US3214380A - Liquid scouring cleanser for removing organic stains from hard surfaces - Google Patents

Liquid scouring cleanser for removing organic stains from hard surfaces Download PDF

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Publication number
US3214380A
US3214380A US221349A US22134962A US3214380A US 3214380 A US3214380 A US 3214380A US 221349 A US221349 A US 221349A US 22134962 A US22134962 A US 22134962A US 3214380 A US3214380 A US 3214380A
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US
United States
Prior art keywords
fatty acid
higher fatty
water
cleanser
hard surfaces
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.)
Expired - Lifetime
Application number
US221349A
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English (en)
Inventor
Gangwisch William Jerome
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.)
Colgate Palmolive Co
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Colgate Palmolive Co
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
Priority to BE636822D priority Critical patent/BE636822A/xx
Priority to NL297442D priority patent/NL297442A/xx
Priority to GB1053246D priority patent/GB1053246A/en
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US221349A priority patent/US3214380A/en
Priority to ES290994A priority patent/ES290994A1/es
Priority to DE19631519054 priority patent/DE1519054B2/de
Priority to AT685763A priority patent/AT244180B/de
Priority to CH1057363A priority patent/CH443539A/de
Priority to DK406763AA priority patent/DK113941B/da
Priority to FR945874A priority patent/FR1367361A/fr
Priority to DO1963001068A priority patent/DOP1963001068A/es
Application granted granted Critical
Publication of US3214380A publication Critical patent/US3214380A/en
Priority to MY1967155A priority patent/MY6700155A/xx
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • 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
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof

Definitions

  • This invention relates to an acidic liquid scouring cleaner containing a particular chelating material which, in the present cleanser composition, acts to remove quickly organic stains which may be adhering to hard surfaces, e.g., porcelain sinks.
  • Scouring cleansers have been employed to remove rust stains and other discolorations from sinks. Bleaching agents also have found utility in converting colored stains to non-colored water soluble form. Liquid scouring cleansers, containing dispersed and suspended solid abrasive materials have been produced and by use of particular surface active agents and emulsifiers have been made of acceptable storage stability, so that they do not separate or settle to an objectionable extent. Despite these accomplishments, it has been difficult to produce a liquid scouring cleanser containing effective acidic and bleaching constituents.
  • the present invention provides a stable liquid bleaching composition in which a bleaching and chelating agent is present with suspended abrasive in an acidic aqueous medium.
  • such a stable and effective liquid scouring cleanser for removing stains from hard surfaces comprises about 0.2 to 5% of oxalic acid, 30 to 75% of very finely divided silex, 1 to 7% of an ionic synthetic organic detergent m a group which is a higher alkyl radical of 12 to 18 carbon atoms or a polymeric lower alkylene oxide chain containing 12 to 18 carbon atoms, 0.5 to of a nonionic thickening agent having surface active and emulsifying properties and to 60% water. It is preferred to have water soluble oxalate present and if present, the ratio of oxalic acid to oxalate should be within the range of 1:1 to 100:1.
  • the pH of the resulting product should be from 1 to 3.8.
  • Such a liquid scouring cleanser has the advantages of being non-settling, of regulatable viscosity, of stable and effective bleaching action, despite relatively long periods of storage and of being surprisingly rapid in its cleaning and bleaching action on persistent stains which are not readily removed by other scouring cleansers or conventional blcaches.
  • the oxalic acid employed is preferably chemically pure material but technical oxalic acid is also acceptable. It is preferably present with a water soluble oxalate, preferably an alkali metal oxalate, such as sodium or potassium oxalate, in such proportion as to form a buffered bleaching composition having a pH within the range of 1 to 3.8.
  • the very finely divided silicon dioxide which is the principal active abrasive material in the present compositions should be of a particle size which will give effective "ice such silex is of particle diameter 99.9% less than 250 microns, 99.0% less than 150 microns and 83 to 93% less than microns.
  • about 99% of the particles, by weight may be smaller than 75 microns, with none greater than 150 microns in diameter.
  • scouring cleanser is not intended for use on polished or delicate surfaces and scratching is not objectionable, other slightly larger particles sizes may be present, e.g., more particles up to about 250 microns, providing that the bulk of such particles will be small enough so that they can be effectively suspended in bleaching liquid abrasive cleansers.
  • the ionic'synthetic organic detergent is preferably an anionic detergent, although in some cases cationic detergents, too, may be employed. Cationic detergents should not usually be present together with anionic materials,
  • anionic detergents it is preferred to employ the water soluble higher alkyl aryl sulfonates in which the alkyl group contains from 12 to 18 carbon atoms, most preferably sodium tridecyl benzene sulfonate, in which the alkyl group is preferably a mixture of propylene tetramer and pentamer.
  • Such detergent makes a product of exceptional stability.
  • Suitable synthetic anionic detergents include the water soluble sulfated and sulfonated detergent salts which contain a hydrophobic alkyl group of from 12 to 18 carbon atoms such as higher alkyl sulfate, e.g., sodium lauryl sulfate; higher fatty acid monoglyceride sulfates, e.g., sodium coconut oil fatty acids monoglyceride sulfate; higher fatty acid amide of amino lower alkylene sulfonic acids, e.g., potassium salt of oleic acid amide of N-methyl taurine; higher alkyl sulfonates; monoand di-salts of alpha sulfo fatty acids; sulfated ethoxylated alcohols and sulfated ethoxylated esters of higher fatty acids; and other detergent materials of equivalent actions.
  • higher alkyl sulfate e.g., sodium lauryl sulfate
  • sulfuric reaction product detergents those derived from phosphoric acid are also useful, among which are water soluble orthophosphoric acid esters of higher polyoxyalkylated alkyl phenols, e.g., disodium salt of mono phosphoric acid ester of nonyl phenol polyoxethylene ethanol and the monosodium salt of the diester of phosphoric acid and nonyl phenol polyoxyethylene ethanol, the alkylene oxide chain being of about 6 ethylene oxides in length.
  • cationic detergents such as di-alkyl di-methyl ammonium chloride or bromide in which the alkyl groups are derived from hydrogenated tallow fatty acids, may also be used.
  • Other equivalent cationic detergents are also useful but, as was previously mentioned, it is highly preferable to employ the anionic detergents instead.
  • the nonionic thickening agent having emulsifying properties is preferably an ethoxylated alkylolamide.
  • a compound is the condensation product of a higher monoethanolamide with ethylene oxide.
  • the higher fatty acid is of 12 to 18 carbon atoms, preferably derived from coconut oil
  • the lower alkylene oxide is ethylene oxide and from about 2 to 6 ethylene oxide groups are present in a chain condensed with the alkylolamide.
  • the higher fatty acid alkylolamides in which the alkylol group is ethanol, the higher fatty acid is of 12 to 18 carbon atoms, preferably coconut oil fatty acids and other useful compounds are monoethanolamides.
  • the ethoxylated compounds posthe surfaces to be cleaned and bleached with the present products. It is preferred to employ silex of which at least 99.9% passes through a 60 mesh sieve (US. Standard Sieve Series) and in which less than 1% by ,weight of particles fail to pass through a 100 mesh sieve,
  • Other nonionic thickening agents may also be found useful in the present products.
  • bleaching compounds and chelating agents may be used, e.g., ethylenediamine tetraacetic acid, as its tetrasodium salt and other organic acids, e.g., tartaric acids and tartrates.
  • Other bleaching agents such as the chlorinated materials, tend to be of poor stability in acidic media and usually should not be included in the invented compositions. It is preferred to employ silica as the sole abrasive material but other abrasives such as feldspar, talc, etc., may also be included with it. Mixtures of the synthetic detergents mentioned may be used and in some circumstances it will be found preferable to mix together different nonionic emulsifying thickeners.
  • the proportions of the disclosed constituents should be carefully regulated so as to obtain a product of most desirable stability and effectiveness. It has been found that in these compositions less than 0.2% of oxalic acid is not adequately effective as a chelating agent for bleaching and more than 5% thereof makes the product too strong for general use. Within the range mentioned, it is preferred to regulate the oxalic acid content so as to be from about 0.6 to 2%.
  • the water soluble oxalate present with the oxalic acid to maintain it at a useful operative pH, is most desirably present at a proportion between 0.2 and 1% and the ratio of water soluble oxalic acid to oxalate is preferably between 1:1.5 and :1, resulting in a pH from 1 to 3.8, most preferably about 1.35.
  • the proportion of synthetic organic detergent present is l to 7% by weight of the finished product and is preferably from 2 to 5% thereof. From 0.5 to 10% of nonionic thickening emulsifier is useful and l to 3% is most satisfactory.
  • Moisture content of the finished product is within the range of to 60%, preferably to 45%, and silex content is preferably 40 to 65%.
  • compositions made according to this invention with the constituents described in the proportions given have unusually stable storage characteristics and exhibit excellent chelating and bleaching potential. They are especially useful for cleaning porcelain or ceramic sinks and for removing organic stains which tend to adhere thereto, held to the porcelain by means of a metallic linking agent such as iron or copper.
  • the abrasive constituent removes from the stained surface any coatings which may inhibit intimate contact of the chelating bleach with the stain.
  • the oxalic acid in water soluble oxalate system acts to attack both the organic and the linking metallic portion of the stain, the chelating function causing the metallic link to be broken and the reducing action of the oxalic acid effectively destroying the colorant in the stain.
  • fluorescent materials for making pressurized compositions
  • propellants for making pressurized compositions
  • compatible auxiliary materials for reinforcing the action of any of the required constituents may be added, providing they exhibit a satisfactory stability in the relatively minor proportions in which they would be employed.
  • compositions made according to this invention are illustrative and are not to be considered as limiting the scope of the claims.
  • An excellent liquid scouring cleanser of the above composition was made by adding the oxalic acid, sodium oxalate, perfume and colorant to the water at room temperature, and then serially adding, with agitation, the silex, detergent slurry and diethoxy coconut oil fatty acids monoethanolamide. Shearing agitation was maintained until a viscosity of 15,000 centipoises, as measured by a Brookfield Viscosimeter resulted. This viscosity is within the desirable range of about 7,000 to 25,000 centipoises, possible with the present compositions.
  • the product obtained was a stable pourable suspension which maintains its stability and bleaching and sequestering powers for over a year of storage at normal ambient temperatures. At 140 F. it is stable for 50 days, remaining in homogeneous dispersion without decomposition or phase separation for that length of time.
  • This product was made according to the method of Example I. It was an excellent stain removing liquid cleanser of 11,000 centipoises viscosity and pH of 2.0 stable for over 50 days at 140 -F. and indefinitely at room temperature. In the standard tea stain removal test mentioned in Example I, of the stain was removed in 30 seconds. After use this cleanser could be removed easily from the cleansed surface by light rinsing with water.
  • This product made as in Example I, was of viscosity of 19,000 centipoises and pH of 2.8. It was good for removing tea stains from a hard surface. It was stable indefinitely at room temperature and for more than 90 days at 140 F.
  • This product was made by the method described previously. It had a pH of 3.7, viscosity of 8,500 centipoises, was stable indefinitely at room temperature and for more than 80 days at 140 F. It was an effective cleanser with useful bleaching and chelating stain removal properties.
  • a stable liquid scouring cleanser effective to remove organic stains from porcelain which comprises 0.2 to 5% of oxalic acid, 0.2 to 1% of a water soluble alkali metal oxalate selected from the group consisting of sodium and potassium oxalate, 30 to 75% of silex of particle size less than 250 microns, 1 to 7% of a higher alkyl benzene sulfonate in which the alkyl radical is of 12 to 18 carbon atoms, 0.5 to 10% of a polyethoxylated monoethanolamide of a fatty acid of 12 to 18 carbon atoms, in which 2 to 6 ethylene oxide groups are in the polyethoxy portion, and to 60% water, of viscosity between about 7,000 and 25,000 centipoises and pH of 1 to 3.8, said percentages being by weight of the composition.
  • a stable liquid scouring cleanser effective quickly to remove organic stains from porcelain and other hard surfaces which comprises 0.6 to 2% of oxalic acid, 0.2 to 1% of sodium oxalate, 40 to 65% of silex, having a particle size such that at least 99% thereof passes through a 100 mesh sieve, US. Standard Series, 2 to 5% of sodium tridecyl benzene sulfonate, 1 to 3% of polyethoxyethanolamide of coconut oil fatty acids, in which the polyethoxy chain is of 2 to 6 ethylene oxide groups and 20 to of water, with a product viscosity between about 7,000 and 25,000 centipoises and a pH of 1 to 3.8, said percentages being by weight of the composition.
  • a stable and effective liquid scouring cleanser for removing stains from hard surfaces which comprises about 0.2 to 5% of oxalic acid, 30 to 75% of silex of particle size less than 250 microns, 1 to 7% of a water-soluble organic non-soap detergent selected from the group consisting of organic, synthetic anionic and cationic detergents, 0.5 to 10% of a nonionic amide thickening agent having surface active and emulsifying properties therefor selected from the group consisting of higher fatty acid ethanolamides and higher fatty acid polyethoxylated ethanolamides containing up to 6 ethylene oxide groups in the polyethoxy portion, the higher fatty acid radical of said amides having 12 to 18 carbon atoms, and 15 to of water, said percentages being by weight of the composition.
  • a stable liquid scouring cleanser effective to remove organic stains from porcelain which comprises 0.2 to 5% of oxalic acid, 30 to of silex of particle size less than 250 microns, 1 to 7% of a water-soluble organic nonsoap detergent selected from the group consisting of organic, synthetic anionic and cationic detergents, 0.5 to 10% of a nonionic higher fatty acid ethanolamide having 12 to 18 carbon atoms in the higher fatty acid radical and 15 to 60% of water, said percentages being by weight of the composition.
  • a stable liquid scouring cleanser effective to remove organic stains from porcelain which comprises 0.2 to 5% of oxalic acid, 30 to 75% of silex of particle size less than 250 microns, 1 to 7% of a water soluble higher alkyl benzene sulfonate in which the higher alkyl radical is of 12 to 18 carbon atoms, 0.5 to 10% of a polyethoxylated ethanolamide, in which 2 to 6 ethylene oxide groups are in the polyethoxy portion and the ethanolamide is of a higher fatty acid containing 12 to 18 carbon atoms, and 15 to 60% water, said percentages being by weight of the composition.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
US221349A 1962-09-04 1962-09-04 Liquid scouring cleanser for removing organic stains from hard surfaces Expired - Lifetime US3214380A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
BE636822D BE636822A (it) 1962-09-04
NL297442D NL297442A (it) 1962-09-04
GB1053246D GB1053246A (it) 1962-09-04
US221349A US3214380A (en) 1962-09-04 1962-09-04 Liquid scouring cleanser for removing organic stains from hard surfaces
DE19631519054 DE1519054B2 (de) 1962-09-04 1963-08-22 Fluessiges scheuermittel
ES290994A ES290994A1 (es) 1962-09-04 1963-08-22 Mejoras introducidas en la fabricación de limpiadores líquidos por frote
AT685763A AT244180B (de) 1962-09-04 1963-08-26 Flüssiges, beständiges und wirksames Scheuermittel
CH1057363A CH443539A (de) 1962-09-04 1963-08-27 Beständiges und zur Fleckentfernung auf harten Flächen wirksames flüssiges Scheuermittel
DK406763AA DK113941B (da) 1962-09-04 1963-08-27 Flydende skurerensemiddel til fjernelse af pletter af organisk materiale fra hårde overflader.
FR945874A FR1367361A (fr) 1962-09-04 1963-08-28 Produit nettoyant liquide de récurage pour retirer les taches organiques de surfaces dures
DO1963001068A DOP1963001068A (es) 1962-09-04 1963-09-05 Limpiador para fregado
MY1967155A MY6700155A (en) 1962-09-04 1967-12-31 Liquid scouring cleaser for removing organic stains from hard surfaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US221349A US3214380A (en) 1962-09-04 1962-09-04 Liquid scouring cleanser for removing organic stains from hard surfaces

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US3214380A true US3214380A (en) 1965-10-26

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US221349A Expired - Lifetime US3214380A (en) 1962-09-04 1962-09-04 Liquid scouring cleanser for removing organic stains from hard surfaces

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US (1) US3214380A (it)
AT (1) AT244180B (it)
BE (1) BE636822A (it)
CH (1) CH443539A (it)
DE (1) DE1519054B2 (it)
DK (1) DK113941B (it)
DO (1) DOP1963001068A (it)
ES (1) ES290994A1 (it)
GB (1) GB1053246A (it)
MY (1) MY6700155A (it)
NL (1) NL297442A (it)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4124523A (en) * 1977-03-07 1978-11-07 Dow Corning Corporation Silicone-containing acidic cleaner and conditioner
US4181622A (en) * 1976-11-01 1980-01-01 Gavin David C Cleaning composition and method for removing marine accumulations from surfaces
US4284533A (en) * 1977-11-28 1981-08-18 Kao Soap Co., Ltd. Liquid abrasive-containing cleanser composition
US4302347A (en) * 1977-10-14 1981-11-24 Colgate-Palmolive Company All-purpose liquid abrasive cleaner
US4347153A (en) * 1978-05-16 1982-08-31 Lever Brothers Company Deodorant abrasive cleaner for surface treatment
US4532066A (en) * 1984-03-05 1985-07-30 Sterling Drug Inc. Stable mildly acidic aqueous polishing cleanser and preparation thereof
US4803008A (en) * 1987-09-23 1989-02-07 The Drackett Company Cleaning composition containing a colorant stabilized against fading
US4822854A (en) * 1987-09-23 1989-04-18 The Drackett Company Cleaning compositions containing a colorant stabilized against fading
US5286403A (en) * 1989-09-29 1994-02-15 Dwyer Michael O Concentrated cleaning compositions
US5460742A (en) * 1993-05-18 1995-10-24 Reckitt & Colman Inc. Aqueous acidic hard surface cleaner with abrasive
US5885952A (en) * 1995-05-19 1999-03-23 Ciba Specialty Chemicals Corporation Multifunctional detergent base
EP1111038A1 (en) * 1999-12-22 2001-06-27 The Procter & Gamble Company Scouring composition
EP1460125A1 (en) * 2003-03-18 2004-09-22 Unilever Plc Abrasive hard surface cleaning compositions
EP2075324A1 (en) * 2007-12-27 2009-07-01 The Procter and Gamble Company Liquid acidic hard surface cleaning composition
US20120318303A1 (en) * 2011-06-14 2012-12-20 Ecolab Usa Inc. Non-bleaching procedure for the removal of tea and coffee stains

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2629696A (en) * 1949-05-16 1953-02-24 Oakite Prod Inc Essentially non-aqueous acid emulsion cleaning composition
US2672449A (en) * 1949-09-15 1954-03-16 Foster D Snell Inc Composition for cleaning metal
US2892795A (en) * 1953-12-29 1959-06-30 Colgate Palmolive Co Paste scouring cleanser
US2920045A (en) * 1955-09-06 1960-01-05 Colgate Palmolive Co Heavy duty liquid detergent compositions
CA635321A (en) * 1962-01-23 Unilever Limited Liquid detergent compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA635321A (en) * 1962-01-23 Unilever Limited Liquid detergent compositions
US2629696A (en) * 1949-05-16 1953-02-24 Oakite Prod Inc Essentially non-aqueous acid emulsion cleaning composition
US2672449A (en) * 1949-09-15 1954-03-16 Foster D Snell Inc Composition for cleaning metal
US2892795A (en) * 1953-12-29 1959-06-30 Colgate Palmolive Co Paste scouring cleanser
US2920045A (en) * 1955-09-06 1960-01-05 Colgate Palmolive Co Heavy duty liquid detergent compositions

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4181622A (en) * 1976-11-01 1980-01-01 Gavin David C Cleaning composition and method for removing marine accumulations from surfaces
US4124523A (en) * 1977-03-07 1978-11-07 Dow Corning Corporation Silicone-containing acidic cleaner and conditioner
US4302347A (en) * 1977-10-14 1981-11-24 Colgate-Palmolive Company All-purpose liquid abrasive cleaner
US4284533A (en) * 1977-11-28 1981-08-18 Kao Soap Co., Ltd. Liquid abrasive-containing cleanser composition
US4347153A (en) * 1978-05-16 1982-08-31 Lever Brothers Company Deodorant abrasive cleaner for surface treatment
US4532066A (en) * 1984-03-05 1985-07-30 Sterling Drug Inc. Stable mildly acidic aqueous polishing cleanser and preparation thereof
US4803008A (en) * 1987-09-23 1989-02-07 The Drackett Company Cleaning composition containing a colorant stabilized against fading
US4822854A (en) * 1987-09-23 1989-04-18 The Drackett Company Cleaning compositions containing a colorant stabilized against fading
US5286403A (en) * 1989-09-29 1994-02-15 Dwyer Michael O Concentrated cleaning compositions
US5460742A (en) * 1993-05-18 1995-10-24 Reckitt & Colman Inc. Aqueous acidic hard surface cleaner with abrasive
US5885952A (en) * 1995-05-19 1999-03-23 Ciba Specialty Chemicals Corporation Multifunctional detergent base
EP1111038A1 (en) * 1999-12-22 2001-06-27 The Procter & Gamble Company Scouring composition
WO2001046378A1 (en) * 1999-12-22 2001-06-28 The Procter & Gamble Company Scouring composition
EP1460125A1 (en) * 2003-03-18 2004-09-22 Unilever Plc Abrasive hard surface cleaning compositions
WO2004083353A1 (en) * 2003-03-18 2004-09-30 Unilever N.V. Abrasive hard surface cleaning compositions
EP2075324A1 (en) * 2007-12-27 2009-07-01 The Procter and Gamble Company Liquid acidic hard surface cleaning composition
EP2075325A1 (en) * 2007-12-27 2009-07-01 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
WO2009083860A1 (en) * 2007-12-27 2009-07-09 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
US20120318303A1 (en) * 2011-06-14 2012-12-20 Ecolab Usa Inc. Non-bleaching procedure for the removal of tea and coffee stains

Also Published As

Publication number Publication date
DE1519054A1 (de) 1969-12-18
ES290994A1 (es) 1963-12-16
GB1053246A (it)
MY6700155A (en) 1967-12-31
DK113941B (da) 1969-05-12
DOP1963001068A (es) 1974-01-29
DE1519054B2 (de) 1973-02-15
BE636822A (it)
CH443539A (de) 1967-09-15
AT244180B (de) 1965-12-27
NL297442A (it)

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