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WO2025116901A1 - Procédés de nettoyage de matériaux textiles - Google Patents

Procédés de nettoyage de matériaux textiles Download PDF

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Publication number
WO2025116901A1
WO2025116901A1 PCT/US2023/081661 US2023081661W WO2025116901A1 WO 2025116901 A1 WO2025116901 A1 WO 2025116901A1 US 2023081661 W US2023081661 W US 2023081661W WO 2025116901 A1 WO2025116901 A1 WO 2025116901A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
textile material
stain
nanocrystalline
stained
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2023/081661
Other languages
English (en)
Inventor
Leticia MENZZANO
Kay ANDREWS
Brandon Walker
Kyle Knappenberger
George NEGRON
Eric STEWARD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Timilon Corp
Original Assignee
Timilon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Timilon Corp filed Critical Timilon Corp
Priority to PCT/US2023/081661 priority Critical patent/WO2025116901A1/fr
Publication of WO2025116901A1 publication Critical patent/WO2025116901A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention is generally directed toward methods for cleaning textile materials, particularly methods of removing stains from stained textile materials.
  • textile materials being laundered in batches may comprise a wide variety of textile materials having stains attributable to a wide variety of sources.
  • Commercially available stain removers may not address all such different types of stains equally, thus requiring application of multiple types of stain removers or detergents. It is burdensome to inspect each textile material in the laundry load, identify and characterize each stain, and select the type of detergent or stain remover needed to remove each stain. Thus, in most cases, textile materials are treated with a single detergent and as a result contain residual stains after they are treated.
  • the present invention is broadly concerned with a method of removing stains from a stained textile material.
  • the method comprises contacting the stained textile material with a detergent composition comprising one or more nanocrystalline metal oxide and/or metal hydroxide particles.
  • the contacting step results in a stain removal index for the portion of the stained textile material bearing the stain of at least 80.
  • the one or more nanocrystalline metal oxide and/or metal hydroxide particles is selected from the group consisting of MgO, CeCh, CaO, TiCh, ZrO 2 , FeO, V2O3, V2O5, MmCh, Fe 2 O3, NiO, CuO, AI2O3, ZnO, SiCh, Ag 2 O, SrO, BaO, Mg(OH) 2 , Ca(OH) 2 , A1(OH) 3 , Ti(OH) 4 , Sr(OH) 2 , Ba(OH) 2 , Fe(OH) 3 , Cu(OH) 2 , Ni(0H) 2 , CO(OH) 2 , Zn(OH) 2 , AgOH, coated metal oxides and hydroxides, doped metal oxides and hydroxides, and mixtures thereof.
  • the contacting step may further comprise dispersing the detergent composition in water to form a wash solution, the wash solution being contacted with the stained textile material.
  • the contacting step may further comprise adding the stained textile material and the detergent composition to a washing machine and commencing an automated washing cycle in which the detergent composition is diluted or dispersed in water to form a wash solution.
  • the present invention is broadly concerned with a method of removing one or more stains from a stained textile material.
  • textile material refers to any material made from natural or synthetic fibers, yams, threads, and/or blends thereof.
  • stain refers to a discoloration produced by foreign matter (i.e., stain-causing substance) having penetrated into or chemically reacted with a material, such as a textile material, that is not easily removed by water and/or conventional detergents that comprise, consist of, or consist essentially of one or more surfactants.
  • Common stains include, but are not limited to peat stains (which may be attributable to the presence of dark-colored organic compounds), chocolate stains (which may be attributable to the presence of cocoa solids and cocoa butter present within the chocolate), blood stains (which may be attributable to the presence of hemoglobin and/or other proteins and lipids making up blood), coffee stains (which can be attributed to Maillard reaction products present within the coffee), plant or grass stains (which may be attributable to the presence of chlorophyll), grease stains (which may be attributable to the presence of lipids, e g., vegetable oils, or petroleum products in the case of motor oil, for example), ink stains (which may be attributable to the presence of pigments or dyes), sauce/condiment stains, including ketchup and mustard stains (which can be
  • the method comprises contacting the stained textile material with a detergent composition, which may be in a powder or liquid form.
  • the detergent composition may comprise one or more nanocrystalline materials, preferably nanocrystalline metal oxide and/or nanocrystalline metal hydroxide particles.
  • Preferred nanocrystalline materials for use in connection with the present invention include the metal oxides and metal hydroxides of Mg, Sr, Ba, Ca, Ti, Zr, Fe, V, Mn, Ni, Cu, Al, Si, Zn, Ag, Mo, Sb, and mixtures thereof. Additional preferred nanocrystalline materials include coated nanocrystalline materials such as those disclosed in U.S. Patent Nos.
  • 6,887,302 and 6,860,924 nanocrystalline materials coated with a surfactant, wax, oil, silyl, synthetic or natural polymer, or resin
  • biocidal doped metal oxides such as silver-doped alumina
  • metal oxide or metal hydroxide particles impregnated with a biocide as described in U.S. Pat. No. 6,827,766, pelletized nanocrystalline materials such as those described in U.S. Pat. No. 6,093,236 and U.S. Reissued Pat. No. RE39,098, and composites using agglomerated nanocrystalline particles with a first material coated by second material such as those described in U.S. Pat. Nos. 7,341,977 and 7,566,393, all of which are incorporated by reference herein in their entireties.
  • the detergent composition comprises, consists essentially of, consists of at least one nanocrystalline metal oxide and/or nanocrystalline metal hydroxide particles selected from the group consisting of MgO, CeCh, CaO, TiO 2 , ZrO 2 , FeO, V2O3, V2O5, Mn 2 O 3 , Fe 2 O 3 , NiO, CuO, AI2O3, ZnO, SiO 2 , Ag 2 O, SrO, BaO, Mg(OH) 2 , Ca(OH) 2 , A1(OH) 3 , Ti(OH) 4 , Sr(OH) 2 , Ba(OH) 2 , Fe(OH)3, Cu(OH) 2 , Ni(0H) 2 , Co(OH) 2 , Zn(OH) 2 , AgOH, coated metal oxides and hydroxides, doped metal oxides and hydroxides, and mixtures thereof.
  • nanocrystalline metal oxide and/or nanocrystalline metal hydroxide particles selected from the group consisting of MgO, CeCh, CaO, Ti
  • the detergent composition comprises, consists essentially of, consists of at least two nanocrystalline metal oxide and/or metal hydroxide particles selected from the group consisting of MgO, TiO 2 , ZnO, AI2O3, Mg(OH) 2 , Ti(OH)4, Zn(OH) 2 , and Al(0H)3.
  • the detergent composition comprises, consists essentially of, consists of at least three nanocrystalline metal oxide and/or metal hydroxide particles selected from the group consisting of MgO, TiO 2 , ZnO, AI2O3, Mg(OH) 2 , Ti(OH) 4 , Zn(OH) 2 , and A1(OH) 3 .
  • the nanocrystalline metal oxide and/or metal hydroxide particles are present in the detergent composition at a level of from about 1% to about 40% by weight, preferably from about 2% to about 30% by weight, more preferably from about 5% to about 20% by weight, and most preferably about 10% by weight. All wt. % ranges expressed herein are based upon the weight of the total detergent composition being 100% unless otherwise specified.
  • the nanocrystalline metal oxide particles comprise, consist essentially of, or consist of nanocrystalline MgO particles, nanocrystalline ZnO particles, and nanocrystalline AI2O3 particles.
  • the MgO particles are present within the detergent composition at a level of from about 0.1% to about 20% by weight, or from about 1% to about 15% by weight, from about 2.5% to about 10% by weight, or about 5% by weight.
  • the ZnO particles are present at a level of from about 0.1% to about 10% by weight, or from about 0.5% to about 7.5% by weight, from about 1% to about 5% by weight, or about 2.5% by weight.
  • the A1 2 O3 particles are present at a level of from about 0.1% to about 10% by weight, or from about 0.5% to about 7.5% by weight, from about 1% to about 5% by weight, or about 2.5% by weight.
  • the MgO particles make up the predominant component of the nanocrystalline metal oxide particles, with ZnO and AI2O3 particles each being minority components of the nanocrystalline metal oxide particles.
  • the nanocrystalline materials preferably present crystallite sizes of less than about 25 nm, more preferably less 20 than nm, and most preferably less than 10 nm.
  • the nanocrystalline particles preferably exhibit a Brunauer-Emmett-Teller (BET) multipoint surface area of at least about 15 m 2 /g, more preferably at least about 70 m 2 /g, and most preferably from about 100-850 m 2 /g.
  • Exemplary nanocrystalline materials are available from Timilon Corporation, Bonita Springs, Florida, under the name NanoActive®.
  • the nanocrystalline materials in the detergent composition are particularly useful in methods of cleaning textile materials, and especially in the removal of stains from stained textile materials.
  • nanocrystalline metal oxide and hydroxide particles have been shown to be useful as destructive adsorbents for various malodors and toxic materials, including acid gases, air pollutants, and chemical and biological warfare agents, due to their high surface reactivity (see e.g., U.S. Pat. Nos. 8,183,426, 8,038,935, 7,956,232, 7,566,393, 7,341,977, 7,335,808, 7,279,129, RE39,098, U.S. Pat. Nos.
  • nanocrystalline particles when used in conjunction with one or more components making up a detergent composition, are capable of removing different types of stains in textile materials.
  • the nanocrystalline materials are capable of adsorbing and neutralizing the stain-causing substances in the textile materials.
  • the detergent composition further comprises one or more additives, such as those disclosed in U.S. Pat. No. 10,362,784, which is incorporated by reference herein in its entirety.
  • the additives may be, but are not limited to, anti-dispersion agents, builders/boosters (e.g., sodium carbonate, aluminosilicates, citrates, and sodium silicate), emulsifying and suspension agents (e.g., sodium metasilicate ), chelators (e.g., organic acids, such as citric acid, sodium and potassium salts of ethylene diaminetetraacetic acid and nitrilotri acetic acid, sodium and potassium salts of methyl glycine diacetic acid, and bisphosphonates, that react with naturally occurring metal ions in water and prevent the ions from interfering with the cleaning action of the surfactants), solubilizing agents (e.g, low molecular weight alcohols such as ethanol, propanol, isopropanol
  • the surfactant may be an anionic surfactant, cationic surfactant, or a nonionic surfactant.
  • anionic surfactants include alkyl sulfates such as sodium lauryl sulfate, sodium laureth (sodium lauryl ether sulfate-SLES) sulfate; ammonium lauryl or laureth sulfate, TEA lauryl or laureth sulfate, MEA lauryl or laureth sulfate, potassium lauryl or laureth sulfate, sodium dodecyl sulfate (SDS), sodium octyl/decyl sulfate, sodium 2-ethyl-hexyl sulfate, sodium octyl sulfate, alkyl ethoxylates, alkyl ethoxylate sulfates, alkyl
  • amphoteric surfactants include the general class of alkyl betaines as laurylamidopropyl betaine, oleyl betaine, ether amine oxides as lauryl dimethyl amine oxide, cocoamidopropyl dimethyl amine oxide and phospholipids composed of diester and triester phosphatides.
  • nonionic surfactants include various linear or non-phenol alcohols or fatty acids, ethers of fatty alcohols, octylphenoxy polyethoxy ethanol, ethoxylated alcohols (e.g., laueth-7, PEG-10, and PEG 400), ethoxylated amines, ether amines and ether diamines as cocoamid DEA, cocoamide MEA, esters as ethylene glycol monostearate, ethylene glycol distearate as polyoxyethylene sorbitan esters, polysorbates, linear ethylene oxide/propylene oxide and/or butylenes oxide block copolymers, poly(5) oxyethylene isodecyloxypropylamine, poly (5) oxyethylene isotridecyloxypropylamine, glycols, and amine oxides as long chain alkyls.
  • ethoxylated alcohols e.g., laueth-7, PEG-10, and PEG 400
  • Preferred nonionic surfactants include polysorbates (e.g., Tween 20, 40, or 80), Igepal, Tritons, and glucosides as decyl glucoside, lauryl glucosides, D-glucopyranoside CIO to C16 alkyl oligomer and D- glucopyranoside C6 to C12 alkyl oligomer.
  • polysorbates e.g., Tween 20, 40, or 80
  • Igepal Tritons
  • Tritons Tritons
  • glucosides as decyl glucoside, lauryl glucosides, D-glucopyranoside CIO to C16 alkyl oligomer and D- glucopyranoside C6 to C12 alkyl oligomer.
  • the nanocrystalline particles comprise, consist essentially of, or consist of nanocrystalline MgO particles, nanocrystalline ZnO particles, nanocrystalline AI2O3 particles, SLS, sodium carbonate, sodium chloride, and sodium metasilicate.
  • the wash solution may be formed according to any method known to one of ordinary skill in the art.
  • the wash solution may advantageously be formed before or during the contacting step.
  • the method may comprise diluting and/or dispersing the detergent composition in a liquid, such as water, to form the wash solution, which is then contacted with the stained textile material.
  • the contacting step may comprise adding the stained textile material and the detergent composition to a washing machine and commencing an automated washing cycle in which the detergent composition is diluted or dispersed in water to form the wash solution.
  • the washing machine may be a residential-type washing machine or a commercial-grade washing machine.
  • the method/contacting step comprises diluting and/or dispersing within a desired quantity of the liquid to form the wash solution from about 1 gram to about 25 grams, preferably from about 4 grams to about 20 grams, and more preferably from about 7.5 grams to about 1 grams of the detergent composition per kilogram of the stained textile material to be cleaned.
  • the contacting step removes at least a portion of the stain.
  • the contacting step results in a stain removal index (SRI) of at least 80, at least 85, at least 90, at least 95, or at least 97.
  • SRI stain removal index
  • the terms “stain removal index” refers to the performance/effectiveness of the detergent composition and/or wash solution in treating a stain and/or stained textile material. That is, the SRI defines the relationship of the appearance of an unstained textile to the appearance of a treated stained textile of the same material. The SRI is a scale from 0-100, with 0 meaning no stain removal, and 100 meaning complete stain removal.
  • the SRI may be measured directly using an instrument, such as a spectrophotometer, or the SRI may be calculated.
  • the degree of the stain/stained textile material should first be evaluated. To do this, averaged reflectance measurements of the stained textile material may be taken using a colorimeter or similar device known to one of ordinary skill in the art. These measurements are preferably taken at three different times: (1) before the textile material is stained, (2) after the textile material is stained, and (3) after the textile material is treated or washed with the detergent composition and/or wash solution. After the degree of the stain is evaluated, the SRI may then be calculated, preferably using the following formula:
  • SRI stain removal index
  • the phrase "and/or," when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed.
  • the composition can contain or exclude A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
  • the present description also uses numerical ranges to quantify certain parameters relating to various embodiments of the invention. It should be understood that when numerical ranges are provided, such ranges are to be construed as providing literal support for claim limitations that only recite the lower value of the range as well as claim limitations that only recite the upper value of the range. For example, a disclosed numerical range of about 10 to about 100 provides literal support for a claim reciting "greater than about 10" (with no upper bounds) and a claim reciting "less than about 100" (with no lower bounds).
  • NP detergent nanocrystalline particles
  • two conventional detergents i.e., Country Save and Tide Free & Gentle
  • mustard, ketchup, and dirt (i.e., soil) stains applied to various controls and test articles (i.e., 1 bath towel, 3 dish cloths, 2 undershirts, and 1 pillowcase).
  • the following stain and washing procedures were followed.
  • the NP detergent formulation comprises 54% sodium carbonate, 18% SLS, 9% NaCl, 9% sodium metasilicate, and 10% nanocrystalline metal oxide powders (2 parts MgO, 1 part AI2O3, 1 part ZnO).
  • each article was labeled with the letter of designated stain (M - mustard, K - ketchup, D - dirt). Finally, each stain was allowed to dry/set for 1 hour, and the color values of the stains (US) were measured using the Colorimeter.
  • Detergent Amounts were determined per laundry load (total weight « 0.83 kg (1.83 lbs.)), which is ⁇ 25% of the standard 8 lbs./ load (medium load).
  • NP detergent 9.3 grams of Country Save, and 11.5 grams of Tide Free & Gentle were used per laundry load.
  • Washing Procedure A laundry load comprising 1 bath towel, 1-3 test articles, 3 dish cloths, 2 undershirts, and 1 pillowcase were washed using a Magic Chef Portable Washing Machine (1.6 cu. ft.), and each article (i.e., bath towel, test articles, dish cloths, undershirts, and pillowcase) was loaded into the washing machine in the foregoing order. After the articles were loaded, the articles were washed (heavy, small washer settings) at a cold temperature setting (unheated tap water). Once washed, the articles were machine dried using a standard household dryeron air dry mode for about 57 minutes and subsequently air dried for about 1 hour. Then, the color values of the stains (WS) were measured using the Colorimeter.
  • Stain Measurements Stain removal measurements were based on ASTM D4265-21 Standard Guide for Evaluating Stain Removal Performance in Home Laundering. This test was used to determine the detergent composition’s cleaning efficiency by removing standard stains. Generally,
  • Colorimeter As discussed in Example 1, a Colorimeter, is used to measure the reflectance (L), redness/greenness (a), and yellowness/blueness (b) of a sample:
  • Stain Removal Index Three color measurements were taken: before stain application, after stain application (before washing), and after washing. Color differences were calculated and used to determine a Stain Removal Index, which may be calculated using the formula below. Index values range from 0 (no stain removal) to 100 (complete stain removal).
  • Stain Removal Index The performance of the detergent composition was evaluated instrumentally by an SRI.
  • the SRI is a scale from 0-100, with 0 meaning no stain removal, and 100 meaning complete stain removal.
  • the SRI is calculated as:
  • AE*(US-UF) Delta-E color difference between the unwashed stain (US) and the unwashed fabric (UF)
  • AE*(WS-UF) Delta-E color difference between the washed stain (WS) and the unwashed fabric (UF).
  • AE* (absolute color difference) is calculated as:
  • AE* A/AL* 2 + Aa* 2 + Ab* 2 .

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des procédés de nettoyage d'un matériau textile, en particulier des procédés d'élimination d'une ou de plusieurs taches d'un matériau textile coloré. Les procédés comprennent la mise en contact du matériau textile coloré avec une composition détergente ou une solution de lavage comprenant une ou plusieurs particules d'oxyde métallique nanocristallin et/ou d'hydroxyde métallique, qui sont avantageusement capables d'adsorber la ou les substances provoquant des taches dans la ou les taches. Avantageusement, l'étape de mise en contact conduit à un indice d'élimination des taches pour la partie du matériau textile coloré portant la tache d'au moins 80.
PCT/US2023/081661 2023-11-29 2023-11-29 Procédés de nettoyage de matériaux textiles Pending WO2025116901A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2023/081661 WO2025116901A1 (fr) 2023-11-29 2023-11-29 Procédés de nettoyage de matériaux textiles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2023/081661 WO2025116901A1 (fr) 2023-11-29 2023-11-29 Procédés de nettoyage de matériaux textiles

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009019076A1 (fr) * 2007-08-03 2009-02-12 Unilever Plc Dispositif de distribution d'enzymes
WO2018009434A1 (fr) * 2016-07-05 2018-01-11 Timilon Technology Acquisitions Llc Compositions et procédés pour former des formulations liquides stables d'oxyde/hydroxyde de métal
CN110252248A (zh) * 2019-07-09 2019-09-20 山东百普瑞世环境科技有限公司 复合二氧化硅抗菌吸附材料、制备方法及用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009019076A1 (fr) * 2007-08-03 2009-02-12 Unilever Plc Dispositif de distribution d'enzymes
WO2018009434A1 (fr) * 2016-07-05 2018-01-11 Timilon Technology Acquisitions Llc Compositions et procédés pour former des formulations liquides stables d'oxyde/hydroxyde de métal
CN110252248A (zh) * 2019-07-09 2019-09-20 山东百普瑞世环境科技有限公司 复合二氧化硅抗菌吸附材料、制备方法及用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LUDLOW DAVID: "Miele W1 WMB120 review", EXPERTREVIEWS.CO.UK, 5 March 2016 (2016-03-05), XP093333138, Retrieved from the Internet <URL:https://www.expertreviews.co.uk/home-garden/large-appliances/miele-w1-wmb120-review> *

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