WO2002006434A1 - Cleaning compositions and their use - Google Patents
Cleaning compositions and their use Download PDFInfo
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- WO2002006434A1 WO2002006434A1 PCT/GB2001/003136 GB0103136W WO0206434A1 WO 2002006434 A1 WO2002006434 A1 WO 2002006434A1 GB 0103136 W GB0103136 W GB 0103136W WO 0206434 A1 WO0206434 A1 WO 0206434A1
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- Prior art keywords
- composition
- locus
- cleaning
- exposure
- change
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Classifications
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- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
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- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0056—Lavatory cleansing blocks
-
- 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
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
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- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0042—Reducing agents
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- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0047—Other compounding ingredients characterised by their effect pH regulated 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-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
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
Definitions
- This invention relates to cleaning compositions and their use.
- Bathroom cleaners are mainly acidic compositions, intended to combat calcium deposits .
- kitchen cleaners are mainly alkaline compositions, intended to combat grease deposits .
- an alkaline composition is required; and in which for kitchen cleaning, an acidic cleaning composition is required.
- the customer has to decide whether to purchase a plethora of different products for different cleaning tasks, or whether to compromise. It would be good to have a single composition which was able to combat the deposits attacked by acidic cleaning compositions and the deposits attacked by alkaline cleaning compositions, but the difficulty in achieving this is self-evident.
- a cleaning composition which comprises reactants which undergo a chemical reaction after exposure to a locus to be cleaned, the reaction being such as to produce a delayed change of pH at that locus .
- a cleaning composition having the property that on exposure to a locus to be cleaned the locus renders acidic or alkaline or neutral, and that after an interval it renders the locus alkaline or neutral (if originally acidic) or acidic or neutral (if originally alkaline) or acidic or alkaline (if originally neutral) .
- composition of any of the aspects may have the property that the locus containing the composition is initially an acidic liquid and after an interval becomes an alkaline liquid.
- composition of any of the aspects may have the property that the locus containing the composition is initially an alkaline liquid and after an interval becomes an acidic liquid.
- the pH change takes place after an induction period (that is, an interval after exposure of the composition to the locus) of at least 10 seconds, more preferably at least 20 seconds, most preferably at least 60 seconds, and, especially, at least 100 seconds.
- an induction period that is, an interval after exposure of the composition to the locus
- the said induction period is not more than 12 hours, preferably not more than 1200 seconds, more preferably not more than 600 seconds, most preferably not more than 400 seconds, and, especially, not more than 300 seconds.
- a composition of the invention could be a single-pack composition, with the reactants being held in stasis if necessary.
- the pH change which takes place may be initiated by addition of an agent from which the reactants were previously protected.
- it could be water, or oxygen, or carbon dioxide, or light.
- the reactants could be kept physically separated from each other prior to their use, as for example in a tablet or dissolvable sachet having two or more zones, which may be layers, portions or encapsulated sections, depending on the type of tablet or sachet, or in a twin-bottle package or twin-tablet package.
- the key measure is that the reactants are combined only at the time of cleaning.
- the composition may be provided in a package which emits the composition as a spray, mousse, gel or liquid jet.
- the package may suitably be a trigger spray or, preferably, an aerosol canister.
- a spray-emitting package of the composition, especially an aerosol canister, constitutes a further aspect of the invention.
- a wipable product for example a sponge or cloth, is impregnated with a composition.
- the composition may be a product for dilution in order to be used, or a product in ready-to-use form.
- a product When a product is for dilution, it may be a solid, for example a powder or tablet, or a liquid, or a gel.
- the composition may be provided in packaging giving unit-dose supply of the composition.
- the composition may be such that the chemical reaction causes a colour change.
- One or more of the reactants responsible for the change of pH may cause a change of colour, for example on exhaustion, or a separate dye or colorant may be included in the composition, responsive to pH change or to the presence of oxidant species, or reductant species, or temperature change in the case of an exothermic reaction.
- system could be arranged to effervesce when the reaction takes place, for example by including a bicarbonate in a system which becomes acidic after the induction period.
- Another method useful in the case of an exothermic reaction employs a fragrance rendered volatile by a temperature rise .
- cleaning may include: removal of soil deposits: prevention of soiling; bleaching; combating of allergens; and combating of microbes, including by one or more of antiseptic, disinfectant, bactericidal, sporicidal, fungicidal and viricidal action.
- the composition is antimicrobial.
- an antimicrobial effect is generated by the reaction, for example by temperature rise when the reaction is exothermic and/or by the pH change at the locus and/or by production of an antimicrobial chemical, in the reaction.
- an antimicrobial chemical is generated in situ by the reaction which changes the pH, and therefore with the same delay.
- the antimicrobial chemical may, for example, comprise an iodate, bromate, thiocyanate or chlorate.
- the composition preferably produces a bleaching effect.
- a bleaching effect is generated by the reaction, for example by the temperature when the reaction is exothermic and/or by the pH change at the locus and/or by production of a bleaching chemical, in the reaction.
- a bleaching agent is produced in situ by the reaction which changes the pH, and therefore with the same delay.
- the composition may include sodium chlorite generating, under acid conditions, sodium hydroxide and chlorine dioxide.
- both a bleaching agent and an alkaline agent may be generated.
- the composition may contain hydrogen peroxide or a precursor to it as a bleaching agent and/or reactant .
- the composition may include one or more surfactants .
- a surfactant used in the present invention may be selected from one or more surfactants which may be anionic, cationic, nonionic or amphoteric (zwitterionic) surface active agents.
- alkoxylated alcohols particularly alkoxylated fatty alcohols. These include ethoxylated and propoxylated fatty alcohols, as well as ethoxylated and propoxylated alkyl phenols, both having alkyl groups of from 7 to 16, more preferably 8 to 13 carbon chains in length.
- alkoxylated alcohols examples include certain ethoxylated alcohol compositions presently commercially available from the Shell Oil Company (Houston, TX) under the general trade name NEODOL (trade mark) , which are described to be linear alcohol ethoxylates and certain compositions presently commercially available from the Union Carbide Company, (Danbury, CT) under the general trade name TERGITOL (trade mark) which are described to be secondary alcohol ethoxylates.
- alkoxylated alkyl phenols examples include certain compositions presently commercially available from the Rh ⁇ ne-Poulenc Company (Cranbury, NJ) under the general trade name IGEPAL (trade mark) , which are described as octyl and nonyl phenols.
- non-ionic surfactants that may be used are sorbitan esters of fatty acids, typically of fatty acids having from 10 to 24 carbon atoms, for example sorbitan mono oleate.
- anionic surface active agents which may be used in the present invention include but are not limited to: alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of one or more of the following compounds: alkyl sulphates, alkyl ether sulphates, alkylamidoether sulphates, alkylaryl polyether sulphates, monoglyceride sulphates, alkylsulphonates, alkylamide sulphonates, alkylarylsulphonates, olefinsulphonates, paraffin sulphonates, alkyl sulfosuccinates , alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl saronsinates , acyl is
- anionic surface active agents which may be used include fatty acid salts, including salts of oleic, ricinoleic, palmitic and stearic acids; copra oils or hydrogenated copra oil acid, and acyl lactylates whose acyl group contains 8 to 20 carbon atoms.
- amphoteric surfactants which may be used in the present invention including amphoteric betaine surfactant compounds having the following general formula:
- R is a hydrophobic group which is an alkyl group containing from 10 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, an alkylaryl or arylalkyl group containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or either linkages; each R x is an alkyl group containing from 1 to 3 carbon atoms; and R 2 is an alkylene group containing from 1 to 6 carbon atoms.
- betaine compounds may be included in the compositions of the invention.
- cationic surfactants which may be used in the present invention include quaternary ammonium compounds and salts thereof, including quaternary ammonium compounds which also have germicidal activity and which may be characterized by the general structural formula:
- R 1( R 2 , R 3 and R 4 is a hydrophobic, aliphatic, aryl aliphatic or aliphatic aryl group containing from 6 to 26 carbon atoms, and the entire cationic portion of the molecule has a molecular weight of at least 165.
- the hydrophobic groups may be long- chain alkyl, long-chain alkoxy aryl, long-chain alkyl aryl, halogen-substituted long-chain alkyl aryl, long- chain alkyl phenoxy alkyl or aryl alkyl .
- the remaining groups on the nitrogen atoms, other than the hydrophobic radicals, are generally hydrocarbon groups usually containing a total of no more than 12 carbon atoms.
- R 1( R 2 , R 3 and R 4 may be straight chain or may be branched, but are preferably straight chain, and may include one or more amide or ester linkages.
- X may be any salt-forming anionic moiety.
- quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, and N-alkyl pyridinium halides such as N-cetyl pyridinium bromide.
- alkyl ammonium halides such as cetyl trimethyl ammonium bromide
- alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide
- N-alkyl pyridinium halides such as N-cetyl pyridinium bromide.
- quaternary ammonium salts include those in which the molecule contains either amide or ester linkages, such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride and N- (laurylcocoaminoformylmethyl) -pyridinium chloride.
- Preferred quaternary ammonium compounds which act as germicides and which are useful in the present invention include those which have the structural formula:
- R 2 and R 3 are the same or different C 8 -C 12 alkyl, or R 2 is C 12 -C ls alkyl, C 8 -C 18 alkylethoxy, C 8 -C 18 alkyl- phenolethoxy and R 3 is benzyl, and X is a halide, for example chloride, bromide or iodide, or methosulphate.
- Alkyl groups R 2 and R 3 may be straight chain or branched, but are preferably substantially linear.
- a mixture of two or more surface active agents may also be used.
- Other known surface active agents not particularly described above may also be used.
- Such surface active agents are described in McCutcheon' s Detergents and Emulsifiers, North American Edition, 1982; Kirk-Othmer, Encyclopaedia of Chemical Technology, 3rd Ed., Vol. 22, pp 346-387.
- compositions of the present invention may include therein one or more organic solvents, such as lower alkyl alcohols, lower alkyl diols or glycol ethers.
- organic solvents such as lower alkyl alcohols, lower alkyl diols or glycol ethers.
- Such compounds may function as a cleaning agent of the compositions, and may be especially useful in glass cleaners due to their lack of tendency to smear.
- the composition is such that after exposure to an locus to be cleaned its temperature rises, preferably caused by the reaction which changes the pH, and therefore with the same delay.
- the reaction responsible for change in pH is preferably exothermic.
- the composition may be such that after one pH change the pH may change in the reverse direction.
- a composition may go from acidic to alkaline and back to to acidic, or from alkaline to acidic and back to alkaline. It is possible that such compositions may undergo further pH changes.
- Each pH change preferably takes place over an induction period as defined above.
- Suitable systems may include those described in the following references:
- the composition may contain components which provide an abrupt pH step.
- the autocatalytic species for the reaction is H + (or, more rarely, OH " ) and pH steps may occur when a solution of a weak acid is oxidised to provide a strong acid, so that H + concentration increases with the extent of reaction.
- the chemical composition, of a typical pH step system will involve an oxidant and a reductant.
- the reductant will be the salt of a weak acid and the corresponding oxidant will be a strong acid.
- a reaction may employ a plurality of oxidants and/or a plurality of reductants.
- the most widely studied pH step reactions are those typified by the Landolt clock reaction, in which the oxidant is of formula XO n " when X is Cl , Br or I and n is 3 when X is Br or I, and 2, 3 or 4 when X is Cl ; and the reductant is S0 3 2" /HS0 3
- the classic Landolt system employs I0 3 " as oxidant and is S0 3 2" /HS0 3 " as reductant.
- the reaction is autocatalytic in I " (depending on the second power of the iodide ion concentration) and is a pH step reaction system even in buffered solution. In unbuffered solution, the reaction is also autocatalytic in H + . Beyond those combinations mentioned above, there are reports of pH step reactions with associated pH changes involving the following reagents:
- precursors of hydrogen peroxide include urea hydrogen peroxide (UHP) and a cyclodextrin complexed with an organic peroxy acid, for example as described in
- EP-A-895777 An example is ⁇ -cyclodextrin complexed with an organic peroxy acid, e-phthalimido peroxyhexanoic acid
- mixed-Landolt system may produce a pH step reaction in which the pH swings from high to low at the end of an induction period, and then back to high pH on a longer timescale.
- An example of a pH step reaction system starting at low pH and changing to high pH at the end of an induction period involves the reduction of H 2 0 2 (which may be delivered by means of a precursor, as described above) by various multidentate complexes of Fe(II) or Co (II) ions, notably using Fe(CN) 6 ⁇ as the anion species, as described in G. Rabai et al, J. m. Chem. Soc . , 1989, III, p. 3870.
- Cleaning compositions of the invention may be used, for example, for textile materials, including carpets and clothes. They may be used in dishwasher cleaning compositions and clothes washing compositions.
- the change of pH may, for example, initiate the dissolution of the coating of a washing tablet or of an insert product contained within a washing tablet, providing in each case delayed release of the contents.
- preferred cleaning composition of the present invention is a hard surface cleaner, for cleaning ceramics, glass, stone, plastics and wood; and particularly for cleaning bathroom and kitchen hard surfaces, for example sinks, bowls, toilets, panels, tiles and worktops.
- acidic When acidic it is particularly effective in combating limescale.
- alkaline When alkaline it is particularly effective in combating grease and proteinaceous deposits.
- Another preferred cleaning composition is adapted for cleaning dentures (normally of polyacrylic material) and is therefore effective in removing staining and/or plaque.
- compositions are adapted for cleaning lavatory bowls and for this purpose the composition may be packaged in an ITB (In the Bowl) or ITC (In the Cistern) device, preferably in a holder which hangs from the rim of the bowl or cistern.
- ITB In the Bowl
- ITC In the Cistern
- the reactants are preferably liquids kept in separate vessels, or solids formulated in separate tablets (for example compressed powders or granules, or gel blocks) or in one tablet with distinct zones for the different reactants.
- the reactants may be mixed and only react in use, in which case a single vessel or simple tablet may be used.
- Another useful cleaning composition is adapted to clean marble surfaces effectively.
- Such a composition is acidic when applied in order to attack certain stains and soils, but becomes alkaline before any dissolution of the marble can occur. When alkaline it attacks other stains and soils, notably greases.
- the induction period (the period between mixing of reactants and commencement of pH swing) and of pH swing with initial reactant concentrations for a dilute solution of bromate and sulphite ions, mixed as solutions at ambient temperature, and using concentrated sulphuric acid to adjust the pH, were determined in a series of experiments.
- the induction period ti n a can be varied between 4 hours and 2 minutes, with t ⁇ n d being approximately inversely proportional to the initial concentrations of both Br0 3 " and H + and independent of the initial concentration of S0 3 2 ⁇ .
- the initial sulphite concentration appears to determine the pH swing, which is typically of the order of 4 to 5 pH units.
- the reaction occurs for compositions with initial pH values in the range 6.6 to 8.9.
- the chlorate ion C10 3 " can also be used as the oxidant in Landolt-type systems.
- a series of experiments were performed on this system. The reaction does not appear to occur starting from pH values higher than ca. 5.0, so the initial pH was adjusted using concentrated H 2 S0 to the range 4.5-5.0 for the experiments reported below. The reaction is strongly exothermic and even for relatively dilute solutions, significant temperature rises (self-heating) occur. The results are set out in Table 6 and 7 below.
- Table 9 above shows how the induction period changes depending on whether the reactants are used in solution or dry powder form.
- the induction period was increased for the dry powder experiments, but this increase was very small and in most cases only increases the induction time by a few seconds. There was no noticeable difference in the temperature rise and initial and final pH between the dry powder and solution experiments. A powder system was accordingly shown to be of possible value in the present invention.
- Sodium lauryl sulphate is a well-known anionic surfactant.
- Polytergent SL-62 is a non-ionic surfactant, a mixture of ethoxylated and propoxylated fatty alcohols, from BASF.
- the glycol ether was DOWANOL DPnB glycol ether.
- Empigen BAC 50 is a cationic surfactant, a benzalkonium chloride, more specifically Cio-i ⁇ (predominantly C ⁇ 2 - 14 ) alkyl dimethyl benzylammonium chloride .
- Polytergent SL-62 1% w/w - 10%w/w
- Dipropylene glycol n-butyl ether 1% w/w - 10%w/w
- Tables 12 and 13 show the results from the experiments In each case the results are the mean results of three replicates.
- Table 12 shows the results for the initial concentrations bromate 0.5M, sulphite 0.65M and bisulphite 0.018M and
- Table 13 shows the results for the initial concentrations bromate 0.7M, sulphite 0.5M and bisulphite 0.018M.
- Dipropylene glycol n-butyl ether 1% w/w - 10%w/w
- the reactants and their initial concentrations were as follows.
- Dipropylene glycol n-butyl ether reduced the final pH. All the other surfactants increased the final pH. • All surfactants decreased the induction period. In the case of Empigen BAC 50, the decrease was significant, lowering the induction time by up to a minute at its lowest concentration. Dipropylene glycol n-butyl ether decreased the induction period the least, but still managed to decrease it by 30 seconds at its lowest concentration.
- test was undertaken (with Sample 1) using sterile purified water and in the absence of any organic soil.
- Sample 2 included two additional test organisms ( P. aeruglnosa and E. hirae) , and were undertaken in hard water (300 ppm CaC0 3 ) and with the addition of organic soil, bovine serum albumin - BSA.
- the test method for Sample 2 was as follows: 1ml bacterial suspension (10 7 cfu/ml) of the selected bacterium was transferred to a flask containing 1ml of a 3% BSA suspension. The culture/ soil mix was vortex mixed and then shaken on an orbital shaker for 2 minutes. To the culture/ soil mix was added 8ml sterile hard water. Mixing was continued for another minute. Without interruption of the shaking, the chemical compounds of the appropriate samples were added to the flask in powder form, in amounts calculated to give the molarities mentioned above. 5 minutes after addition of the sample, shaking was stopped and a 1ml aliquot of the test mixture was transferred to 9.0ml neutralising medium.
- test sample 1 was serially diluted and used to prepare pour plates which were subsequently incubated at 36°C for 48 hours before enumerating surviving bacteria. As an inactive control, testing was repeated without the addition of the test sample.
- the test method for Sample 1 was similar but as noted above did not employ hard water or BSA.
- a hard surface cleaning composition has the following composition.
- a hard surface cleaner has the following composition:
- Ethoxylated fatty alcohol (C12-1 4 ; 3EO) 1% w/w (non-ionic surfactant)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT01954112T ATE307874T1 (en) | 2000-07-18 | 2001-07-17 | CLEANING PROCEDURE FOR HARD SURFACES |
AU2001276461A AU2001276461A1 (en) | 2000-07-18 | 2001-07-17 | Cleaning compositions and their use |
DE60114422T DE60114422T2 (en) | 2000-07-18 | 2001-07-17 | CLEANING PROCEDURE OF HARD SURFACES |
EP01954112A EP1303583B1 (en) | 2000-07-18 | 2001-07-17 | Cleaning method of hard surfaces |
US10/333,180 US20040072710A1 (en) | 2000-07-18 | 2001-07-17 | Cleaning compositions and their use |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0017549.7 | 2000-07-18 | ||
GBGB0017549.7A GB0017549D0 (en) | 2000-07-18 | 2000-07-18 | Improvements in or relating to chemical compositions and their use |
Publications (1)
Publication Number | Publication Date |
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WO2002006434A1 true WO2002006434A1 (en) | 2002-01-24 |
Family
ID=9895831
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2001/003136 WO2002006434A1 (en) | 2000-07-18 | 2001-07-17 | Cleaning compositions and their use |
Country Status (9)
Country | Link |
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US (1) | US20040072710A1 (en) |
EP (1) | EP1303583B1 (en) |
AR (1) | AR029847A1 (en) |
AT (1) | ATE307874T1 (en) |
AU (1) | AU2001276461A1 (en) |
DE (1) | DE60114422T2 (en) |
ES (1) | ES2248360T3 (en) |
GB (2) | GB0017549D0 (en) |
WO (1) | WO2002006434A1 (en) |
Cited By (4)
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WO2006010889A1 (en) | 2004-07-24 | 2006-02-02 | Reckitt Benckiser (Uk) Limited | Improvements in or relating to cleaning |
US7682403B2 (en) * | 2004-01-09 | 2010-03-23 | Ecolab Inc. | Method for treating laundry |
US7776812B2 (en) | 2003-04-16 | 2010-08-17 | Reckitt Benckiser (Uk) Limited | Multiple emulsion hard surface cleaning compositions |
US10494591B2 (en) | 2017-06-22 | 2019-12-03 | Ecolab Usa Inc. | Bleaching using peroxyformic acid and an oxygen catalyst |
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US7883640B2 (en) * | 2004-11-10 | 2011-02-08 | The United States Of America As Represented By The Secretary Of The Army | Chemical combination for generation of disinfectant and heat |
US20090215909A1 (en) * | 2008-02-21 | 2009-08-27 | Wortley Russell B | Cleaning composition that provides residual benefits |
AU2009215861C1 (en) * | 2008-02-21 | 2016-01-21 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion and providing residual benefits |
US8143206B2 (en) * | 2008-02-21 | 2012-03-27 | S.C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion and providing residual benefits |
US9410111B2 (en) * | 2008-02-21 | 2016-08-09 | S.C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
US8980813B2 (en) | 2008-02-21 | 2015-03-17 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits |
US9481854B2 (en) | 2008-02-21 | 2016-11-01 | S. C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
US8993502B2 (en) | 2008-02-21 | 2015-03-31 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits |
US9103038B2 (en) * | 2012-05-29 | 2015-08-11 | Ecolab Usa Inc. | Acidic compositions including reducing agents for scale and decolorization of metal stains |
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- 2000-07-18 GB GBGB0017549.7A patent/GB0017549D0/en not_active Ceased
-
2001
- 2001-07-16 GB GB0117274A patent/GB2367832B/en not_active Expired - Fee Related
- 2001-07-17 AR ARP010103428A patent/AR029847A1/en unknown
- 2001-07-17 AT AT01954112T patent/ATE307874T1/en not_active IP Right Cessation
- 2001-07-17 EP EP01954112A patent/EP1303583B1/en not_active Revoked
- 2001-07-17 WO PCT/GB2001/003136 patent/WO2002006434A1/en not_active Application Discontinuation
- 2001-07-17 DE DE60114422T patent/DE60114422T2/en not_active Revoked
- 2001-07-17 AU AU2001276461A patent/AU2001276461A1/en not_active Abandoned
- 2001-07-17 ES ES01954112T patent/ES2248360T3/en not_active Expired - Lifetime
- 2001-07-17 US US10/333,180 patent/US20040072710A1/en not_active Abandoned
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EP0273467A2 (en) * | 1986-10-30 | 1988-07-06 | Colgate-Palmolive Company | Solid detergent composition, reusable cleaning pad containing same and method of manufacture |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7776812B2 (en) | 2003-04-16 | 2010-08-17 | Reckitt Benckiser (Uk) Limited | Multiple emulsion hard surface cleaning compositions |
US7682403B2 (en) * | 2004-01-09 | 2010-03-23 | Ecolab Inc. | Method for treating laundry |
WO2006010889A1 (en) | 2004-07-24 | 2006-02-02 | Reckitt Benckiser (Uk) Limited | Improvements in or relating to cleaning |
US7638470B2 (en) | 2004-07-24 | 2009-12-29 | Reckitt Benckiser (Uk) Limited | Cleaning |
EP2157161A1 (en) * | 2004-07-24 | 2010-02-24 | Reckitt-Benckiser (UK) Limited | Improvements in or relating to cleaning |
AU2005266182B2 (en) * | 2004-07-24 | 2011-01-06 | Reckitt Benckiser (Uk) Limited | Improvements in or relating to cleaning |
US10494591B2 (en) | 2017-06-22 | 2019-12-03 | Ecolab Usa Inc. | Bleaching using peroxyformic acid and an oxygen catalyst |
Also Published As
Publication number | Publication date |
---|---|
US20040072710A1 (en) | 2004-04-15 |
EP1303583B1 (en) | 2005-10-26 |
ES2248360T3 (en) | 2006-03-16 |
EP1303583A1 (en) | 2003-04-23 |
DE60114422D1 (en) | 2005-12-01 |
GB2367832B (en) | 2003-03-19 |
GB2367832A (en) | 2002-04-17 |
DE60114422T2 (en) | 2006-07-27 |
GB0117274D0 (en) | 2001-09-05 |
ATE307874T1 (en) | 2005-11-15 |
AU2001276461A1 (en) | 2002-01-30 |
GB0017549D0 (en) | 2000-09-06 |
AR029847A1 (en) | 2003-07-16 |
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