WO2005100522A1 - Zero to low voc glass and general purpose cleaner - Google Patents

Zero to low voc glass and general purpose cleaner Download PDF

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Publication number
WO2005100522A1
WO2005100522A1 PCT/US2005/011948 US2005011948W WO2005100522A1 WO 2005100522 A1 WO2005100522 A1 WO 2005100522A1 US 2005011948 W US2005011948 W US 2005011948W WO 2005100522 A1 WO2005100522 A1 WO 2005100522A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
hard surface
voc
volatile
surfactant
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.)
Ceased
Application number
PCT/US2005/011948
Other languages
English (en)
French (fr)
Inventor
James J. Leskowicz
Loretta G. Lynch
Jacqueline V. Lepow
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.)
SC Johnson and Son Inc
Original Assignee
SC Johnson and Son Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SC Johnson and Son Inc filed Critical SC Johnson and Son Inc
Priority to EP05737586.7A priority Critical patent/EP1735417B1/en
Priority to AU2005233608A priority patent/AU2005233608B2/en
Priority to CA2561759A priority patent/CA2561759C/en
Priority to JP2007507528A priority patent/JP5265185B2/ja
Publication of WO2005100522A1 publication Critical patent/WO2005100522A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D3/43—Solvents
    • 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
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the present invention relates to compositions for cleaning hard surfaces, including glass surfaces.
  • the compositions contain from zero to low amounts only of one or more volatile organic compounds (VOCs) .
  • VOCs volatile organic compounds
  • Glass and general purpose cleaning compositions desirably have good cleaning; characteristics which include good detergency, evaporatability, and no streaking or hazing.
  • glass and general purpose cleaners depend on the usage of a combination of alcohols, high-volatile glycol ethers, low-volatile glycol ethers, and surfactants to obtain cleaning and acceptable drying rates.
  • Alcohols and high-volatile glycol ethers, such as used in conventional formulas are classified as VOCs while low-volatile glycol ethers and surfactants, as useful in trie present invention, are classified as non-VOCs.
  • non-VOC solvents are termed low-volatile non-VOC solvents.
  • a primary object of the present invention is to provide a glass and general purpose cleaning composition which has zero to low volatile organic compound (VOC) content while having acceptable cleaning and drying rates.
  • a further primary object is to provide a cleaning composition which delivers the attributes of streak-free cleaning and acceptable drying rates w-fcrate containing from zero to low, i.e., 0 to about 4% -by wt . , of VOCs.
  • a further primary object is to provide a glass and general purpose cleaning composition w-tiich provides acceptable cleaning and drying rates in the absence of volatile organic compounds, in particular alcohols.
  • the glass and general purpose cleaning composition of the invention has from greater than 0 to about 30% by weight of at least one low-volatile non-VOC organic compound as an evaporative solvent and from 0 to about 4% by weight of one or more VOC solvents. The solvents serve to provide both cleaning and acceptable drying rates .
  • the cleaning composition of the invention includes an aqueous carrier, one or more low-volatile non-VOC organic evaporative solvents, one or more surfactants, optionally one or more co-solvents, and. optionally one or more adjuvants such as pH adjusting agent (s) , colorant(s), fragrance (s) , coalescent ( s) and the like.
  • the components are included, in ranges of about greater than 0 to about 20% by wt. of the one or more J-3924A low-volatile non-VOC evaporative solvents, about greater than 0 to about 10% by wt. of the one or more surfactants, about 50 to about 99.9% by wt .
  • the cleaning composition of the invention is useful as a general surface cleaner, anti-bacterial cleaner, low VOC degreaser, soap scum remover, floor cleaner, and the like.
  • the cleaning composition can be dispensed by conventional means, such as in liquid, spray, aerrosol or gel form, either as a concentrate or in a ready to use dilute form.
  • a concentrate the composition can be diluted on use, e.g. by mixture with water in a bucket or by hose-end application.
  • the glass and general purpose cleaning composition of the invention has zero to low volatility based on the use of at least one low-volatile non-VOC evaporative solvent, such as low-volatile non-VOC glycol ether (s), in combination with one or more surfactants serving as cleaning agents, and an aqueous carrier and, optionally, at least one co-solvent different from the low-volatile non-VOC evaporative solvent.
  • the low volatile non-VOC evaporative solvents useful in the invention have limited solubility in water of less than 20% and reduce surface tension of the composition to less than 40 dynes/cm.
  • the sur actant is J-3924A preferably low-streaking and can be amphoteric, an ionic, nonionic, cationic or a mixture thereof.
  • the surfactant (s) and optional co-solvent (s) provide for good solubilization of the other components present in the composition in addition to acting as a cleaning agent.
  • the cleaning composition of the invention has a VOC content of from 0 to about 4% by wt . , preferably from about 0 to about 1% by wt . , more preferably from about 0 to about 0.5% by wt . , and most preferably about 0% by wt .
  • the low-volatile non-VOC evaporative solvent (s) is (are) preferably non-VOC glycol ethers. Such provide for streak-free cleaning.
  • Non-VOC glycol ethers suitable for use in the composition of the invention include those having a formula as follows: R ⁇ -0-R 2 wherein R- ⁇ is a C ⁇ -C 8 linear, branched or cyclic al-kyl or alkenyl, optionally substituted with -OH, -0CH 3 , or -OCH 2 CH 3 ; and R 2 is a C ⁇ -C 6 linear, branched or cyclic alkyl or alkenyl substituted with -OH.
  • R x is an optionally substituted
  • Ri is an unsubstituted or monosubstituted linear or branched C 3 -C 6 alkyl
  • R 2 is a monosubstituted C 2 -C 4 linear or branched alkyl.
  • i is an unsubstituted n-C 3 -C 4 or n-C ⁇ linear alkyl or J- 39 24 A -CH 2 CHCH 3 , I OH
  • Suitable non-VOC glycol ethers include tripropylene glycol n-propyl ether, ethylene glycol n-hexyl ether, diethylene glycol n-hexyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether and propylene glycol phenyl ether.
  • the preferred non-VOC glycol ether for inclusion in the cleaning composition is ethylene glycol n-hexyl ether, also known as hexyl cellosolve.
  • Other compounds suitable for use as the low- volatile non-VOC evaporative solvent include, but are not limited to, non-VOC glycol ethers, esters, polyhydric alcohols, amines, or other organic compounds with limited solubility in water, i.e., less than 20%, and serve to reduce surface tension of the aqueous composition to less than 40 dynes/cm. These solvents serve generally to provide cleaning of most oils, grease and dirt.
  • non-VOC evaporative solvents which are suitable for use include: (1) esters such as diethylene glycol monobutyl ether acetate; (2) polyhydric alcohols such as 2-ethyl-l,3- hexanediol (octanediol) , diethylene glycol; and (3) amines with limited solubility in water, i.e., less than 20%, and serve to reduce the surface tension of the aqueous composition to less than 40 dynes/cm.
  • the low-volatile non-VOC evaporative solvent is preferably present in an amount in a range of about 0.1 J-3924A to about 20% by wt . , more preferably about 0.1 to about 5% by wt. and most preferably about 0.1 to about 1% by wt .
  • Co-solvents suitable for use include non-VOC and VOC-type glycol ethers, aliphatic and polyhydric alcohols, ketones, acids, and amines.
  • the co-solvent (s) may be partially or fully soluble in water.
  • Such co-solvents serve to control drying and application properties.
  • These co-solvents can also provide additional cleaning of most oils, grease and dirt.
  • the co-solvent is a low volatile non-VOC solvent, such solvent has either a different water solubility or different tension reduction capacity as compared to the low volatile non-VOC evaporative solvent.
  • co-solvents different from the low-volatile non-VOC evaporative glycol ether solvents described above which are also suitable for use include (1) non-VOC and VOC glycols and glycol ethers such as tripropylene glycol methyl ether, diethylene glycol n- butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol n-butyl ether, ethylene glycol n-butyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, and propylene glycol n-propyl ether; (2) non-VOC and VOC esters such as methyl acetate, ethyl acetate, dipropylene glycol methyl ether acetate; (3) non VOC and VOC aliphatic and polyhydric alcohols such as, isopropanol, propylene glycol, 1, 3-butanedio
  • Such co-solvents are preferably present in an amount of from 0 to about 30% by wt . , more preferably about 0 to about 5% by wt . , and most preferably about 0 to about 1% by wt . of the cleaning composition. Necessarily if a VOC compound is used as a co-solvent, such compound is present in an amount so that the composition has less than about 4% by weight VOC content.
  • One or more surfactants can be present in the composition of the invention to provide cleaning and solubilization of the other components present in the composition.
  • the surfactant (s) can be amphoteric, anionic, nonionic, cationic or a mixture thereof. Preferably such surfactants are selected from low streaking surfactant compounds .
  • the one or more surfactants are present in an amount in a range of about 0 to about 10% by wt . ,, more preferably about 0 to about 3% by wt . , and most preferably about 0 to about 0.6% by wt .
  • Amphoteric surfactants suitable for use include, for example, betaines, alkyl imidazolines, coco- amphopropionates, or combinations thereof.
  • a preferred amphoteric surfactant is disodium cocoamphodipropionate (also known as cocoimidazoline carboxylate) such as sold under the tradename MACKAM 2CSF.
  • the amphoteric surfactant is preferably used under alkaline conditions to render the anionic portion of the amphoteric compound active. J-3924A
  • Suitable anionic surfactants for use include alkyl sulfates, alkyl benzene sulfonates, ⁇ -olefin sulfonates, alkyl taurates, alkyl sacrosinates, alkyl diphenyloxide disulfonates, alkyl naphthalene sulfonates, alkyl ether sulfates, alkyl ether sulfonates, sulfosuccinates, and other anionic surfactants as known for use in cleaning compositions.
  • the surfactants are typically available as the alkali metal, alkaline earth and ammonium salts thereof.
  • Preferred anionic surfactants are linear C 8 _i 6 alkyl sulfates, C 8 _ ⁇ 6 alkyl sulfonates, C 8 _ ⁇ 6 alkyl benzene sulfonates and C 8 _i 6 alkyl diphenyloxide disulfonates.
  • Most preferred anionic surfactants for use in the composition of the invention are decyl sulphophenoxy benzene/oxybis decyl benzene sulfonic acid disodium salt (such as sold under the tradename DOWFAX C10L surfactant) , and sodium octane sulfonate, sodium dodecyl sulfonate, and sodium lauryl sulfate.
  • Suitable nonionic surfactants for use in the cleaning composition include alkoxylated alcohols, alkoxylated ether phenols, silicone-based compounds such as silicone glycol copolymers, and semi-polar nonionics such as trialkyl a ine oxides .
  • Preferred nonionics are ethoxylated (EO) and/or propoxylated (PO) alcohols, such as EO and/or PO C 6 .
  • Cationic surfactants are also available for inclusion, both for cleaning ability and, upon suitable selection, anti-bacterial/germicidal characteristics, e.g. quaternary ammonium compounds.
  • useful cationic surfactants include N-alkyl trimethyl ammonium J-3 92 -4 A chloride, and dimethyl dicoco quaternary ammonium chloride.
  • the aqueous carrier is preferably water in an amount of about 30 to about 99.5% by wt . , more preferably- about 90 to about 99.5% by wt . and most preferably about 95 to about 99.5% by wt .
  • An additional component which can advantageously be., present in the zero to low VOC glass or general purpose cleaners of the invention is a polymer or copolymer, most notably an acrylic polymer or copolymer.
  • an acrylic (co) polymer in the formulas of the invention have been found to provide water-sheeting properties to the surfaces cleaned with the formulas of the invention containing the acrylic (co) polymer.
  • An acrylic copolymer suitable for use is POLYQUART AMPHO 149» as sold by Cognis Corporation. POLYQUART AMPHO 149 (CASR-No.
  • 192003-74-0 is the sodium salt of the polymer with ethyl 2-propenoate and N,N,N-trimethyl-3- ( (2-methyl— l-oxo-2-propenyl) amino) -1-propanaminium chloride.
  • Suitable adjuvants include pH adjusting agents, hydrotropes, fragrances, dyes or colorants, preservatives, anti-bacterial agents, thickeners, and the like as known for use in cleaning compositions.
  • Adjuvants are typically present in low amounts, e.g. below about 5% by wt .
  • Suitable agents to adjust pH include conventional acids, bases, and salts thereof, such as C 2 - 4 alkanolamines, ammonia, alkali metal hydroxides, silicates, borates, carbonates, bicarbonates , citrates, citric acid, or mixtures thereof.
  • Preferred examples of pH adjusting agents include ammonium hydroxide and monoethanolamine . J-3924 A
  • Monoethanolamine can also provide cleaning.
  • the cleaning composition of the invention preferably has a pH in the range of 2 or above, more preferably in the range of about 9 to about 13, and most preferably about 10 to about 11.5.
  • the pH adjusting agent is added in an amount appropriate to reach the desired pH. Examples The following examples are provided as illustrative of the present invention of a glass and general purpose cleaning composition.
  • VOC Content 0 . 4 ! 100% J-3924A
  • Example 5 Ingredients % by wt .
  • Soft Water 96.1426 Hexyl Cellosolve 0.60 Isopropanol, anhydrous 1.50 MACKAM 2CSF 0.30 DOWFAX C10L Surfactant 0.15 Sodium Dodecyl Benzene Sulfonate 0.15 Monoethanolamine 0.40 Sodium Octane Sulfonate . 0.15 Propylene Glycol 0.25 Ammonium Hydroxide 0.30 Fragrance 0.05 Colorant 0.0074 VOC Content 1.9% 100%

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  • Chemical & Material Sciences (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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
PCT/US2005/011948 2004-04-09 2005-04-08 Zero to low voc glass and general purpose cleaner Ceased WO2005100522A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP05737586.7A EP1735417B1 (en) 2004-04-09 2005-04-08 Zero to low voc glass and general purpose cleaner
AU2005233608A AU2005233608B2 (en) 2004-04-09 2005-04-08 Zero to low VOC glass and general purpose cleaner
CA2561759A CA2561759C (en) 2004-04-09 2005-04-08 Zero to low voc glass and general purpose cleaner
JP2007507528A JP5265185B2 (ja) 2004-04-09 2005-04-08 ゼロないし低ｖｏｃガラス用及び一般用クリーナー

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/822,301 2004-04-09
US10/822,301 US20050227898A1 (en) 2004-04-09 2004-04-09 Zero to low VOC glass and general purpose cleaner

Publications (1)

Publication Number Publication Date
WO2005100522A1 true WO2005100522A1 (en) 2005-10-27

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ID=34966311

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/011948 Ceased WO2005100522A1 (en) 2004-04-09 2005-04-08 Zero to low voc glass and general purpose cleaner

Country Status (7)

Country Link
US (1) US20050227898A1 (enExample)
EP (1) EP1735417B1 (enExample)
JP (1) JP5265185B2 (enExample)
AU (1) AU2005233608B2 (enExample)
CA (1) CA2561759C (enExample)
TW (1) TW200540264A (enExample)
WO (1) WO2005100522A1 (enExample)

Cited By (5)

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US7741265B2 (en) 2007-08-14 2010-06-22 S.C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
JP2010530137A (ja) * 2007-06-15 2010-09-02 エスビーエー マテリアルズ，インコーポレイテッド． 低ｋ誘電
WO2011049626A1 (en) * 2009-10-22 2011-04-28 S. C. Johnson & Son, Inc. Low voc hard surface treating composition providing anti-fogging and cleaning benefits
WO2012067962A1 (en) * 2010-11-16 2012-05-24 Dow Global Technologies Llc Hard surface cleaners comprising low voc, low odor alkanolamines
WO2013191919A1 (en) * 2012-06-22 2013-12-27 The Procter & Gamble Company Low voc hard surface cleaning composition

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US7604702B2 (en) * 2004-10-29 2009-10-20 Crest Ultrasonics Corp. Method, apparatus, and system for bi-solvent based cleaning of precision components
US20070253926A1 (en) * 2006-04-28 2007-11-01 Tadrowski Tami J Packaged cleaning composition concentrate and method and system for forming a cleaning composition
US8808464B2 (en) 2011-02-15 2014-08-19 Ecolab Usa Inc. Method for removal of a hydrophobic and particulate soil composition
US8349782B2 (en) 2011-02-15 2013-01-08 Ecolab Usa Inc. Hydrophobic and particulate soil removal composition
WO2013043705A2 (en) 2011-09-21 2013-03-28 Ecolab Usa Inc. Bio-based glass cleaner
US8641827B2 (en) 2011-09-21 2014-02-04 Ecolab Usa Inc. Cleaning composition with surface modification polymer
US8648027B2 (en) 2012-07-06 2014-02-11 The Clorox Company Low-VOC cleaning substrates and compositions comprising a cationic biocide
US9096821B1 (en) 2014-07-31 2015-08-04 The Clorox Company Preloaded dual purpose cleaning and sanitizing wipe
US11884897B2 (en) 2016-11-28 2024-01-30 S. C. Johnson & Son, Inc. Hard surface cleaners including fluorosurfactants
US10975341B2 (en) 2017-09-18 2021-04-13 The Clorox Company Cleaning wipes having particular MABDF characteristics
US10982177B2 (en) 2017-09-18 2021-04-20 The Clorox Company Cleaning wipes with particular lotion retention and efficacy characteristics
US10973385B2 (en) 2017-09-18 2021-04-13 The Clorox Company Cleaning wipes having particular pore volume distribution characteristics
US10973386B2 (en) 2017-09-18 2021-04-13 The Clorox Company Cleaning wipes system having particular performance characteristics
US11472164B2 (en) 2018-12-21 2022-10-18 The Clorox Company Multi-layer substrates comprising sandwich layers and polyethylene
IT202300010548A1 (it) * 2023-05-25 2024-11-25 Daniela Menconi Composizione liquida per impedire la formazione di condensa

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EP1735417B1 (en) 2013-06-12
CA2561759A1 (en) 2005-10-27
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EP1735417A1 (en) 2006-12-27
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