WO1994024259A1 - Hygienic cleaning composition and apparatus for spraying said composition - Google Patents
Hygienic cleaning composition and apparatus for spraying said composition Download PDFInfo
- Publication number
- WO1994024259A1 WO1994024259A1 PCT/EP1994/001175 EP9401175W WO9424259A1 WO 1994024259 A1 WO1994024259 A1 WO 1994024259A1 EP 9401175 W EP9401175 W EP 9401175W WO 9424259 A1 WO9424259 A1 WO 9424259A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hypochlorite
- alkyl
- spray
- composition
- droplets
- Prior art date
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
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
-
- 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
- C11D3/0031—Carpet, upholstery, fur or leather cleansers
-
- 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
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
-
- 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/345—Phosphates or phosphites
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
Definitions
- the present invention relates to a hygienic cleaning composition packaged in a container adapted to produce a spray.
- Hygienic cleaning compositions always have some type of anti-microbial activity and in particular generally have an anti-bacterial activity.
- Hard-surface cleaning compositions in commercial use as hygienic cleaning compositions for sanitary porcelain, work-surfaces, white goods and the like can be classified into two groups, hypochlorite-based products and hypochlorite-free products. In general, these products are liquids.
- Hypochlorite-free products comprise a variety of aqueous acids, quaternary ammonium salts, peroxy acids and solvents as the anti-microbial agents.
- the efficacy of these products varies with the type of anti-microbial agent used.
- Quaternary ammonium compounds and peroxy acids are general biocides.
- Solvents and aqueous acids are less effective especially against spore-forming bacteria.
- commercial hypochlorite-free cleaning compositions are less effective against moulds, fungi and yeasts than similar compositions which contain hypochlorite.
- Hypochlorite-based products generally contain aqueous sodium hypochlorite.
- Hypochlorite is known to be the one of the most effective hygiene agents, especially at low concentrations, and is available in commercial quantities at acceptable cost. Hypochlorite is an effective hygiene agent, providing a hygiene benefit against a wide range of microbes including bacteria, moulds, yeast and fungi.
- Hypochlorite cleaning compositions typically contain ' , in addition to the hypochlorite, one or more surfactants.
- surfactants used in hypochlorite solution are generally amine oxides and/or water soluble alkyl sulphates, although certain betaines and soaps have also been used.
- the surfactants present in hypochlorite solutions must be free of readily oxidisable groups. In some products, these surfactants are present to improve cleaning performance. In other products, these surfactants are present as a part of a thickening system.
- Typical concentrations of hypochlorite, in solution have ranged from l-15%wt: with concentrations towards the lower end of this range (less than 3%wt) being used for general purpose hygienic cleaners which find utility in both kitchens and bathrooms.
- Hypochlorite and hypochlorite-free cleaning compositions have traditionally been delivered to surfaces by use of a carrier such as a cloth or sponge onto which the composition is poured or which is dipped into a solution of the composition. This mode of application results in some wastage of the product due to absorbtion onto the cloth or sponge.
- liquid, hypochlorite-free products have been provided in a package adapted to produce a fine spray (aerosol) or jet of the product to facilitate delivery to a surface.
- Typical spray heads comprise a single, relatively small, aperture to which product is fed by pump means operated by a trigger mechanism.
- the deciding factors in determining whether a particular spray head will produce a mist or a jet include product properties, spray aperture geometry and spray pressure.
- JP 62/286000 (filed 4th June 1986 as JP 129852/86) of Unicharm K.K. describes sprayable, foaming, liquid, detergent compositions which comprise hypochlorite, an alkali, a hypochlorite stable surface active agent, and a solvent.
- the solvent is particularly characterised as being a linear polyethylene glycol or linear polypropylene glycol which is methyl-capped at both ends of the molecule.
- Preferred solvents include those with a short glycol chain. It is believed that the presence of this specific class of solvent promotes the formation of a stable foam on the surface to be cleaned and that this foam prevents the release of chlorine from the foam into the ambient.
- hypochlorite-containing product packaged in a container adapted to produce a spray which has a reduced tendency to cause respiratory irritation.
- a spray head which contains a plurality of apertures disposed so as to produce a spray of foam droplets rather than produce a jet, mist of droplets or aerosol.
- 'foam' droplets are droplets having air entrained therein.
- the present invention provides an aqueous, liquid, hypo-chlorite-containing cleaning composition
- aqueous, liquid, hypo-chlorite-containing cleaning composition comprising, 0.05%wt-3.0%wt aqueous alkali metal hypochlorite, 0.l%wt-5.0%wt of a hypochlorite-stable surfactant, said composition being packaged in a container adapted to produce a spray of foam droplets.
- an advantage of the present invention is that the product can be sprayed directly onto a surface and the use of a cloth or sponge as a carrier can be avoided. Moreover, the compositions of the present invention do not require the solvent of JP 62/286000 to be present in order to prevent droplets being formed at the surface being treated by spraying.
- the use of a spray head which forms droplets of foam avoids the formation of a fine mist of liquid droplets either through the direct action of the spray head or as a result of the impact of the product on a hard surface.
- This requires the presence of a suitable surfactant which is both foaming and sufficiently stable in the presence of the levels hypochlorite found in the product to give an acceptable shelf life. Further details on the preferred features of the invention are given below.
- Hypochlorite is an essential component of the composition according to the present invention.
- hypochlorite levels range from 0.15-2.0%wt on product. Lower levels of hypochlorite are less effective whereas the' risk of respiratory irritation increases with higher concentrations of hypochlorite. Hypochlorite levels of
- 0.15-1.0%wt, particularly 0.2-0.4wt% are preferred as this provides sufficient hypochlorite to provide a hygiene benefit without a serious risk that respiratory irritation will occur.
- compositions of the present invention are not intended to be excluded.
- surfactant is not intended to be excluded.
- a hypochlorite-stable surfactant is an essential component of the cleaning composition according to the present invention. It is important that this surfactant foams to the extent necessary to form foam droplets when sprayed.
- the surfactant comprises at least one or more of amine-oxides, betaines, sarcosinates, taurates, alkyl sulphates, alkyl sulphonates, alkyl aryl sulphonates, alkyl phenol ether sulphates, alkyl diphenyl oxide sulphanates, alkyl phosphate esters.
- amine-oxides betaines, sarcosinates, taurates, alkyl sulphates, alkyl sulphonates, alkyl aryl sulphonates, alkyl phenol ether sulphates, alkyl diphenyl oxide sulphanates, alkyl phosphate esters.
- the surfactant comprises one or more of alkyl sulphates, alkyl sulphonates and betaines.
- the surfactant is a secondary alkyl sulphonate.
- secondary alkyl sulphonate can be irritant when sprayed in a fine mist, it is particularly well adapted to the formulations of the present invention where such a fine mist is not formed.
- Particularly preferred secondary alkane sulphonates comprise a mixture of materials of the general formulation:
- R. and R 2 are the same or different, each being a straight or branched chain alkyl group having at least one carbon atom, the alkyl chain length being in the range 13- 18, and X is a solubilising cation.
- the surfactant level is l-3wt% on product.
- Lower levels of surfactant reduce cleaning efficiency whereas higher levels of surfactant can lead to an increased incidence of respiratory irritation.
- Surfactant levels of around 2%, i.e. 1.5-2.5% are particularly preferred as these provide sufficient cleaning and foaming effect without excessive use of surfactant.
- composition according to the present invention is packaged in a container adapted to produce a spray of foam droplets.
- the spray comprises less than 1000 microns/m 3 of droplets having a particle size of less than 7 microns. More preferably, the spray contains less than 500 microns/m 3 of droplets having a particle size of less than 7 microns.
- the current UK legal limit for irritant/nuisance dust and gasses is 500 mg/cubic litre.
- potentially irritant droplets are considered to have a droplet size of less than 7 microns.
- spray heads are capable of producing a foam.
- Several modifications can be made to the conventional, single aperture, spray head described above to ensure that a foam is formed and modified spray heads are commercially available.
- a typical foam-forming spray head such as that employed in the AFA 7585-4 [ex. SPRAYCHEM Ltd] bottle cap, the product is delivered to the spray head by conventional trigger-operated pump-means and ejected via a plurality of apertures comprising a grid-like plate to form a number of streams which recombine so as to entrain air within the droplets formed and thereby produce a foam.
- foaming trigger spray head being designed to deliver hypochlorite-free cleaning compositions to a surface. Many of these alternatives share the common feature of having a plurality of apertures through which the product is dispensed.
- the spray head is detachable from the body of the container in which the composition of the invention is stored so that an empty body may be replaced by a full one.
- Stabilizers are preferably present to prevent or retard decomposition of the hypochlorite during storage.
- Suitable stabilizers include transition metal sequestering agents, preferably selected from the group comprising, alkaline alkali metal silicates, phosphonates, periodates and mixtures thereof.
- a particularly preferred stabilizer comprises sodium silicate at a level of 0.1-0.5%wt on product. This is effective as a metal sequesterant in alkaline solutions. p ⁇
- products according to the present invention are alkaline, more preferably of a pH of 10-13, most preferably, 11-12. This pH is conveniently attained by the inclusion of a strong alkali such as sodium hydroxide. It is preferred that compositions according to the present invention comprise around 0.1%wt alkali metal hydroxide.
- inessential components of the formulation according to the present invention can include a colouring agent comprising one or more copper phthalocyanides.
- compositions according to the present invention can further comprise one or more of perfumes and solvents.
- formulations comprise an initial, low level of a hypo-chlorite-sensitive antifoam component which is decomposed during storage of the product.
- Silicones are particularly suited as hypochlorite sensitive antifoams.
- typical embodiments of the present invention comprise:
- composition being formulated at a pH of 10-13, packaged in a container adapted to produce a spray of foam droplets, said spray comprising less than 500 microns/m 3 of droplets having a particle size of less than 7 microns.
- composition according to the present invention was prepared from the components as listed in Table 1 below. Components are identified as follows:
- SAS Secondary alkyl sulphonate [HOSTAPUR 30-X, ex. Hoechst, RTM] , received as 30% active solution.
- Silicate Sodium silicate solution [CLAYSIL ex.
- CROSSFIELDS of Warrington] supplied as 100 Twaddle, comprising 18% NaOH, 28% silica.
- Silicone DB-100 ex.
- DOW [RTM] hypochlorite sensitive antifoam.
- Components were mixed by adding half the batch water into a stirred mixing vessel at a temperature of 50-60 Celcius: adding SAS, silicate, perfume, NaOH and silicone to the heated water, quenching with the balance of the water to around 30 Celcius and adding hypo finally.
- composition was packaged in a plastic container provided with a trigger spray head type AFA 7585-4, ex. SPRAYCHEM Ltd.
- compositions according to the present invention spraying experiments were performed to compare the potential for respiratory irritation of the present invention with that of other products.
- Compositions were sprayed, using the specified trigger head and ten trigger operations, in a 512 liter glove-box provided with an air inlet and an air outlet, onto a vertical metal surface from a distance of 1 10-30 cm.
- the particle size distribution of the airborne particles scattered within the chamber was monitored over five minutes in drawn-off air samples. Results are given in Table 2 below, for commercially available products, embodiments of the invention and other comparative examples.
- Results as presented in Table 2 are given as 'RC: the concentration of particles having a mean size below 7 microns in micrograms per cubic metre.
- 'Embodiment 1' is the composition of table 1 and the RC is that obtained using the AFA 7585-4 spray head mentioned above.
- the 'comparative' example is the composition of Table 1 using a commercially available dual mode trigger head (T-8100 ex. Continental Sprayers Inc.) in the non- foam producing spray mode, whereas 'embodiment 2' is the same dual mode spray head in the foaming mode.
- Embodiment 3 is the composition given in Table 1 with the addition of a further 0.2%wt SAS (a 10% increase in surfactant) .
- Embodiment 4 is the composition given in Table 1 with the addition of a further 0.02%wt available chlorine as hypochlorite (a 10% increase in ' hypochlorite) .
- the levels of both surfactant and available chlorine were increased 10%) .
- the commercial products are hypochlorite-free compositions used with the sprays as supplied with the product.
- VIF BATHROOM and CIF MULTIUSO are commercially available neutral and acidic cleaners and are essentially free of strongly biocidal components.
- the packaging of the 'Brand-X' product advises that the product should not be sprayed directly onto a hard surface, but should be sprayed onto a cloth for subsequent application: this product is believed to contain a quaternary ammonium compound as a biocide.
- the 'Brand-Z' composition is believed to contain relatively low levels of potentially respiratory-irritant components and to contain solvents; i.e. the product is relatively free of strongly biocidal components.
- Embodiment 1 209 0.2%
- Embodiment 3 (+SAS) 176 0.2%
- Embodiment 4 (+Hypo) 158 0.22%
- Embodiment 5 (+SAS/Hypo) 165 0.22%
- compositions of the present invention in combination with the foam producing spray head, have a low potential to cause respiratory irritation.
- the 'comparative' example produces a potentially irritant droplet cloud, and the commercially available products, which are generally free of irritants show varied droplet sizes but due to the absence of available chlorine as hypochlorite would be expected to have poor germ-kill as compared with the compositions of the present invention.
- Embodimen k k k k k
- the composition of the present invention and 'Brand-X' achieved a complete germ-kill, whereas 'Brand-Y' did not exhibit such marked antimicrobial or germicidal properties. It is noted that the composition of the present invention and 'Brand-Y' could be applied directly, whereas 'Brand-X' required the use of a cloth or sponge.
- the hypochlorite products of the present invention provide for complete kill of the entire range of microbial populations while reducing hazard and inconvenience to the user: a combination of properties not exhibited by the prior art.
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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)
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Cosmetics (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94914381A EP0694061B1 (en) | 1993-04-15 | 1994-04-12 | Hygienic cleaning composition and apparatus for spraying said composition |
AU66783/94A AU6678394A (en) | 1993-04-15 | 1994-04-12 | Hygienic cleaning composition and apparatus for spraying said composition |
DE69404032T DE69404032D1 (de) | 1993-04-15 | 1994-04-12 | Hygienische reinigungszusammensetzung und vorrichtung zum spruehen von dieserzusammensetzung |
SK1252-95A SK280780B6 (sk) | 1993-04-15 | 1994-04-12 | Čistiaci výrobok so zníženou dráždivosťou |
PL94311085A PL176537B1 (pl) | 1993-04-15 | 1994-04-12 | Higieniczna kompozycja czyszcząca |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB939307804A GB9307804D0 (en) | 1993-04-15 | 1993-04-15 | Hygienic spray cleaner |
GB9307804.6 | 1993-04-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994024259A1 true WO1994024259A1 (en) | 1994-10-27 |
Family
ID=10733894
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1994/001175 WO1994024259A1 (en) | 1993-04-15 | 1994-04-12 | Hygienic cleaning composition and apparatus for spraying said composition |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0694061B1 (cs) |
AU (1) | AU6678394A (cs) |
CZ (1) | CZ283899B6 (cs) |
DE (1) | DE69404032D1 (cs) |
ES (1) | ES2103586T3 (cs) |
GB (1) | GB9307804D0 (cs) |
HU (1) | HU216801B (cs) |
PL (1) | PL176537B1 (cs) |
SK (1) | SK280780B6 (cs) |
TR (1) | TR28732A (cs) |
WO (1) | WO1994024259A1 (cs) |
ZA (1) | ZA942580B (cs) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0783036A1 (en) * | 1995-12-07 | 1997-07-09 | The Procter & Gamble Company | Sprayable bleaching compositions for reduced irritation of the respiratory systems |
EP0794244A1 (en) * | 1996-03-04 | 1997-09-10 | The Procter & Gamble Company | Method of cleaning carpets |
EP0805198A1 (en) * | 1996-05-03 | 1997-11-05 | The Procter & Gamble Company | Cleaning compositions |
EP0805197A1 (en) * | 1996-05-03 | 1997-11-05 | The Procter & Gamble Company | Cleaning compositions |
WO1998001528A1 (de) * | 1996-07-04 | 1998-01-15 | Henkel Kommanditgesellschaft Auf Aktien | Mittel für die reinigung harter oberflächen |
WO1998059029A1 (en) * | 1997-06-23 | 1998-12-30 | Unilever Plc | Process for treatment of surfaces |
US6022840A (en) * | 1998-02-25 | 2000-02-08 | Reckitt & Colman Inc. | Aqueous cleaning compositions containing 2-ethylhexyl sulfate and C8 -C10 alkyldimethylamine oxide for removing soap scum |
US6036789A (en) * | 1998-02-25 | 2000-03-14 | Reckitt & Colman Inc. | Aqueous cleaning compositions containing 2-ethylhexyl sulfate and optionally myristyldimethylamine oxide for removing soap scum |
WO2001044429A1 (en) * | 1999-12-16 | 2001-06-21 | Unilever N.V. | Household cleaning products |
EP1130083A1 (en) * | 2000-03-03 | 2001-09-05 | Unilever Plc | Cleaning compositions |
WO2002097018A1 (en) * | 2001-05-30 | 2002-12-05 | Reckitt Benckiser Inc | Foam alkaline hard surface cleaner |
EP1497404A2 (en) * | 2002-04-01 | 2005-01-19 | Fiber Engineering, Inc. | Removing stubborn mildew stain |
RU2520168C2 (ru) * | 2012-10-08 | 2014-06-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Санитарно-гигиеническое чистящее средство |
Citations (10)
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FR2253826A1 (cs) * | 1973-12-11 | 1975-07-04 | Kao Corp | |
GB1466560A (en) * | 1974-02-05 | 1977-03-09 | Jeyes Group Ltd | Bleach compositions |
US4071463A (en) * | 1975-09-11 | 1978-01-31 | The Dow Chemical Company | Stable cleaning agents of hypochlorite bleach and detergent |
US4228048A (en) * | 1979-05-25 | 1980-10-14 | Chemed Corporation | Foam cleaner for food plants |
US4367155A (en) * | 1981-05-07 | 1983-01-04 | Coustic-Glo International, Inc. | Low-residue brightening compositions and methods for using them |
JPS62286000A (ja) * | 1986-06-04 | 1987-12-11 | ユニ・チヤ−ム株式会社 | 起泡性液体洗浄剤組成物 |
EP0298172A1 (en) * | 1987-07-06 | 1989-01-11 | The Dow Chemical Company | Thickened bleach compositions and method for preparing the same |
EP0335584A2 (en) * | 1988-03-31 | 1989-10-04 | Unilever Plc | Bleaching composition |
EP0447261A1 (en) * | 1990-03-15 | 1991-09-18 | Unilever Plc | Bleaching composition |
EP0478086A2 (en) * | 1990-09-25 | 1992-04-01 | Colgate-Palmolive Company | Stable microemulsion disinfecting detergent composition |
-
1993
- 1993-04-15 GB GB939307804A patent/GB9307804D0/en active Pending
-
1994
- 1994-04-12 SK SK1252-95A patent/SK280780B6/sk unknown
- 1994-04-12 PL PL94311085A patent/PL176537B1/pl unknown
- 1994-04-12 EP EP94914381A patent/EP0694061B1/en not_active Expired - Lifetime
- 1994-04-12 ES ES94914381T patent/ES2103586T3/es not_active Expired - Lifetime
- 1994-04-12 DE DE69404032T patent/DE69404032D1/de not_active Expired - Lifetime
- 1994-04-12 AU AU66783/94A patent/AU6678394A/en not_active Abandoned
- 1994-04-12 WO PCT/EP1994/001175 patent/WO1994024259A1/en active IP Right Grant
- 1994-04-12 CZ CZ952659A patent/CZ283899B6/cs not_active IP Right Cessation
- 1994-04-12 HU HU9501989A patent/HU216801B/hu not_active IP Right Cessation
- 1994-04-14 TR TR00331/94A patent/TR28732A/xx unknown
- 1994-04-14 ZA ZA942580A patent/ZA942580B/xx unknown
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JPS62286000A (ja) * | 1986-06-04 | 1987-12-11 | ユニ・チヤ−ム株式会社 | 起泡性液体洗浄剤組成物 |
EP0298172A1 (en) * | 1987-07-06 | 1989-01-11 | The Dow Chemical Company | Thickened bleach compositions and method for preparing the same |
EP0335584A2 (en) * | 1988-03-31 | 1989-10-04 | Unilever Plc | Bleaching composition |
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EP0478086A2 (en) * | 1990-09-25 | 1992-04-01 | Colgate-Palmolive Company | Stable microemulsion disinfecting detergent composition |
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0783036A1 (en) * | 1995-12-07 | 1997-07-09 | The Procter & Gamble Company | Sprayable bleaching compositions for reduced irritation of the respiratory systems |
EP0794244A1 (en) * | 1996-03-04 | 1997-09-10 | The Procter & Gamble Company | Method of cleaning carpets |
EP0805198A1 (en) * | 1996-05-03 | 1997-11-05 | The Procter & Gamble Company | Cleaning compositions |
EP0805197A1 (en) * | 1996-05-03 | 1997-11-05 | The Procter & Gamble Company | Cleaning compositions |
WO1998001528A1 (de) * | 1996-07-04 | 1998-01-15 | Henkel Kommanditgesellschaft Auf Aktien | Mittel für die reinigung harter oberflächen |
WO1998059029A1 (en) * | 1997-06-23 | 1998-12-30 | Unilever Plc | Process for treatment of surfaces |
US6022840A (en) * | 1998-02-25 | 2000-02-08 | Reckitt & Colman Inc. | Aqueous cleaning compositions containing 2-ethylhexyl sulfate and C8 -C10 alkyldimethylamine oxide for removing soap scum |
US6036789A (en) * | 1998-02-25 | 2000-03-14 | Reckitt & Colman Inc. | Aqueous cleaning compositions containing 2-ethylhexyl sulfate and optionally myristyldimethylamine oxide for removing soap scum |
WO2001044429A1 (en) * | 1999-12-16 | 2001-06-21 | Unilever N.V. | Household cleaning products |
EP1130083A1 (en) * | 2000-03-03 | 2001-09-05 | Unilever Plc | Cleaning compositions |
WO2002097018A1 (en) * | 2001-05-30 | 2002-12-05 | Reckitt Benckiser Inc | Foam alkaline hard surface cleaner |
EP1497404A2 (en) * | 2002-04-01 | 2005-01-19 | Fiber Engineering, Inc. | Removing stubborn mildew stain |
EP1497404A4 (en) * | 2002-04-01 | 2005-04-20 | Fiber Engineering Inc | ELIMINATION OF COLORING TENACE OF MOLD |
RU2520168C2 (ru) * | 2012-10-08 | 2014-06-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Санитарно-гигиеническое чистящее средство |
Also Published As
Publication number | Publication date |
---|---|
ES2103586T3 (es) | 1997-09-16 |
DE69404032D1 (de) | 1997-08-07 |
SK125295A3 (en) | 1996-02-07 |
CZ265995A3 (en) | 1996-05-15 |
HU216801B (hu) | 1999-08-30 |
SK280780B6 (sk) | 2000-07-11 |
EP0694061A1 (en) | 1996-01-31 |
PL176537B1 (pl) | 1999-06-30 |
HU9501989D0 (en) | 1995-09-28 |
EP0694061B1 (en) | 1997-07-02 |
TR28732A (tr) | 1997-02-20 |
CZ283899B6 (cs) | 1998-07-15 |
AU6678394A (en) | 1994-11-08 |
PL311085A1 (en) | 1996-02-05 |
HUT72729A (en) | 1996-05-28 |
ZA942580B (en) | 1995-10-16 |
GB9307804D0 (en) | 1993-06-02 |
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