EP0813585B1 - Reinigungsmittel - Google Patents

Reinigungsmittel Download PDF

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Publication number
EP0813585B1
EP0813585B1 EP96944872A EP96944872A EP0813585B1 EP 0813585 B1 EP0813585 B1 EP 0813585B1 EP 96944872 A EP96944872 A EP 96944872A EP 96944872 A EP96944872 A EP 96944872A EP 0813585 B1 EP0813585 B1 EP 0813585B1
Authority
EP
European Patent Office
Prior art keywords
composition
amine oxide
acid
viscosity
weight
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
EP96944872A
Other languages
English (en)
French (fr)
Other versions
EP0813585A1 (de
Inventor
Balvinder Adat
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
Publication of EP0813585A1 publication Critical patent/EP0813585A1/de
Application granted granted Critical
Publication of EP0813585B1 publication Critical patent/EP0813585B1/de
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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • 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
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • 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
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • This invention relates to foamable cleaning compositions for use in removing limescale stains from surfaces.
  • Tap water always contains a certain amount of solubilized ions which eventually deposit as salts, on surfaces in contact with the water, as it evaporates.
  • salts include calcium carbonate, commonly referred to as limescale.
  • limescale This phenomenon of limescale accumulation on surfaces which are often in contact with water may damage surfaces and affects the functioning of taps or appliances, such as irons.
  • the accumulation of limescale in the toilet bowl is aesthetically unpleasant and favors the deposition of further soil and the growth of microorganisms. It is therefore important to control this limescale accumulation.
  • EP-A-0,589,761 discloses a thickened acidic aqueous cleaner for bathtubs and other hard surfaced items, which removes limescale, soap scum and greasy soil from surfaces of such items without damaging such surfaces.
  • composition of the reference comprises:
  • EP-A-0,606,712 discloses a thickened buffered aqueous acidic composition.
  • composition of the reference comprises citric acid and sodium citrate, and in the composition suitable thickeners include conventional thickeners such as xanthan gum, polymers, alkyl amines, and surfactant based thickeners as well as nonionic and amine oxide surfactants.
  • suitable thickeners include conventional thickeners such as xanthan gum, polymers, alkyl amines, and surfactant based thickeners as well as nonionic and amine oxide surfactants.
  • the composition of the reference does not include sulphamic acid.
  • EP-A-0,666,304 discloses compositions comprising as a first essential ingredient an organic acid such as maleic acid. It is preferred in the invention of the reference to use maleic acid either alone or together with sulfonic acids such as sulfamic acid.
  • compositions according to the reference invention comprises as a second essential ingredient a surfactant or mixtures thereof.
  • the compositions comprise said surfactant in an appropriate amount below 1% by weight of the total composition.
  • the composition of the reference does not include amine oxide surfactants.
  • the compositions of the reference comprise thickeners.
  • WO-A-94 28108 concerns over cleaning compositions and does not deal with acidic limescale removing compositions.
  • EP-A-0130786 discloses an acidic cleaning composition comprising water, a mixture of a weak inorganic acid and a weak organic acid, an amine oxide surfactant, and a surface-tension-reducing co-solvent.
  • the subject invention is directed to a limescale removing composition which can be delivered as a foam.
  • the subject invention provides an aqueous liquid storage-stable foamable limescale removing composition consisting of:
  • the subject invention provides a method of removing limescale from a substrate comprising the steps of:
  • the composition of the invention comprises a mixture of sulphamic acid and at least one organic carboxylic acid.
  • the sulphamic acid and the at least one other acid are preferably mixed in synergistically effective limescale removing amounts.
  • the organic carboxylic acid has a molecular weight of 60-250. More preferably, the carboxylic acid is lactic acid, citric acid, or another hydroxy acid where the hydroxy group is ⁇ to at least one of the acid moieties.
  • the mixture of acids is present in the range 5-20 weight percent of the aqueous cleaning composition and more preferably 10-20 weight percent.
  • the composition of the invention can be dispensed as a foam through a foam dispenser.
  • the composition may tend to be difficult to dispense in this way if the composition in use has a final viscosity which is much above 300 cps. All viscosity measurements stated herein are taken using a Brookfield viscometer, at 20°C using #3 spindle at 30 rpm. Preferably, the final viscosity is in the range 200-300 cps.
  • the maximum viscosity of the composition of the invention is limited by the need for the composition to be dispensable through a foam dispenser, one aspect of particular importance is storage stability.
  • the composition of the subject invention relies on a complex blend of components and inevitably the composition will be placed into its final package some long time before it comes into use in the hands of the ultimate consumer. It is important that the viscosity of the composition is maintained within parameters during storage to allow delivery through the foam dispenser. Long term stability of the viscosity is mainly determined by the optimized level and type of thickening agents. Thickeners which are effective in the composition of the subject invention are selected from the group consisting of acrylic emulsion polymer thickeners, xanthan gums, rhamsan gums, welan gums and polyurethanes. The preferred thickener is xanthan gum with altered rheology. The thickener is present in an amount of 0.001-5 weight percent based on the weight of the cleaning composition.
  • the storage stable composition of the subject invention will preferably be dispensable as a foam through a foam dispenser after storage at room temperature for 6 months, and more preferable after storage at room temperature for 1 year.
  • the storage stable composition of the subject invention will not show phase separation or precipitation after said storage, the viscosity of the composition remaining constant during said storage.
  • the foaminess index ⁇ is between 15-50 and more typically between 20-30.
  • the amount of thickener is instrumental in allowing the composition to remain storage stable, it should also be noted that the presence of particular amounts of other components in the composition may effect viscosity.
  • the amine oxide surfactant can be expected to have an effect on the viscosity of the composition.
  • composition is dispensable as a foam.
  • Dispensing as a foam allows the composition to remain on the limescale stain for an effective time.
  • the composition should be able to remain in contact with and be able to wet and penetrate the limescale stain for a sufficient time to have an effective descaling effect. Subsequently, the composition must be able to be washed away easily with water.
  • foams can be loose airy type foams, while at the other extreme, foams can be tight mousse like type foams.
  • the composition of the subject invention ideally produces a foam which is roughly halfway between a loose airy type foam and a tight mousse type foam in order to give maximum descaling and a good cling parameter.
  • Cling is measured by spraying about 10g of product onto the underside of a preweighed suspended plate weighing about 200g. The plate is left to hang for 5 minutes and is then re-weighed. The cling is determined by the amount of product remaining on the plate after 5 minutes.
  • the cling parameter of the composition of the subject invention is 50 - 70% of product remaining on the surface after 5 minutes.
  • the nature and amount of the amine oxide surfactant present in the composition of the invention will generally determine the foam profile and cling parameter of the composition. Additionally, however, the cling parameter is dependent on the amount of thickener present in the composition.
  • the amine oxide preferably has the formula RR' R"NO, where R is a substituted or unsubstituted alkyl or alkene group containing from 8 to 30, preferably from 10 to 20, more preferably 10 to 16 carbon atoms.
  • R is an unsubstituted alkyl group.
  • Groups R' and R" are each substituted or unsubstituted alkyl or alkene groups containing from 1 to 18, preferably from 1 to 4, carbon atoms. More preferably, R' and R" are each methyl groups.
  • the amine oxide detergent surfactant can be prepared by known and conventional methods.
  • One such method involves the oxidation of tertiary amines in the manner set forth in U.S. Patent No. 3,223,647 and British Patent 437,566.
  • amine oxides are prepared by the controlled oxidation of the corresponding tertiary amines.
  • the surfactant will be lauryl dimethyl amine oxide.
  • the amine oxide surfactant is present in the amount of 2.0-8.0% by weight of the total composition.
  • composition can contain other optional components appropriate to limescale removing compositions including dyes and fragrances.
  • composition of the invention (to 100 weight percent) is deionized water.
  • composition of the invention is dispensable through a conventional foam dispenser.
  • compositions of the invention are now set out below:
  • Example 3 had a viscosity of 250 cps and on dispensing through a conventional foam dispenser produced a foam with a cling parameter of 50 - 70% over a 5 minute period.
  • the composition was stable on storage at room temperature for one year.
  • Example 3 The composition of Example 3 was tested for effectiveness by the marble cube test as follows:
  • the average % weight loss (for the 3 cubes) ranged from 35 - 40%.
  • a commercially available maleic acid limescale removing composition was tested in the same way as above and the % weight loss ranged from 20 - 30%.
  • the subject invention provides a limescale removing composition which may be produced using conventional manufacturing methods and packaging.
  • the foamable limescale removing composition maintains its foaming and rheological properties after shelf storage at room temperature for 6 months, preferably one year. This shelf stability will allow a consumer to effectively utilize the descaling composition even though the composition may be placed into its final package a long time prior to its purchase and use.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Surgical Instruments (AREA)
  • Valve Device For Special Equipments (AREA)
  • Valve-Gear Or Valve Arrangements (AREA)

Claims (9)

  1. Wässrige, flüssige, lagerungsbeständige, schäumbare Zusammensetzung zur Entfernung von Kalkablagerungen, die besteht aus:
    a. 5 bis 20 Gew.-% einer Mischung von Sulfamidsäure und einer organischen Carbonsäure;
    b. 0,001 bis 5 Gew.-% eines Verdickungsmittels, ausgewählt aus Acrylemulsionspolymer-Verdickungsmitteln, Xanthangummis, Rhamsangummis, Welangummis und Polyurethan;
    c. 2 bis 8 Gew.-% eines Aminoxid-Tensids,
    d. gegebenenfalls einem Farbstoff;
    e. gegebenenfalls einem Duftstoff; und
    f. entionisiertem Wasser als Rest;
    wobei die Viskosität der Zusammensetzung 300 mPa.s (cps) oder weniger beträgt, bestimmt unter Verwendung eines Brookfield-Viskosimeters bei 20°C unter Verwendung einer Spindel #3 bei 30 UpM.
  2. Zusammensetzung nach Anspruch 1, worin die Viskosität der Zusammensetzung in dem Bereich von 200 bis 300 mPa.s (cps) liegt, bestimmt unter Verwendung eines Brookfield-Viskosimeters bei 20°C unter Verwendung einer Spindel #3 bei 30 UpM.
  3. Zusammensetzung nach Anspruch 1, worin die Zusammensetzung einen Anhaftungs-Parameter von 50 bis 70 % aufweist, bestimmt durch Aufsprühen einer Menge der Zusammensetzung auf die Unterseite einer aufgehängten Platte und erneutes Wiegen der Platte und der an der Platte anhaftenden Zusammensetzung nach 5 min.
  4. Zusammensetzung nach Anspruch 1, worin die organische Carbonsäure ausgewählt ist aus der Gruppe, die besteht aus Milchsäure, Citronensäure, Hydroxysäuren, in denen die Hydroxygruppe in α-Stellung zu mindestens einem der Säurereste steht, und Mischungen davon.
  5. Zusammensetzung nach Anspruch 1, worin das Aminoxid-Tensid ein Alkylaminoxid-Tensid ist.
  6. Zusammensetzung nach Anspruch 5, worin das Alkylaminoxid-Tensid ein C10-C16-Alkyldimethylaminoxid ist.
  7. Zusammensetzung nach Anspruch 6, worin das Alkylaminoxid-Tensid Lauryldimethylaminoxid ist.
  8. Wässrige, flüssige, lagerungsbeständige, schäumbare Zusammensetzung zur Entfernung von Kalkablagerungen, die besteht aus:
    5 bis 20 Gew.-% einer Mischung von Sulfamidsäure und einer organischen Carbonsäure, ausgewählt aus der Gruppe, die besteht aus Milchsäure, Citronensäure, Hydroxysäuren, in denen die Hydroxygruppe in α-Stellung zu mindestens einem der Säurereste steht, und Mischungen davon;
    0,001 bis 5 Gew.-% eines Verdickungsmittels, ausgewählt aus der Gruppe, die besteht Acrylemulsionspolymeren, Xanthangummis, Rhamsangummis, Welangummis und Polyurethan;
    2 bis 8 Gew.-% eines Aminoxid-Tensids;
    gegebenenfalls einem Farbstoff;
    gegebenenfalls einem Duftstoff;
    entionisiertem Wasser als Rest,
    wobei die Viskosität der Zusammensetzung 300 mPa.s (cps) oder weniger beträgt, bestimmt unter Verwendung eines Brookfield-Viskosimeters bei 20°C unter Verwendung einer Spindel #3 bei 30 UpM.
  9. Verfahren zur Entfernung von Kalkablagerungen von einem Substrat, das die Stufen umfasst:
    Aufbringen der Zusammensetzung nach einem der vorhergehenden Ansprüche auf ein Substrat, das Kalkablagerungen enthält;
    Stehenlassen der Zusammensetzung im Kontakt mit dem Substrat für eine Zeitspanne, die ausreicht, um einen Ablagerungsentfernungseffekt zu erzielen; und
    Entfernen der Zusammensetzung von dem Substrat.
EP96944872A 1996-01-03 1996-12-19 Reinigungsmittel Expired - Lifetime EP0813585B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9600030 1996-01-03
GBGB9600030.2A GB9600030D0 (en) 1996-01-03 1996-01-03 Cleaning compositions
PCT/US1996/020219 WO1997025401A1 (en) 1996-01-03 1996-12-19 Cleaning compositions

Publications (2)

Publication Number Publication Date
EP0813585A1 EP0813585A1 (de) 1997-12-29
EP0813585B1 true EP0813585B1 (de) 2002-03-27

Family

ID=10786532

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96944872A Expired - Lifetime EP0813585B1 (de) 1996-01-03 1996-12-19 Reinigungsmittel

Country Status (12)

Country Link
EP (1) EP0813585B1 (de)
KR (1) KR19980702727A (de)
CN (1) CN1181105A (de)
AT (1) ATE215121T1 (de)
AU (1) AU713065B2 (de)
BR (1) BR9607812A (de)
CA (1) CA2214524A1 (de)
DE (1) DE69620158T2 (de)
DK (1) DK0813585T3 (de)
ES (1) ES2170887T3 (de)
GB (1) GB9600030D0 (de)
WO (1) WO1997025401A1 (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE291073T1 (de) * 1997-10-31 2005-04-15 Procter & Gamble Saure flüssige zusammensetzungen zum entfernen von kesselstein verpackt in einem sprühspender
US6333299B1 (en) 1997-10-31 2001-12-25 The Procter & Gamble Co. Liquid acidic limescale removal composition packaged in a spray-type dispenser
US5895781A (en) * 1997-12-22 1999-04-20 S. C. Johnson & Son, Inc. Cleaning compositions for ceramic and porcelain surfaces and related methods
FR2841802B1 (fr) * 2002-07-08 2005-03-04 Commissariat Energie Atomique Composition, mousse et procede de decontamination de surfaces
US20040229763A1 (en) * 2003-02-28 2004-11-18 The Procter & Gamble Company Cleaning kit and/or a dishwashing kit containing a foam-generating dispenser and a cleaning and/or dishwashing composition
US7402554B2 (en) 2003-02-28 2008-07-22 The Procter & Gamble Company Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant
CN1753985A (zh) * 2003-02-28 2006-03-29 宝洁公司 包含泡沫生成分配器与清洁和/或盘碟洗涤组合物的清洁套件和/或盘碟洗涤套件
WO2004078902A1 (en) * 2003-02-28 2004-09-16 The Procter & Gamble Company Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant
US7651992B2 (en) 2003-02-28 2010-01-26 The Procter & Gamble Company Foam-generating kit containing a foam-generating dispenser and a composition containing a high level of surfactant
DE102004020017A1 (de) * 2004-04-21 2005-11-17 Henkel Kgaa Stark saurer Sanitärreiniger mit stabilisiertem Viskositäts-und Phasenverhalten
JP4732115B2 (ja) * 2005-10-14 2011-07-27 花王株式会社 硬質表面用酸性洗浄剤組成物
CN110498867B (zh) * 2018-05-17 2021-08-03 中国石油化工股份有限公司 改性韦兰胶及其制备方法和水基压裂液组合物及水基压裂液

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1240469A (en) * 1967-08-08 1971-07-28 Atlas Preservative Company Ltd Improvements in or relating to cleaning compositions
FR2469450A1 (fr) * 1979-11-12 1981-05-22 Solitaire Produits Entretien F Produit de detartrage et de nettoyage en particulier de surfaces en faience emaillee telles que des cuvettes de w.c.
US4587030A (en) * 1983-07-05 1986-05-06 Economics Laboratory, Inc. Foamable, acidic cleaning compositions
KR950006289B1 (ko) * 1986-07-17 1995-06-13 알 앤드 시 프로덕츠 피티와이. 리미티드 아민-산 증점 조성물
DE69329398T2 (de) * 1993-11-29 2001-04-12 Procter & Gamble Zusammensetzungen zum Entfernen von Kesselstein

Also Published As

Publication number Publication date
WO1997025401A1 (en) 1997-07-17
EP0813585A1 (de) 1997-12-29
CA2214524A1 (en) 1997-07-17
AU1337497A (en) 1997-08-01
BR9607812A (pt) 1998-07-07
DE69620158D1 (de) 2002-05-02
KR19980702727A (ko) 1998-08-05
CN1181105A (zh) 1998-05-06
ES2170887T3 (es) 2002-08-16
AU713065B2 (en) 1999-11-25
DK0813585T3 (da) 2002-07-08
ATE215121T1 (de) 2002-04-15
DE69620158T2 (de) 2002-08-14
GB9600030D0 (en) 1996-03-06

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