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EP2069469A1 - Nettoyant sanitaire à base d'une nouvelle combinaison d'acides - Google Patents

Nettoyant sanitaire à base d'une nouvelle combinaison d'acides

Info

Publication number
EP2069469A1
EP2069469A1 EP06807364A EP06807364A EP2069469A1 EP 2069469 A1 EP2069469 A1 EP 2069469A1 EP 06807364 A EP06807364 A EP 06807364A EP 06807364 A EP06807364 A EP 06807364A EP 2069469 A1 EP2069469 A1 EP 2069469A1
Authority
EP
European Patent Office
Prior art keywords
acid
amount
composition according
cleaning composition
sulfamic
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.)
Granted
Application number
EP06807364A
Other languages
German (de)
English (en)
Other versions
EP2069469B1 (fr
Inventor
Elena Cabero Rego
Christian Liko
Matthias Menzel
Stephan Uhl
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.)
Ecolab Inc
Original Assignee
Ecolab 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 Ecolab Inc filed Critical Ecolab Inc
Publication of EP2069469A1 publication Critical patent/EP2069469A1/fr
Application granted granted Critical
Publication of EP2069469B1 publication Critical patent/EP2069469B1/fr
Active 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043—For use with aerosol devices
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof

Definitions

  • the present invention relates to an aqueous sanitary cleaning com- position and to the use of said cleaning composition for cleaning of, disinfecting of, and/or lime removal from surfaces, especially from surfaces in bathrooms, kitchens and the like.
  • Aqueous cleaning compositions for the removal of dirt and lime in sanitary or kitchen areas are already well-known. These compositions normally are based on inorganic and/or organic acids as well as surfactants. As additional agents these compositions often further comprise colouring agents, perfumes, viscosity control agents, disinfecting and bleaching agents, preservatives, and further auxiliary substances.
  • cleaning compositions For the removal of persistent lime scale it is required that the cleaning compositions have a high acidity. Since strong inorganic acids such as hydrochloric acid and sulphuric acid lead to corrosion of metallic surfaces, material incompatibility and cause environmental pollution nowadays cleaning compositions are widely used which are based on sulfamic acid. Sulfamic-acid-based cleaning compositions have a high scale-removing capability. Additional advantages of these cleaning compositions are that they can be used safely and that they are eco-friendly. [0004] On the other hand, cleaning compositions merely based on sulfamic acid have some disadvantages with respect to labelling regulations, material compatibility, perfume stability, and oxidation problems.
  • sulfamic acid has some drawbacks with respect to its oxidative properties. Sulfamic acid causes corrosion when it comes into contact with metal surfaces. In contact with plastic surfaces it causes an accelerated aging of the plastic materials which may lead to, for example, stress corrosion cracking. Another problem which is sometimes observed with cleaning compositions accord- ing to the state of the art is that the plastic bottles in which the compositions are filled begin to shrink after a certain storage time. This is not acceptable for safety and aesthetical reasons. Therefore, it is also desirable to provide a sanitary cleaning composition being less corrosive to metal surfaces and more compatible to various other materials such as plastics.
  • aqueous sanitary cleaning composition which is less irritant to the skin, has an increased material compatibility, enables higher perfume stability, and is less corro- sive to metal surfaces such as steel and aluminium, but nevertheless has good lime-removing capacity and good cleaning properties.
  • Said cleaning composition of the invention comprises an sulfamic acid in an amount of up to 8 wt.%, a hydroxycarboxylic acid and water, wherein the weight ratio of the sulfamic acid to the hydroxycarboxylic acid is 80:20 to 20:80.
  • the sulfamic acid is in an alternative embodiment of the invention present in an amount of only up to 6 wt.- %, preferably in an amount of below 5 wt.-%.
  • the sulfamic acid is preferably present in a minimum amount of 1 wt.-% and more preferably in a minimum amount of 2 wt.-%.
  • the sulfamic acid to be used is favourably sulfamic acid itself but is not limited to this acid. Also N-alkyl, N-aryl, or N-allyl derivatives thereof if highly soluble in water can be used.
  • Hydrocarboxylic acids are defined as organic acids having at least one hydroxyl group and at least one carboxyl group in the molecule. A wide range of hydrocarboxylic acids can be used in the cleaning compositions according to the invention.
  • acids are for example lactic acid, maleic acid, citric acid, gly- colic acid, tartaric acid, hydracylic acid, ⁇ -hydroxybutyric acid, glyceric acid, tartronic acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, gallic acid, mandelic acid, and tropic acid or mixtures thereof.
  • the preferred acid is lactic acid.
  • Lactic acid has the further advantage that it is slightly antimicrobial. That is why lactic acid is notified as having dis- infecting properties whereas, for example, sulfamic acid is not notified accordingly. Notification procedures follow European biocide regulations. In Germany they are integrated in the chemical regulations stated in the year 2002.
  • the advantage of using lactic acid as component in a sanitary cleaning composition therefore is that such a composition additionally has disinfecting properties and is allowed to be labelled accordingly.
  • the hydroxycarboxylic acid of the sanitary cleaning composition according to the invention is present in an amount of up to 10 wt. -%.
  • An amount of up to 6 wt. -% or even below 4 wt.-% is also sufficient with respect to the aimed properties of the cleaning composition according to the invention.
  • the hydroxycarboxylic acid is preferably present in a minimum amount of 1 wt.-% and more preferably in a minimum amount of 2 wt.-%.
  • the weight ratio of the sulfamic acid and the hydroxycarboxylic acid in the sanitary cleaning composition according to the invention is 80:20 to 20:80 as mentioned above. However, in a preferred embodiment of the invention the ratio is below 60:40 to 40:60, and more preferred between below 60:40 and 50:50.
  • the sanitary cleaning composition comprises urea.
  • the cleaning composition according to the invention comprises urea especially in the case that also perfumes are contained in the composition. The reason therefore is that urea increases the solubility and stability of the perfumes in the aqueous cleaning composition. If urea is used it is present in an amount of 0.5 to 10 wt.-%, preferably 2 to 8 wt.-%, and more preferably in an amount of 4 to 6 wt.-%.
  • composition according to the invention may comprise one ore more surfactants, preferably selected from the group consisting of non-ionic, anionic and/or amphoteric surfactants, or mixtures thereof.
  • the preferred surfactants are non-ionic surfactants. If surfactants are used they are usu- ally present in the composition in an amount of 0.1 to 10 wt.-%, preferably 0.5 to 5 wt.-%, and more preferably in an amount of 1 to 4 wt.-%.
  • Non-ionic, anionic and amphoteric surfactants which are usable in context with aqueous cleaning compositions are well-known for the person skilled in the art. All members of these known surfactants can be used in the cleaning compositions according to the present invention as long as they are compatible with the other compounds used in these compositions. Furthermore, it is within the routine work of a person skilled in the art to choose an appropriate surfactant from the groups of non-ionic, anionic and amphoteric surfactants or a mixture of more than one such surfactants.
  • the surfactant or the mixture of surfactants is preferably selected from the group of non-ionic and/or anionic surfactants which comprises, for example, ethoxylates of alcohols, amines, amides and acids.
  • Preferred su rfactants are alcohol ethoxylates.
  • perfumes and dyes are used as auxiliary compounds in the sanitary cleaning composition. If one or more perfumes are used in the cleaning composition of the invention they are usually present in an amount of 0.01 to 2 wt.-%, preferably in an amount of 0.05 to 0.8 wt.-%, and most preferably in an amount of 0.1 to 0.6 wt.-%. If one or more dyes are used they are usually present in an amount of 0.0001 to 0.1 wt.-%, preferably in an amount of 0.0005 to 0.01 wt.-%, and most preferably in an amount of 0.001 to 0.005 wt.-%.
  • An auxiliary compound which may also be comprised in the cleaning composition according to the invention is one or more alcohols.
  • the alcohol can 5 be used to solve the perfume and/or other auxiliary compounds in a premix solution which is then used to formulate the cleaning composition.
  • the preferred alcohol is ethanol. If one or more alcohols are used they are usually present in an amount of 0.05 to 10 wt.-%, preferably in an amount of 0.1 to 5 wt.-%, and most preferably in an amount of 0.5 to 2 wt.-%.
  • the sanitary cleaning composition of the invention may optionally comprise additional agents like disinfecting agents, preservatives, corrosion inhibitors, complex builders, enzymes and bleaching agents.
  • the pH value of the freshly formulated cleaning composition ac- i5 cording to the invention is adjusted to be equal or above 0.8, preferably equal or above 0.9, and most preferably equal or above 1.05.
  • a cleaning composition according to the invention which had an pH value of, for ex-
  • a further advantage of the present inventive cleaning composition is that the shrinking effect of plastic bottles observed with 1 -liter PE-bottles filled with a cleaning composition according to the state of the art was not observed with the 25 same bottles filled with a cleaning composition according to the invention.
  • the shrinking effect means that the PE-bottles filled with cleaning compositions or the like begin after a few weeks or month of storage to loose their original shape, mostly observed as a shrinking of the bottles.
  • the cleaning composition comprises sulfamic acid in an amount of up to 6 wt.-%, lactic acid in an amount of up to 6 wt.-%, one or more surfactants in an amount of 0.5 to 5 wt.-%, urea in an amount of 2 to 8 wt.-%, one or more alcohols in an amount of 0.1 to 5 wt.-%, one or more perfumes in an amount of 0.05 to 0.8 wt.-%, one or more dyes in an amount of 0.0005 to 0.01 wt.-% and water, wherein the weight ratio of the sulfamic acid to the lactic acid is between below 60:40 and 40:60.
  • the cleaning composition comprises sulfamic acid in an amount of 1 to below 5 wt.-%, lactic acid in an amount of 1 to below 4 wt.-%, one or more non-ionic surfactants in an amount of 1 to 4 wt.-%, urea in an amount of 4 to 6 wt.-%, one or more alcohols in an amount of 0.5 to 2 wt.-%, one or more perfumes in an amount of 0.1 to 0.6 wt.- %, one or more dyes in an amount of 0.001 to 0.005 wt.-% and water, wherein the weight ratio of the sulfamic acid to the lactic acid is between below 60:40 and 50:50.
  • the sanitary cleaning composition does not comprise any thickening agents, for example does not comprise polysaccharide thickener.
  • thickening agents may also be present in the sanitary cleaning composition according to the inven- tion.
  • the cleaning composition according to the invention normally does not comprise ammonium sulfate as an auxiliary compound.
  • ammonium sulfate may be comprised in the composition.
  • the cleaning composition comprises sulfamic acid in an amount of 2 to below 5 wt.-%, lactic acid in an amount of 2 to below 4 wt.-%, one or more non-ionic and/or anionic surfactants in an amount of 1 to 4 wt.-%, urea in an amount of 4 to 6 wt.-%, ethanol in an amount of 0.5 to 2 wt.-%, one or more perfumes in an amount of 0.1 to 0.6 wt.- %, one or more dyes in an amount of 0.001 to 0.005 wt.-% and water, wherein the weight ratio of the sulfamic acid to the lactic acid is between below 60:40 and 50:50 and wherein no thickening agent and no ammonium sulfate is present in the composition.
  • the sanitary cleaning composition according to the invention can be used for cleaning of, disinfecting of, and/or lime removal from various surfaces.
  • surfaces which can be found in sanitary or kitchen areas are brass, copper, aluminium, stainless steel, zinc, polyvinylchloride (PVC), polypro- pylene, acrylonitrile butadiene styrene (ABS), polyacetat, polystyrene, polyethylene (PE), polymethyl methacrylate (PMMA, plexiglas), polycarbonate, ceramic, tiles, porcelain, painted and plastic coated surfaces and enamel or any other surfaces in sanitary or kitchen areas.
  • PVC polyvinylchloride
  • ABS acrylonitrile butadiene styrene
  • ABS acrylonitrile butadiene styrene
  • PES acrylonitrile butadiene styrene
  • PMMA polymethyl methacrylate
  • polycarbonate ceramic, tiles, porcelain, painted and plastic coated surfaces and enamel or any other surfaces in sanitary
  • the sanitary cleaning composition according to the invention can be used as a concentrated composition. However, typically it is used as a ready-to- use solution in any desired dilution in the range of 10:1 to 1 :400 of the composition in water. A preferred dilution is 1 :10 in water.
  • the ready-to-use solution can be applied by spraying or as a foam cleaner.
  • the aqueous sanitary cleaning composition according to the inven- tion can be formed by mixing together all compounds comprised in the composition, preferably beginning with water. Then the other compounds are added to the water. If desired, a ready-to-use composition can then be prepared as mentioned above.
  • An additional pre-mix step is normally not required especially not for the perfume added to the aqueous mixture.
  • cleaning compositions which are only sulfamic-acid-based according to the state of the art it is normally necessary to solve the perfume compound in, for example, ethanol and then to add this pre-mix to the aqueous mixture prepared before. Therefore, it is a further advantage of the sanitary cleaning composition of the present invention that this pre-mix step can be avoided. Examples
  • the lime-removal capacity was tested using the marble-block method according to which marble blocks of 30x30x20 mm dimension were brushed under water and dried for 24 hours in a drying chamber at 50 0 C.
  • the marble-block is put for 1 hour at room temperature in 200 ml of the aqueous sanitary cleaning composition to be tested.
  • the lime- removing capacity is the amount of marble in mg which dissolves within the 1 hour the block was in the 200 ml aqueous cleaning solution. The difference in weight of the marble block at the beginning and in the end of the dissolving procedure is equalled to the lime-removing capacity.
  • Table 2 shows the lime-removing capacity at room temperature (RT) of the cleaning compositions according to the examples listed in table 1.
  • the lime- removing capacity was tested with freshly formulated compositions (column 2) and with compositions stored for 1 , 2, 3 and 4 month at 38 0 C (columns 3-6).
  • the cleaning capacity is measured using a test procedure recommended by the IKW (Industrie notion K ⁇ rperintuit- und Waschstoff e.V.). The details of the test conditions can be found in SOFW-Journal, 130, 10-2004, 83-93.
  • the test were made with pure compositions (examples 2 and 6) and with diluted use compositions (concentration: 2 %, examples 2b and 6b). The test results are shown in table 3.
  • perfumes in the aqueous sanitary cleaning compositions according to the invention are stable ( ⁇ ) at 0 0 C, 25°C and 40 0 C for at least 4 month. Furthermore, perfume stability for at least 4 month can also be observed when the temperature of the composition is increased from -10 0 C to 40 0 C within 24 hours every day. In case that the temperature is increased to 50 0 C the compositions according to example 6c separates into two phases. However, this phenomenon is reversible when the temperature is decreased again. In this case the perfumes do not decompose.
  • the cleaning composition according to comparative example 1c shows after 3 months at 25°C and 40°C a film on the bottom. How- ever, these "two phases" do not reversibly combine to one phase when the temperature is decreased again. This is an indication of decomposition of the perfume.
  • composition according to comparative example 1c has an unpleasant smell of sulfamic acid after a certain time of storage whereas the cleaning compositions according to example 6c do not show a change in smell after three months at both 40 0 C and changing temperatures.
  • test samples of steel and aluminium 50x20x2 mm.
  • the loss of mass of the test samples was evaluated after their exposure to the cleaning composition for three weeks at 55°C.
  • the test samples were entirely submerged in the aqueous sanitary cleaning composition and in a second test only half the surface of the metal sheet was exposed to the cleaning composition. The results are listed in table 5.
  • the cleaning compositions according to the invention have an increased material compatibility, enables higher perfume stability, and are less corrosive to metal surfaces such as steel and aluminium, but nevertheless have good lime-removing capacity and good cleaning properties compared to cleaning compositions of the state of the art which are merely sulfamic-acid-based.

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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)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention porte sur une composition aqueuse de nettoyage sanitaire comprenant un acide sulfamique dans une quantité allant jusqu'à 8 % en poids, un acide hydroxycarboxylique et de l'eau, le rapport en poids de l'acide sulfamique à l'acide hydroxycarboxylique étant de 80:20 à 20:80. Ladite composition de nettoyage peut être utilisée pour le nettoyage, la désinfection, et/ou le retrait de chaux de surfaces faites de laiton, de cuivre, d'aluminium, d'acier inoxydable, de zinc, de poly(chlorure de vinyle) (PVC), de polypropylène, de copolymère acrylonitrile butadiène styrène (ABS), de polyacétate, de polystyrène, de polyéthylène, de poly(méthacrylate de méthyle) (PMMA, plexiglas), de polycarbonate, de céramique, de tuiles, de porcelaine, de surfaces peintes et revêtues de matière plastique et d'émail ou de toutes autres surfaces, par exemple, des surfaces sanitaires ou de cuisine.
EP06807364A 2006-10-17 2006-10-17 Nettoyant sanitaire à base d'une nouvelle combinaison d'acides Active EP2069469B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2006/067522 WO2008046449A1 (fr) 2006-10-17 2006-10-17 Nettoyant sanitaire à base d'une nouvelle combinaison d'acides

Publications (2)

Publication Number Publication Date
EP2069469A1 true EP2069469A1 (fr) 2009-06-17
EP2069469B1 EP2069469B1 (fr) 2012-08-08

Family

ID=38180156

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06807364A Active EP2069469B1 (fr) 2006-10-17 2006-10-17 Nettoyant sanitaire à base d'une nouvelle combinaison d'acides

Country Status (2)

Country Link
EP (1) EP2069469B1 (fr)
WO (1) WO2008046449A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2091997B1 (fr) * 2006-12-21 2016-08-17 Diversey, Inc. Procédé de lavage d'un article en polycarbonate
WO2012084036A1 (fr) * 2010-12-22 2012-06-28 Ecolab Inc. Neutralisant solide pour retraitement automatisé d'instrument
US9103038B2 (en) * 2012-05-29 2015-08-11 Ecolab Usa Inc. Acidic compositions including reducing agents for scale and decolorization of metal stains
US9534190B2 (en) 2012-12-20 2017-01-03 Ecolab Usa Inc. Citrate salt bathroom cleaners
US9790456B2 (en) 2012-12-20 2017-10-17 Ecolab Usa Inc. Citrate salt bathroom cleaners

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5346302A (en) * 1976-10-08 1978-04-25 Sanpooru Kk Liquid acid detergent
US4587030A (en) * 1983-07-05 1986-05-06 Economics Laboratory, Inc. Foamable, acidic cleaning compositions
GB2340501B (en) * 1998-08-11 2002-07-03 Reckitt & Colman Inc Improvements in or relating to organic compositions
WO2003040282A1 (fr) * 2001-11-09 2003-05-15 Jiro Sakurai Detergent pour produit metallique
US20050155628A1 (en) * 2004-01-16 2005-07-21 Andrew Kilkenny Cleaning composition for disposable cleaning head
DE102004020017A1 (de) * 2004-04-21 2005-11-17 Henkel Kgaa Stark saurer Sanitärreiniger mit stabilisiertem Viskositäts-und Phasenverhalten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008046449A1 *

Also Published As

Publication number Publication date
EP2069469B1 (fr) 2012-08-08
WO2008046449A1 (fr) 2008-04-24

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