elements of Groups 1 or 11 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
    • 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
    • D06M11/36Treating 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 oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • 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
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188Monocarboxylic acids; Anhydrides, halides or salts thereof

Definitions

  • This disclosure relates to a fabric having ultraviolet radiation protection, and more specifically, to a fabric having ultraviolet (UV) radiation protection incorporated into the fabric by use of a laundry additive or photographing.
  • UV ultraviolet
  • Ecological friendly fabrics or Eco-friendly fabrics are gaining in popularity and use in clothing.
  • An Eco-friendly fabric may be a natural fiber such as cotton, hemp, or bamboo which has been grown in soil that has not been treated with pesticides for a number of years.
  • Some examples of other Eco-friendly fabrics are organic cotton, sisal, a combination of hemp and recycled rayon, a combination of hemp and cotton, broadcloth, denim, linen, and a combination of bamboo and recycled rayon.
  • Natural fibers, which may be derived from plants or animals, such as wool, angora, silk, alpaca, cashmere, and silk are also examples of Eco-friendly fabrics.
  • Synthetic fabrics which may be made from synthetic sustainable products, such as nylon, rayon, olefin, spandex, and tencel are also examples of Eco-friendly fabrics.
  • UPF Ultraviolet Protection Factor
  • Clothing having a rating of UPF 50 are able to block out 98% of the sun's ultraviolet radiation. Further, by way of example, a garment having a rating of UPF 15-24 will only block out 93.3% to 95.9% of ultraviolet radiation. Exposure to the sun's harmful ultraviolet radiation (known as UVA/UVB rays) can damage the skin, can cause sunburn, and can lead to skin cancer over prolonged exposure.
  • UVA/UVB rays Exposure to the sun's harmful ultraviolet radiation
  • UVA/UVB rays can damage the skin, can cause sunburn, and can lead to skin cancer over prolonged exposure.
  • the level of ultraviolet radiation protection provided by a fabric There are a number of factors that affect the level of ultraviolet radiation protection provided by a fabric and the UPF rating. Some factors are the weave of the fabric, the color of the fabric, the weight of the fabric, the fiber composition of the fabric, the stretch of the fabric, moisture content of the fabric. If the fabric has a tight weave or a high thread count then the fabric will have a higher UPF rating. However, even though the fabric has a higher UPF rating, the fabric may be less comfortable because a tighter weave or higher thread count means that the fabric is heavy or uncomfortable to wear. Another factor that affects protection is the addition of chemicals such as UV absorbers or UV diffusers during the manufacturing process. As can be appreciated, some of the features that make a garment comfortable to wear also make the garment less protective. A challenge for a clothing manufacturer is to provide clothing having both protection from the sun and being comfortable to wear.
  • a method for treating mercerized cotton for incorporating ultraviolet radiation protection into the mercerized cotton comprises the steps of placing the mercerized cotton into a solution of Zn(II), removing the mercerized cotton from the solution, and washing the mercerized cotton.
  • a method for treating cotton for incorporating ultraviolet radiation protection into the cotton comprises the steps of placing the cotton into a concentrated mercerization strength NaOH solution, placing the cotton into a solution of Zn(II), removing the cotton from the solution of Zn(II), and washing the cotton.
  • a method for treating cotton for incorporating ultraviolet radiation protection into the cotton comprises the steps of placing the cotton into a concentrated mercerization strength NaOH solution, placing the cotton into a solution of Zn(II), placing the cotton into a solution of NaOH, removing the cotton from the solution of NaOH, and washing the cotton.
  • the present disclosure provides a fabric having ultraviolet radiation protection which is lightweight and can be worn in any temperature.
  • the present disclosure provides a fabric having ultraviolet radiation protection which provides enhanced protection from both UVA and UVB radiation when worn by an individual.
  • the present disclosure also provides a fabric having ultraviolet radiation protection which retains ultraviolet radiation protection after use or after cleaning.
  • the present disclosure provides a fabric having ultraviolet radiation protection which is comfortable to wear.
  • the present disclosure provides a fabric having antimicrobial protection incorporated therein.
  • the present disclosure also provides a fabric having ultraviolet radiation protection which can be manufactured without increasing the cost of the fabric.
  • the present disclosure provides a fabric having ultraviolet radiation protection that may be incorporated into the fabric by use of a laundry additive.
  • the present disclosure provides a fabric having ultraviolet radiation protection that is incorporated into active wear clothing or athletic clothing.
  • UV-blocking nanoparticles on Eco-friendly fabric to incorporate UV protection in the fabric.
  • the Eco-friendly fabric will be able to protect a wearer of the fabric from UV radiation.
  • One method comprises direct immobilization from in situ formation of the particles.
  • a second method comprises carboxylation or phosphorylation of the fabric followed by binding of the UV-blocking nanoparticles to the modified fabric.
  • a third method comprises modifying UV-blocking nanoparticles with a self-assembled monolayer (SAM) or polymer layer containing an active chemical group capable of binding to the fabric and deposited on the fabric from solution.
  • SAM self-assembled monolayer
  • ZnO (zinc oxide) nanoparticles are generally formed by the precipitation of a zinc salt (acetate, sulfate, nitrate, chloride) using either aqueous hydroxide or an amine.
  • a zinc salt acetate, sulfate, nitrate, chloride
  • amine aqueous hydroxide
  • the following examples disclose direct immobilization from in situ formation of the ZnO nanoparticles.
  • a fabric may be treated to have ultraviolet radiation protection incorporated in the fabric by the steps of dissolving zinc acetate or other zinc salt in a liquid to form a solution containing Zn(II) ions, adding a fabric to the solution, mixing the solution and the fabric, and adding a base to the solution when the solution and the fabric are being mixed to form a suspension of zinc oxide nanoparticles in contact with the fabric.
  • Phosphorylated cellulose should form covalent linkages with ZnO and TiO 2 nanoparticles.
  • the interaction between phosphonates and oxide surfaces are used for modification of the oxide surfaces.
  • the procedure consists of condensing the cellulose textile with a bis(phosphonic acid), phosphonate, or phosphate species, either organic or inorganic. Urea may be added to forestall discoloration of the textile. Phosphorylation takes place driven by the elimination of water. The resulting phosphorylated textile will directly bind both zinc oxide and titanium oxide nanoparticles.
  • a sample of cotton textile is wetted with a 10% v/v solution of phosphoric acid or bis-phosphonic acid containing 10-30% w/v urea.
  • the textile is pressed to remove excess solution and baked in an oven at 85-100° C. for 5 minutes to dry, then at 170° C. for 2-4 minutes to cure unreacted groups.
  • the textile is removed from the oven and washed with water. The textile is then used without further modification in subsequent deposition steps.
  • a sample of cotton textile (ca. 1 g) is added to a solution composed of 90 mL water with 10 mg (0.065 mmol) TEMPO and 0.22 g (2 mmol) sodium bromide. Hydrogen peroxide 3% is added (0.9 mL, 1 mmol) and the reaction stirred at RT for 10 minutes to 2 hours. The material is washed with water, dried, and used without further modification in the following ZnO deposition step.
  • nanoparticles 1 mg/mL nanoparticles are suspended in water, ethyl alcohol, or other solvent.
  • the phosphorylated or carboxylated cellulose textile is added to the suspension and the suspension is gently mixed over a reaction period of 1 to 12 hours.
  • the textile is removed from the suspension and subjected to tumble drying or another drying procedure to force surface condensation and cure remaining groups.
  • the following example discloses modifying UV-blocking nanoparticles with a self-assembled monolayer (SAM) or polymer layer containing an active chemical group capable of binding to the fabric and deposited on the fabric from solution.
  • SAM self-assembled monolayer
  • ZnO particles are synthesized separately by any of the means discussed in Examples 1-3 or the ZnO particles may be purchased commercially.
  • the ZnO particles are suspended in water or a weak non-nucleophilic aqueous buffer and an organosilane or phosphonate with one of the given combinations of reactive groups, as shown in Table 1, is added.
  • Multidentate ligand or polymeric silanes may also be added to this mixture to facilitate the formation of a durable reactive layer and an oxide, alkoxide, or salt of another metal such as Ti or Si may be added first to form a surface layer of another oxide in the ZnO particles. After a reaction time of 1 to 12 hours, the particles are collected by centrifugation and washed with water.
  • the particles are then resuspended in water or buffer and added to the textile.
  • the conditions for binding of the particles to the textile vary depending on the headgroup, as shown in Table 1, but may involve direct application of the particles to the textile similarly to the process disclosed in Example 6, raising the pH of the suspension containing the textile, or heating the textile either in or after removal from the suspension.
  • This process has the advantage of yielding extremely fine control over the nature of the linkage between particle and textile.
  • This process has a further advantage in that the treated textile will be durable due to the robustness of self-assembled siloxane layers on oxide.
  • fabric or “textile” are intended to include fibers, filaments, yarn, textiles, material, woven and non-woven fabric, knits, and finished products such as garments.
  • the methods described above may be used in treating fibers, filaments, yarn, textiles, and fabrics.
  • fibers may be initially treated by use of one or more of the above disclosed methods and the fibers may be manufactured into a fabric or a textile. Once manufactured into a fabric, the fabric may be treated by use of one or more of the disclosed methods. In this manner, individual fibers and the entire fabric are treated to incorporate UV protection.
  • the treated fabric may be used to manufacture a garment such as, by way of example only, shirts, pants, hats, coats, jackets, shoes, socks, uniforms, athletic clothing, and swimwear. It is also possible and contemplated that the treated fabric may be used to construct non-apparel items such as blankets, sheets, sleeping bags, backpacks, and tents.
  • Oxides that can be deposited in this manner include SiO 2 from tetraethoxysilane (TEOS) or sodium silicate, and Al 2 O 3 and TiO 2 either from the appropriate alkoxides, aluminate/titanate compounds, or other hydrolyzable aluminum or titanium compounds.
  • TEOS tetraethoxysilane
  • TiO 2 aluminum oxide 3
  • a second oxide shell of this type may enhance the formation and stability of both directly applied ZnO-textile conjugates and those formed by modification of nanoparticles with an organic monolayer.
  • ZnO can also be modified by the addition of a multidentate silane along with a silane containing the desired functional group.
  • the multidentate silane yields a more densely crosslinked siloxane surface than monodentate silanes alone, forming a more stable layer on ZnO.
  • the methods may comprise the self-assembly of certain polyanionic materials onto a ZnO surface to create a linker which will bind the particles to a cellulose (cotton) surface.
  • Several acidic or oxyanion functional groups are capable of self-assembly onto ZnO. These functional groups include siloxane, silanol, carboxylic acid, carboxylate, phosphonic acid, phosphonate, boronic acid or other groups capable of binding to oxide layers.
  • Boronic acid is capable of forming very strong interactions with carbohydrates, including the glycosidically linked glucose units making up cellulose.
  • One method or approach is to prepare a polymer bearing boronic acid groups and use that polymer to bind ZnO to cotton.
  • cellulose-to-oxide method A second method is termed the oxide-to-cellulose method.
  • oxide-to-cellulose method A third method is described as the free mixing method.
  • cotton garments are pre-treated with boronic acid polymer resulting in cloth or fabric coated with boronic acid groups capable of binding to suspended uncoated ZnO particles.
  • a home washing machine having the capability of adding a substance on a delayed basis may be used.
  • boronic acid polymer is added to laundry detergent or added at the beginning of the laundry cycle.
  • a suspension of ZnO particles may be added to a compartment in the washing machine that will dispense the particles on a delayed basis.
  • several washing machines have a compartment for storing bleach which is dispensed later on in the laundry cycle. The suspension of ZnO particles may be placed in the bleach compartment to be dispensed at the time that bleach would normally be dispensed into the washing machine.
  • the washing machine would initially mix the clothing with the boronic acid material. This will result in the clothing bearing boronate groups. At the end of the delayed period the washing machine will dispense the suspension of ZnO particles into the washing machine. The ZnO particles will bind to the boronate groups and become attached to the clothing. It is also possible and contemplated that the suspension of ZnO particles may be manually added to the washing machine in a delayed manner. Manually adding the suspension may be required if the washing machine is not equipped with a compartment for adding bleach on a delayed basis.
  • ZnO particles are treated with boronic acid polymer. Once prepared, these particles may be either mixed with laundry detergent and distributed in that form or sold as a separate additive that may be added to laundry detergent. The particles mixed with the laundry detergent or the separate additive is used in the washing machine as normal. During the course of the wash cycle, the boronic acid groups attach to the ZnO particles would assemble on and bind to cotton or other cellulose clothing. This results in a ultraviolet protected garment.
  • boronic acid polymer and ZnO particles are incorporated into the laundry detergent preparation in the solid phase.
  • the detergent and water When added to a laundry cycle or wash cycle the detergent and water will solubilize these materials causing boronic acid polymer to assemble on both ZnO and cellulose. This will result in linked ZnO material.
  • This method may require more boronic acid polymer and ZnO particles then the more controlled methods disclosed in Examples 8 and 9 to yield adequate grafting densities of ZnO on clothing.
  • any of the methods disclosed in Examples 8, 9, or 10 will result in ZnO particles being bound to the fabric that is being washed in a conventional household washing machine. Once the ZnO particles are bound to the fabric, the fabric will have incorporated therein ultraviolet radiation protection. It is also possible and contemplated that the various methods described in Examples 8, 9, and 10 may be used more than once to incorporate ultraviolet radiation protection into clothing. For example, clothing may be treated by use of one or more of these methods and over time and after numerous washings the ultraviolet radiation protection may diminish. If there is any concern about the ultraviolet radiation protection of the garment, the garment may be washed using the various methods discussed in Examples 8, 9, and 10. Further, it is possible that a consumer may purchase a garment that has been treated using the methods described in Examples 1-7. Again, over time the ultraviolet radiation protection of the garment may decline. The consumer may use the methods disclosed in Example 8, 9, and 10 to wash the garment to again incorporate ultraviolet radiation protection into the garment.
  • All synthetic material such as polyester and nylon that is used in the manufacture of athletic clothing or active wear clothing may be rendered UV-absorbing using a ZnO preparation. These types of fabrics may resist treatment using the methods as outlined with respect to Examples 8, 9, and 10.
  • One solution to this problem is to prepare ZnO particles coated with functional groups capable of being grafted directly to polyester or nylon materials. This may be accomplished by using benzophenone photografting chemistry.
  • the following examples and methods are applicable to the manufacturing process in which ultraviolet radiation protection is incorporated into the artificial or synthetic fabric, textile, or garment when initially produced.
  • the following methods provide for the direct grafting of ZnO particles to nonpolar, non-natural polymers such as nylon and polyester.
  • Nylon and polyester have little in the way of chemical functionality, containing only alphatic and aromatic C-H bonds and amide or ester linkages between monomers.
  • the method is capable of directly functionalizing C-H bonds.
  • the following method describes preparing ZnO particles coated with functional groups capable of being grafted directly to polyester or nylon materials by using the photografting reaction of benzophenone.
  • an artificial fabric composed of polyester, nylon, or other polymer lacking hydroxyl functional group is modified by use of a preparation of a zinc oxide particle modified with a layer of reactive groups capable of C-H activation.
  • the reactive functional group capable of C-H activation are benzophenone, sulfonylazides, aryl azides, or diazonium salts.
  • the prepared particles are coated onto the fabric and a reaction is initiated using UV light, heat, or both. By way of example only, a mercury-vapor UV lamp may be used and the time for exposure may be one hour. Unbound particles are washed off the fabric.
  • This second step, a curing step bonds the prepared particles to the fabric.
  • This method adds a second UV-absorbing chromophore which cross-links and becomes further bonded to the polymer surface of the fabric upon exposure to UV light.
  • zinc oxide particles can be composed of pure zinc oxide or zinc oxide coated with aluminum, titanium, or silicon oxides in a core-shell configuration. The result is an artificial fabric with photografted zinc oxide particles.
  • the zinc oxide particles were prepared in the following manner. Five grams of zinc oxide nanoparticles were used and suspended in a solution of 98% ethyl alcohol. Two grams of benzophenone silane linker were suspended in this solution and the pH of the solution was adjusted to 12. After 12 hours, the zinc oxide particles were recovered by centrifugation and dried overnight at 50-60° C. in an oven.
  • Some cotton fabrics or yarns are mercerized through a series of processes to add luster to the fabrics or yarns.
  • the mercerization process typically requires that cotton be held under tension for a specific amount of time while having between 21%-23% caustic soda (NaOH) applied to the cotton at room temperature.
  • the process may include neutralizing the cotton by washing with water or by using an acid bath.
  • the cotton fabric or yarn has increased luster, increased strength, is easier to dye, and resists mildew.
  • the treated cotton does not include any ultraviolet radiation protection.
  • mercerized fabric, textile, or a garment may be made an ultraviolet radiation protected fabric, textile, or garment for an end user.
  • the word or term “cotton” is intended to mean or include fibers, filaments, yarn, textiles, material, woven and non-woven fabric, knits, and finished products such as garments.
  • the methods may comprise impregnating cotton with ZnO that involves treating the textile with aqueous Zn(II) solution followed by addition of ca. 2M NaOH solution with subsequent washing steps.
  • cotton is pretreated with a solution of NaOH followed by transfer to Zn(II) solution.
  • the pretreatment step is to place the cotton in a concentrated mercerization strength NaOH solution before placing the cotton into Zn(II) solution. Since mercerization generally greatly enhances absorption of dyes on cellulose, the cotton will readily incorporate the deposition of ZnO on or in the mercerized cotton.
  • a solution of ca. 2M NaOH may be added. After a sufficient time, the cotton is removed from the NaOH solution and may be washed or rinsed and then dried. It is possible that the cotton may be washed or rinsed more than once.
  • cotton is swelled with a strong NaOH solution and after the optional step of pressing and/or stretching the cotton as part of the mercerization process, the cotton is transferred to a Zn(II) solution. Retained NaOH in the cotton reacts with the Zn(II), depositing ZnO on the cotton and in the fibers of the cotton. After a sufficient time, the cotton is removed from the Zn(II) solution, washed or rinsed, and then allowed to dry. This method does not require an acid recycling step.
  • previously mercerized cotton is used.
  • the mercerized cotton is placed into a Zn(II) solution.
  • the ZnO is deposited on the cotton and in the fibers of the cotton.
  • the cotton is removed from the Zn(II) solution after a period of time, washed or rinsed, and then allowed to dry.
  • the solution of Zn(II) or the ZnO nanoparticles may be produced by any of the methods described above in Examples 1-3 to be used in Examples 12-14.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A method for treating mercerized cotton for incorporating ultraviolet radiation protection into the mercerized cotton is disclosed which comprises the steps of placing the mercerized cotton into a solution of Zn(II), removing the mercerized cotton from the solution, and washing the mercerized cotton. Other methods for treating cotton for protection from ultraviolet radiation are also disclosed.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation-in-part of U.S. patent application Ser. No. 13/632,223 filed on Oct. 1, 2012, which is now U.S. Pat. No. 8,690,964, which was a continuation-in-part of U.S. patent application Ser. No. 13/317,152 filed on Oct. 11, 2011, which is now U.S. Pat. No. 8,277,518.
  • BACKGROUND
  • This disclosure relates to a fabric having ultraviolet radiation protection, and more specifically, to a fabric having ultraviolet (UV) radiation protection incorporated into the fabric by use of a laundry additive or photographing.
  • Ecological friendly fabrics or Eco-friendly fabrics are gaining in popularity and use in clothing. An Eco-friendly fabric may be a natural fiber such as cotton, hemp, or bamboo which has been grown in soil that has not been treated with pesticides for a number of years. Some examples of other Eco-friendly fabrics are organic cotton, sisal, a combination of hemp and recycled rayon, a combination of hemp and cotton, broadcloth, denim, linen, and a combination of bamboo and recycled rayon. Natural fibers, which may be derived from plants or animals, such as wool, angora, silk, alpaca, cashmere, and silk are also examples of Eco-friendly fabrics. Synthetic fabrics, which may be made from synthetic sustainable products, such as nylon, rayon, olefin, spandex, and tencel are also examples of Eco-friendly fabrics.
  • To assist an individual in determining whether a garment has protection against ultraviolet radiation, a rating system has been developed. This rating system is known in the industry as the UPF (Ultraviolet Protection Factor) rating system. Clothing having a rating of UPF 50 are able to block out 98% of the sun's ultraviolet radiation. Further, by way of example, a garment having a rating of UPF 15-24 will only block out 93.3% to 95.9% of ultraviolet radiation. Exposure to the sun's harmful ultraviolet radiation (known as UVA/UVB rays) can damage the skin, can cause sunburn, and can lead to skin cancer over prolonged exposure.
  • There are a number of factors that affect the level of ultraviolet radiation protection provided by a fabric and the UPF rating. Some factors are the weave of the fabric, the color of the fabric, the weight of the fabric, the fiber composition of the fabric, the stretch of the fabric, moisture content of the fabric. If the fabric has a tight weave or a high thread count then the fabric will have a higher UPF rating. However, even though the fabric has a higher UPF rating, the fabric may be less comfortable because a tighter weave or higher thread count means that the fabric is heavy or uncomfortable to wear. Another factor that affects protection is the addition of chemicals such as UV absorbers or UV diffusers during the manufacturing process. As can be appreciated, some of the features that make a garment comfortable to wear also make the garment less protective. A challenge for a clothing manufacturer is to provide clothing having both protection from the sun and being comfortable to wear.
  • Therefore, it would be desirable to provide a fabric that can be treated to protect an individual from the effects of the sun. Moreover, there is a need for a controllable process for attaching UV protection to a fabric after the fabric has been manufactured so that the treated fabric may be used to protect an individual from UV radiation. Furthermore, it would be advantageous to incorporate adequate protection in a garment, fabric, or textile to protect against exposure to UV radiation, to increase the UV resistance of a garment, fabric, or textile, or to enhance UV radiation absorption of a garment, fabric, or textile to protect an individual from UV radiation.
  • BRIEF SUMMARY
  • In one form of the present disclosure, a method for treating mercerized cotton for incorporating ultraviolet radiation protection into the mercerized cotton is disclosed which comprises the steps of placing the mercerized cotton into a solution of Zn(II), removing the mercerized cotton from the solution, and washing the mercerized cotton.
  • In another form of the present disclosure, a method for treating cotton for incorporating ultraviolet radiation protection into the cotton comprises the steps of placing the cotton into a concentrated mercerization strength NaOH solution, placing the cotton into a solution of Zn(II), removing the cotton from the solution of Zn(II), and washing the cotton.
  • In yet another form of the present disclosure, a method for treating cotton for incorporating ultraviolet radiation protection into the cotton comprises the steps of placing the cotton into a concentrated mercerization strength NaOH solution, placing the cotton into a solution of Zn(II), placing the cotton into a solution of NaOH, removing the cotton from the solution of NaOH, and washing the cotton.
  • The present disclosure provides a fabric having ultraviolet radiation protection which is lightweight and can be worn in any temperature.
  • The present disclosure provides a fabric having ultraviolet radiation protection which provides enhanced protection from both UVA and UVB radiation when worn by an individual.
  • The present disclosure also provides a fabric having ultraviolet radiation protection which retains ultraviolet radiation protection after use or after cleaning.
  • The present disclosure provides a fabric having ultraviolet radiation protection which is comfortable to wear.
  • The present disclosure provides a fabric having antimicrobial protection incorporated therein.
  • The present disclosure also provides a fabric having ultraviolet radiation protection which can be manufactured without increasing the cost of the fabric.
  • The present disclosure provides a fabric having ultraviolet radiation protection that may be incorporated into the fabric by use of a laundry additive.
  • The present disclosure provides a fabric having ultraviolet radiation protection that is incorporated into active wear clothing or athletic clothing.
  • DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
  • Various methods or processes are disclosed herein for the immobilization of UV-blocking nanoparticles on Eco-friendly fabric to incorporate UV protection in the fabric. Once the UV-blocking nanoparticles are attached, the Eco-friendly fabric will be able to protect a wearer of the fabric from UV radiation. One method comprises direct immobilization from in situ formation of the particles. A second method comprises carboxylation or phosphorylation of the fabric followed by binding of the UV-blocking nanoparticles to the modified fabric. A third method comprises modifying UV-blocking nanoparticles with a self-assembled monolayer (SAM) or polymer layer containing an active chemical group capable of binding to the fabric and deposited on the fabric from solution.
  • ZnO (zinc oxide) nanoparticles are generally formed by the precipitation of a zinc salt (acetate, sulfate, nitrate, chloride) using either aqueous hydroxide or an amine. The following examples disclose direct immobilization from in situ formation of the ZnO nanoparticles.
  • EXAMPLE 1 Solution Sol-Gel Process, Hydroxide Base
  • 4.39 g. zinc acetate (20 mmol) is dissolved in 100 mL deionized or distilled water. A textile is added to this solution and 100 mL 0.4M NaOH is added while mixing. The suspension is mixed for 2 hours to form a suspension of zinc oxide nanoparticles in contact with the fabric. The textile is removed from the nanoparticle suspension and laundered in a household washing machine. As can be appreciated, a fabric may be treated to have ultraviolet radiation protection incorporated in the fabric by the steps of dissolving zinc acetate or other zinc salt in a liquid to form a solution containing Zn(II) ions, adding a fabric to the solution, mixing the solution and the fabric, and adding a base to the solution when the solution and the fabric are being mixed to form a suspension of zinc oxide nanoparticles in contact with the fabric.
  • EXAMPLE 2 Solution Sol-Gel Process, Amine Base
  • 4.39 g. zinc acetate (20 mmol) is dissolved in 100 mL deionized water. A textile is added to this solution while mixing and 40 mmol amine is added while mixing. Amines used may include ethanolamine, ethylenediamine, (tris)hydroxymethylaminomethane, or others. The textile is removed from the nanoparticle suspension and laundered in a household washing machine.
  • EXAMPLE 3 Mechanochemical Process
  • 5.75 g. zinc sulfate heptahydrate (20 mmol) and 0.88 g (15 mmol) sodium chloride are powered finely and blended, then placed with a textile in a ball mill or similar mechanical mixer. 1.6 g (40 mmol) sodium hydroxide is powdered and added to the mixer. After twenty minutes, the textile is removed and rinsed thoroughly with water.
  • The following examples disclose carboxylation or phosphorylation of the fabric followed by binding of the UV-blocking nanoparticles to the modified fabric.
  • EXAMPLE 4 Modification of Textile with Phosphonic Acid Groups
  • For this process it will be necessary to modify a textile with phosphonic acid groups. This can be accomplished in a number of ways, but it is desirable to use materials that are non-toxic and/or renewably sourced chemicals. Phosphorylated cellulose should form covalent linkages with ZnO and TiO2 nanoparticles. The interaction between phosphonates and oxide surfaces are used for modification of the oxide surfaces. In essence, the procedure consists of condensing the cellulose textile with a bis(phosphonic acid), phosphonate, or phosphate species, either organic or inorganic. Urea may be added to forestall discoloration of the textile. Phosphorylation takes place driven by the elimination of water. The resulting phosphorylated textile will directly bind both zinc oxide and titanium oxide nanoparticles. It will be necessary to restrict the degree of phosphorylation of the textile to prevent great alteration in the properties of the textile by controlling a reaction time. This process does not require in situ synthesis of the zinc oxide nanoparticles. Commercially available zinc oxide nanoparticles may be used.
  • A sample of cotton textile is wetted with a 10% v/v solution of phosphoric acid or bis-phosphonic acid containing 10-30% w/v urea. The textile is pressed to remove excess solution and baked in an oven at 85-100° C. for 5 minutes to dry, then at 170° C. for 2-4 minutes to cure unreacted groups. The textile is removed from the oven and washed with water. The textile is then used without further modification in subsequent deposition steps.
  • EXAMPLE 5 Modification of a Textile by Partial TEMPO-H2O2 Oxidation
  • A sample of cotton textile (ca. 1 g) is added to a solution composed of 90 mL water with 10 mg (0.065 mmol) TEMPO and 0.22 g (2 mmol) sodium bromide. Hydrogen peroxide 3% is added (0.9 mL, 1 mmol) and the reaction stirred at RT for 10 minutes to 2 hours. The material is washed with water, dried, and used without further modification in the following ZnO deposition step.
  • EXAMPLE 6 Immobilization of Nanoparticles on a Phosphorylated or Carboxylated Cellulose Surface
  • Ca. 1 mg/mL nanoparticles are suspended in water, ethyl alcohol, or other solvent. The phosphorylated or carboxylated cellulose textile is added to the suspension and the suspension is gently mixed over a reaction period of 1 to 12 hours. The textile is removed from the suspension and subjected to tumble drying or another drying procedure to force surface condensation and cure remaining groups.
  • The following example discloses modifying UV-blocking nanoparticles with a self-assembled monolayer (SAM) or polymer layer containing an active chemical group capable of binding to the fabric and deposited on the fabric from solution.
  • EXAMPLE 7 Grafting to Attachment of Cellulose to Nanoparticles Through Reactive Groups
  • In this method, ZnO particles are synthesized separately by any of the means discussed in Examples 1-3 or the ZnO particles may be purchased commercially. The ZnO particles are suspended in water or a weak non-nucleophilic aqueous buffer and an organosilane or phosphonate with one of the given combinations of reactive groups, as shown in Table 1, is added. Multidentate ligand or polymeric silanes may also be added to this mixture to facilitate the formation of a durable reactive layer and an oxide, alkoxide, or salt of another metal such as Ti or Si may be added first to form a surface layer of another oxide in the ZnO particles. After a reaction time of 1 to 12 hours, the particles are collected by centrifugation and washed with water. The particles are then resuspended in water or buffer and added to the textile. The conditions for binding of the particles to the textile vary depending on the headgroup, as shown in Table 1, but may involve direct application of the particles to the textile similarly to the process disclosed in Example 6, raising the pH of the suspension containing the textile, or heating the textile either in or after removal from the suspension. This process has the advantage of yielding extremely fine control over the nature of the linkage between particle and textile. This process has a further advantage in that the treated textile will be durable due to the robustness of self-assembled siloxane layers on oxide.
  • TABLE 1
    Molecule name (if
    commercially Commercially
    available) Linker Headgroup available?
    3-glycidoxypropyl- Triethoxysilane Glycidyl ether Yes
    triethoxysilane
    2-(3,4-cyclohexyloxy) Triethoxysilane Cyclohexyl oxide Yes
    ethyltriethoxysilane
    Hydroxymethyl- Triethoxysilane Hydroxymethyl Yes
    triethoxysilane
    Isocyanatopropyl Trimethoxysilane Isocyanate Yes
    trimethoxysilane
    Bis(triethoxysilyl) Triethoxysilane (2) N/A Yes
    ethane
    6-azidosulfonylhexyl Triethoxysilane Axidosulfonyl Yes
    triethoxysilane
    Triethoxysilane Vinylsulfone No
    Triethoxysilane Aryl azide No
    Phosphonate Glycidyl ether No
    Phosphonate Cyclohexyl oxide No
    Phosphonate Azidosulfonyl No
    Phosphonate Vinylsulfone No
    Phosphonate Aryl azide No
    Bis(triethoxysilyl) Triethoxysilane (2) Secondary amine Yes
    propylamine
    APTES/EGDE Triethoxysilane Amine/Ethylene Yes, 2 components
    glycol diglycidyl ether
  • The terms “fabric” or “textile” are intended to include fibers, filaments, yarn, textiles, material, woven and non-woven fabric, knits, and finished products such as garments. The methods described above may be used in treating fibers, filaments, yarn, textiles, and fabrics. For example, fibers may be initially treated by use of one or more of the above disclosed methods and the fibers may be manufactured into a fabric or a textile. Once manufactured into a fabric, the fabric may be treated by use of one or more of the disclosed methods. In this manner, individual fibers and the entire fabric are treated to incorporate UV protection. As can be appreciated, the treated fabric may be used to manufacture a garment such as, by way of example only, shirts, pants, hats, coats, jackets, shoes, socks, uniforms, athletic clothing, and swimwear. It is also possible and contemplated that the treated fabric may be used to construct non-apparel items such as blankets, sheets, sleeping bags, backpacks, and tents.
  • Further, it is also possible to further modify ZnO particles with a thin layer of other oxides in a “core-shell” type procedure by adding a reactive precursor to a suspension of the ZnO oxides. Oxides that can be deposited in this manner include SiO2 from tetraethoxysilane (TEOS) or sodium silicate, and Al2O3 and TiO2 either from the appropriate alkoxides, aluminate/titanate compounds, or other hydrolyzable aluminum or titanium compounds. A second oxide shell of this type may enhance the formation and stability of both directly applied ZnO-textile conjugates and those formed by modification of nanoparticles with an organic monolayer. ZnO can also be modified by the addition of a multidentate silane along with a silane containing the desired functional group. The multidentate silane yields a more densely crosslinked siloxane surface than monodentate silanes alone, forming a more stable layer on ZnO.
  • Although the above examples and methods are applicable to the manufacturing process in which ultraviolet radiation protection is incorporated into the fabric, textile, or garment when initially produced, the following discloses various methods of incorporating ultraviolet radiation protection directly to clothing being laundered. By use of the following methods, a garment after purchase may be made a protected garment by an end user.
  • In general, the methods may comprise the self-assembly of certain polyanionic materials onto a ZnO surface to create a linker which will bind the particles to a cellulose (cotton) surface. Several acidic or oxyanion functional groups are capable of self-assembly onto ZnO. These functional groups include siloxane, silanol, carboxylic acid, carboxylate, phosphonic acid, phosphonate, boronic acid or other groups capable of binding to oxide layers. Boronic acid is capable of forming very strong interactions with carbohydrates, including the glycosidically linked glucose units making up cellulose. One method or approach is to prepare a polymer bearing boronic acid groups and use that polymer to bind ZnO to cotton.
  • Various methods or processes are disclosed herein for the treatment of fabric to incorporate UV protection in the fabric by use of a laundry additive. One method is identified as the cellulose-to-oxide method. A second method is termed the oxide-to-cellulose method. A third method is described as the free mixing method.
  • EXAMPLE 8 The Cellulose-To-Oxide Method
  • In this method, cotton garments are pre-treated with boronic acid polymer resulting in cloth or fabric coated with boronic acid groups capable of binding to suspended uncoated ZnO particles. A home washing machine having the capability of adding a substance on a delayed basis may be used. In particular, boronic acid polymer is added to laundry detergent or added at the beginning of the laundry cycle. A suspension of ZnO particles may be added to a compartment in the washing machine that will dispense the particles on a delayed basis. For example, several washing machines have a compartment for storing bleach which is dispensed later on in the laundry cycle. The suspension of ZnO particles may be placed in the bleach compartment to be dispensed at the time that bleach would normally be dispensed into the washing machine. The washing machine would initially mix the clothing with the boronic acid material. This will result in the clothing bearing boronate groups. At the end of the delayed period the washing machine will dispense the suspension of ZnO particles into the washing machine. The ZnO particles will bind to the boronate groups and become attached to the clothing. It is also possible and contemplated that the suspension of ZnO particles may be manually added to the washing machine in a delayed manner. Manually adding the suspension may be required if the washing machine is not equipped with a compartment for adding bleach on a delayed basis.
  • EXAMPLE 9 Oxide-To-Cellulose Method
  • In this method, ZnO particles are treated with boronic acid polymer. Once prepared, these particles may be either mixed with laundry detergent and distributed in that form or sold as a separate additive that may be added to laundry detergent. The particles mixed with the laundry detergent or the separate additive is used in the washing machine as normal. During the course of the wash cycle, the boronic acid groups attach to the ZnO particles would assemble on and bind to cotton or other cellulose clothing. This results in a ultraviolet protected garment.
  • EXAMPLE 10 Free Mixing Method
  • In this method, boronic acid polymer and ZnO particles (untreated) are incorporated into the laundry detergent preparation in the solid phase. When added to a laundry cycle or wash cycle the detergent and water will solubilize these materials causing boronic acid polymer to assemble on both ZnO and cellulose. This will result in linked ZnO material. This method may require more boronic acid polymer and ZnO particles then the more controlled methods disclosed in Examples 8 and 9 to yield adequate grafting densities of ZnO on clothing.
  • Use of any of the methods disclosed in Examples 8, 9, or 10 will result in ZnO particles being bound to the fabric that is being washed in a conventional household washing machine. Once the ZnO particles are bound to the fabric, the fabric will have incorporated therein ultraviolet radiation protection. It is also possible and contemplated that the various methods described in Examples 8, 9, and 10 may be used more than once to incorporate ultraviolet radiation protection into clothing. For example, clothing may be treated by use of one or more of these methods and over time and after numerous washings the ultraviolet radiation protection may diminish. If there is any concern about the ultraviolet radiation protection of the garment, the garment may be washed using the various methods discussed in Examples 8, 9, and 10. Further, it is possible that a consumer may purchase a garment that has been treated using the methods described in Examples 1-7. Again, over time the ultraviolet radiation protection of the garment may decline. The consumer may use the methods disclosed in Example 8, 9, and 10 to wash the garment to again incorporate ultraviolet radiation protection into the garment.
  • All synthetic material such as polyester and nylon that is used in the manufacture of athletic clothing or active wear clothing may be rendered UV-absorbing using a ZnO preparation. These types of fabrics may resist treatment using the methods as outlined with respect to Examples 8, 9, and 10. One solution to this problem is to prepare ZnO particles coated with functional groups capable of being grafted directly to polyester or nylon materials. This may be accomplished by using benzophenone photografting chemistry. The following examples and methods are applicable to the manufacturing process in which ultraviolet radiation protection is incorporated into the artificial or synthetic fabric, textile, or garment when initially produced.
  • The following methods provide for the direct grafting of ZnO particles to nonpolar, non-natural polymers such as nylon and polyester. Nylon and polyester have little in the way of chemical functionality, containing only alphatic and aromatic C-H bonds and amide or ester linkages between monomers. The method is capable of directly functionalizing C-H bonds. The following method describes preparing ZnO particles coated with functional groups capable of being grafted directly to polyester or nylon materials by using the photografting reaction of benzophenone.
  • EXAMPLE 11 Grafting ZnO onto Artificial or Synthetic Fibers
  • In this method, an artificial fabric composed of polyester, nylon, or other polymer lacking hydroxyl functional group is modified by use of a preparation of a zinc oxide particle modified with a layer of reactive groups capable of C-H activation. Examples of the reactive functional group capable of C-H activation are benzophenone, sulfonylazides, aryl azides, or diazonium salts. The prepared particles are coated onto the fabric and a reaction is initiated using UV light, heat, or both. By way of example only, a mercury-vapor UV lamp may be used and the time for exposure may be one hour. Unbound particles are washed off the fabric. This second step, a curing step, bonds the prepared particles to the fabric. This method adds a second UV-absorbing chromophore which cross-links and becomes further bonded to the polymer surface of the fabric upon exposure to UV light. In this method, zinc oxide particles can be composed of pure zinc oxide or zinc oxide coated with aluminum, titanium, or silicon oxides in a core-shell configuration. The result is an artificial fabric with photografted zinc oxide particles.
  • By way of example, the zinc oxide particles were prepared in the following manner. Five grams of zinc oxide nanoparticles were used and suspended in a solution of 98% ethyl alcohol. Two grams of benzophenone silane linker were suspended in this solution and the pH of the solution was adjusted to 12. After 12 hours, the zinc oxide particles were recovered by centrifugation and dried overnight at 50-60° C. in an oven.
  • It is also possible to prepare a phosphoether of 4-hydroxybenzophenone and use this self-assembling molecule to functionalize ZnO particles. The resulting particles, having a monolayer of nonpolar molecules, will be substantially nonpolar and will adhere to nonpolar polyester and nylon. In order to bond the particles to the polymer surface an UV light may be used to initiate a reaction. Again, the process has the advantage of adding a second UV absorbing chromophore which cross-links and becomes further bonded to the polymer surface upon exposure to UV light.
  • It is also known that some cotton fabrics or yarns are mercerized through a series of processes to add luster to the fabrics or yarns. The mercerization process typically requires that cotton be held under tension for a specific amount of time while having between 21%-23% caustic soda (NaOH) applied to the cotton at room temperature. The process may include neutralizing the cotton by washing with water or by using an acid bath. Once the process is completed, the cotton fabric or yarn has increased luster, increased strength, is easier to dye, and resists mildew. However, the treated cotton does not include any ultraviolet radiation protection.
  • Although the above examples and methods are applicable to the manufacturing process in which ultraviolet radiation protection is incorporated into the fabric, textile, or garment when initially produced, the following discloses various methods of incorporating ultraviolet radiation protection into mercerized cotton. By use of the following methods, mercerized fabric, textile, or a garment may be made an ultraviolet radiation protected fabric, textile, or garment for an end user. In the following examples and the claims appended hereto, the word or term “cotton” is intended to mean or include fibers, filaments, yarn, textiles, material, woven and non-woven fabric, knits, and finished products such as garments.
  • In general, the methods may comprise impregnating cotton with ZnO that involves treating the textile with aqueous Zn(II) solution followed by addition of ca. 2M NaOH solution with subsequent washing steps. By use of the following methods it is possible to incorporate ultraviolet radiation protection into mercerized cotton.
  • EXAMPLE 12 Pretreatment
  • In this method, cotton is pretreated with a solution of NaOH followed by transfer to Zn(II) solution. The pretreatment step is to place the cotton in a concentrated mercerization strength NaOH solution before placing the cotton into Zn(II) solution. Since mercerization generally greatly enhances absorption of dyes on cellulose, the cotton will readily incorporate the deposition of ZnO on or in the mercerized cotton. After the cotton is treated in the Zn(II) solution, a solution of ca. 2M NaOH may be added. After a sufficient time, the cotton is removed from the NaOH solution and may be washed or rinsed and then dried. It is possible that the cotton may be washed or rinsed more than once.
  • EXAMPLE 13 Treatment of Cotton Followed by Neutralization
  • In this method, cotton is swelled with a strong NaOH solution and after the optional step of pressing and/or stretching the cotton as part of the mercerization process, the cotton is transferred to a Zn(II) solution. Retained NaOH in the cotton reacts with the Zn(II), depositing ZnO on the cotton and in the fibers of the cotton. After a sufficient time, the cotton is removed from the Zn(II) solution, washed or rinsed, and then allowed to dry. This method does not require an acid recycling step.
  • EXAMPLE 14 Mercerized Cotton
  • In this method, previously mercerized cotton is used. The mercerized cotton is placed into a Zn(II) solution. The ZnO is deposited on the cotton and in the fibers of the cotton. The cotton is removed from the Zn(II) solution after a period of time, washed or rinsed, and then allowed to dry.
  • The solution of Zn(II) or the ZnO nanoparticles may be produced by any of the methods described above in Examples 1-3 to be used in Examples 12-14.
  • From all that has been said, it will be clear that there has thus been shown and described herein a fabric having ultraviolet radiation protection incorporated into the fabric which fulfills the various advantages sought therefore. It will become apparent to those skilled in the art, however, that many changes, modifications, variations, and other uses and applications of the subject fabric having ultraviolet radiation protection incorporated into the fabric are possible and contemplated. All changes, modifications, variations, and other uses and applications which do not depart from the spirit and scope of the disclosure are deemed to be covered by the disclosure, which is limited only by the claims which follow.

Claims (20)

What is claimed is:
1. A method for treating mercerized cotton for incorporating ultraviolet radiation protection into the mercerized cotton comprising the steps of:
placing the mercerized cotton into a solution of Zn(II);
removing the mercerized cotton from the solution; and
washing the mercerized cotton.
2. The method of claim 1 further comprising the step of drying the mercerized cotton.
3. The method of claim 1 wherein the solution of Zn(II) comprises zinc acetate dissolved in water.
4. The method of claim 3 wherein the solution of Zn(II) further comprises 4.39 g. of zinc acetate (20 mmol) dissolved in 100 mL of deionized water.
5. The method of claim 3 wherein the solution of Zn(II) further comprises 4.39 g. of zinc acetate (20 mmol) dissolved in 100 ml of distilled water.
6. The method of claim 1 wherein the solution of Zn(II) comprises zinc acetate dissolved in water and amine added added to the zinc acetate dissolved in water.
7. The method of claim 6 wherein the amine comprises ethanolamine, ethylenediamine, or (tris)hydroxymethylaminomethane.
8. The method of claim 1 wherein the solution of Zn(II) comprises zinc sulfate heptahydrate, sodium chloride, and sodium hydroxide.
9. The method of claim 8 wherein the zinc sulfate heptahydrate comprises 5.75 g. zinc sulfate heptahydrate (20 mmol), the sodium chloride comprises 0.88 g (15 mmol) sodium chloride, and the sodium hydroxide comprises 1.6 g. (40 mmol) sodium hydroxide.
10. A method for treating cotton for incorporating ultraviolet radiation protection into the cotton comprising the steps of:
placing the cotton into a concentrated mercerization strength NaOH solution;
placing the cotton into a solution of Zn(II);
removing the cotton from the solution of Zn(II); and
washing the cotton.
11. The method of claim 10 further comprising the step of drying the cotton.
12. The method of claim 10 wherein the solution of Zn(II) comprises zinc acetate dissolved in water.
13. The method of claim 12 wherein the solution of Zn(II) further comprises 4.39 g. of zinc acetate (20 mmol) dissolved in 100 mL of deionized water.
14. The method of claim 12 wherein the solution of Zn(II) further comprises 4.39 g. of zinc acetate (20 mmol) dissolved in 100 ml of distilled water.
15. The method of claim 10 wherein the solution of Zn(II) comprises zinc sulfate heptahydrate, sodium chloride, and sodium hydroxide.
16. The method of claim 15 wherein the zinc sulfate heptahydrate comprises 5.75 g. zinc sulfate heptahydrate (20 mmol), the sodium chloride comprises 0.88 g (15 mmol) sodium chloride, and the sodium hydroxide comprises 1.6 g. (40 mmol) sodium hydroxide.
17. A method for treating cotton for incorporating ultraviolet radiation protection into the cotton comprising the steps of:
placing the cotton into a concentrated mercerization strength NaOH solution;
placing the cotton into a solution of Zn(II);
placing the cotton into a solution of NaOH;
removing the cotton from the solution of NaOH; and
washing the cotton.
18. The method of claim 17 further comprising the step of drying the cotton.
19. The method of claim 17 wherein the solution of Zn(II) comprises zinc acetate dissolved in water.
20. The method of claim 17 wherein the solution of Zn(II) comprises zinc sulfate heptahydrate, sodium chloride, and sodium hydroxide.
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US10443159B2 (en) 2013-08-15 2019-10-15 Arun Agarwal Proliferated thread count of a woven textile by simultaneous insertion within a single pick insertion event of a loom apparatus multiple adjacent parallel yarns drawn from a multi-pick yarn package
US10808337B2 (en) 2013-08-15 2020-10-20 Arun Agarwal Proliferated thread count of a woven textile by simultaneous insertion within a single pick insertion event of a loom apparatus multiple adjacent parallel yarns drawn from a multi-pick yarn package
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US9708737B2 (en) 2013-08-15 2017-07-18 Arun Agarwal Proliferated thread count of a woven textile by simultaneous insertion within a single pick insertion event of a loom apparatus multiple adjacent parallel yarns drawn from a multi-pick yarn package
US9481950B2 (en) 2013-08-15 2016-11-01 Arun Agarwal Proliferated thread count of a woven textile by simultaneous insertion within a single pick insertion event of a loom apparatus multiple adjacent parallel yarns drawn from a multi-pick yarn package
US10066324B2 (en) 2013-08-15 2018-09-04 Arun Agarwal Proliferated thread count of a woven textile by simultaneous insertion within a single pick insertion event of a loom apparatus multiple adjacent parallel yarns drawn from a multi-pick yarn package
US10472744B2 (en) 2013-08-15 2019-11-12 Arun Agarwal Proliferated thread count of a woven textile by simultaneous insertion within a single pick insertion event of a loom apparatus multiple adjacent parallel yarns drawn from a multi-pick yarn package
US9131790B2 (en) 2013-08-15 2015-09-15 Aavn, Inc. Proliferated thread count of a woven textile by simultaneous insertion within a single pick insertion event of a loom apparatus multiple adjacent parallel yarns drawn from a multi-pick yarn package
US9777411B2 (en) 2014-03-20 2017-10-03 Arun Agarwal Woven shielding textile impervious to visible and ultraviolet electromagnetic radiation
US9394634B2 (en) 2014-03-20 2016-07-19 Arun Agarwal Woven shielding textile impervious to visible and ultraviolet electromagnetic radiation
US10428445B2 (en) 2014-05-29 2019-10-01 Arun Agarwal Production of high cotton number or low denier core spun yarn for weaving of reactive fabric and enhanced bedding
US9708736B2 (en) 2014-05-29 2017-07-18 Arun Agarwal Production of high cotton number or low denier core spun yarn for weaving of reactive fabric and enhanced bedding
US11225733B2 (en) 2018-08-31 2022-01-18 Arun Agarwal Proliferated thread count of a woven textile by simultaneous insertion within a single pick insertion event of a loom apparatus multiple adjacent parallel yarns drawn from a multi-pick yarn package

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