WO1998040465A1 - Compositions antimicrobiennes, leur preparation et utilisation - Google Patents

Compositions antimicrobiennes, leur preparation et utilisation Download PDF

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Publication number
WO1998040465A1
WO1998040465A1 PCT/GB1998/000719 GB9800719W WO9840465A1 WO 1998040465 A1 WO1998040465 A1 WO 1998040465A1 GB 9800719 W GB9800719 W GB 9800719W WO 9840465 A1 WO9840465 A1 WO 9840465A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
silver
antimicrobial
water
carrier
Prior art date
Application number
PCT/GB1998/000719
Other languages
English (en)
Inventor
Malcolm Tom Mckechnie
Original Assignee
Reckitt & Colman Products Limited
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 Reckitt & Colman Products Limited filed Critical Reckitt & Colman Products Limited
Priority to AU64088/98A priority Critical patent/AU6408898A/en
Publication of WO1998040465A1 publication Critical patent/WO1998040465A1/fr

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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
    • C11D3/12—Water-insoluble 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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

  • Antimicrobial Compositions their Preparation and Use
  • This invention relates to compositions suitable for use as toilet cleanser blocks, which include an antimicrobial agent for disinfecting water in, for example, the toilet bowl of a water closet.
  • this invention relates to the incorporation of antimicrobial silver ions into such compositions.
  • compositions in the form of coherent self-supporting blocks for use in treating the water in toilet bowls.
  • such blocks are mounted in cage-like containers near the rim of the bowl in a position where, on each occasion the toilet bowl is flushed, the flushing water enters the container and contacts the block to leach out the composition.
  • the flushing water entering the toilet bowl already includes the composition.
  • the composition in the blocks comprises a simple mixture of a surfactant, a fragrance and a dye to provide a basic cleaning affect and to counter malodours.
  • an antimicrobial agent present in toilet blocks. It is known to include chlorine-generating agents in the blocks to provide antimicrobial activity, but it is difficult to find fragrances and dyes which are stable in the presence of such chlorine-generating agents. Silver ions are also known to be antimicrobial agents. However, it is well known that, in situations where silver has been used as an antimicrobial, electrochemical methods have been employed to generate the silver ions, such as in swimming pools or coolant systems, which are clearly inapplicable to toilet blocks.
  • European patent specification no. EP 494 373 discloses a composition for treating swimming pools comprising copper sulphate, silver nitrate, sodium gluconate and zinc chloride or sulphate with water and a complexone such as EDTA.
  • Japanese patent abstract no. JP 87143655 discloses a bath cleaner comprising a granulated soluble glass of silica, soda, boria, alumina and silver nitrate.
  • Other combinations involving silica and silver nitrate are also known, for example, from Japanese patent abstract no. JP 8333210.
  • a coherent self-supporting body formed of an antimicrobial composition
  • an antimicrobial composition comprising a source of silver ions as antimicrobial agent, the composition being such that silver ions are released from the composition when the body is in contact with water.
  • a solid in-the-cistem (ITC) or in-the-bowl (ITB) antimicrobial block containing a source of silver ions the block being such that it provides a controlled-release of silver ions when the composition is in contact with water.
  • composition suitable for use as a toilet block which composition comprises a) an antimicrobial composition comprising a silver compound deposited on a support material, preferably a physiologically inert oxidic synthetic particulate support material; and b) a carrier for the antimicrobial composition, which carrier is adapted to render the composition suitable for use as a toilet block.
  • the carrier comprises (i) a water-soluble detergent or surfactant;
  • the carrier preferably is in the form of a coherent self-supporting body which incorporates the antimicrobial composition.
  • the antimicrobial composition is selected from those disclosed in European patent specification no. 251 783, the contents of which are incorporated herein by reference in their entirety.
  • the antimicrobial silver compound is preferably one which has relatively low solubility in aqueous media and in which the silver is present as an ionic species.
  • the form of the compound should thereby be such that release of ionic silver in solution at an effective level for antimicrobial but non-toxic effect is facilitated.
  • the source of the silver ions is a silver salt such as a silver halide, for example silver chloride.
  • the composition includes a support material for the source of silver ions.
  • the antimicrobial silver compound may be present at a level of from 1 to 75% by weight of the support material, preferably from 10 to 60% by weight.
  • the support material is porous so that it can absorb the silver compound and protect it from ambient light.
  • Suitable support materials are physiologically inert oxidic materials, that is, they comprise either an oxide or a hydroxide, or contain a complex oxy-anion species such as phosphate or sulphate. Suitable materials are essentially insoluble and stable in water or aqueous environments and will not form hydrates.
  • stable in water or aqueous environments we mean to distinguish between those compounds which, in contact with water, form a chemically-bound hydrate on the one hand and those which may absorb water to form an associated aqueous species on the other hand, and to indicate the latter.
  • Synthetic oxidic materials which may be suitable as physiologically inert supports in antimicrobial compositions according to the invention include oxides of titanium, magnesium, aluminium, silicon, cerium, zirconium, hafnium, niobium and tantalum, calcium hydroxyapatite and barium sulphate, in which the oxidic material is stable in water or aqueous environments.
  • titanium dioxide which is a preferred material for use in the present invention
  • the crystalline forms anatase, rutile and brookite are substantially chemically anhydrous, and one or more of these forms is suitable for use in the present invention. Fully hydrated or hydratable oxides of titanium are excluded.
  • the particle size of support materials for use in the invention is preferably less than 25 micrometres, more preferably in the range of from 1 to 15 micrometres. In general, smaller size particles are preferred, including those in the sub-micrometre range, commensurate with achieving the desired antimicrobial effect.
  • the morphology is preferably such that the structure is highly open.
  • the materials may comprise approximately spherical clusters of crystallites having large physical voidage therebetween. Surface areas may extend from 1 or 2 m 2 /g up to approximately 240 m 2 /g, preferably in the range of from 5 to 100 m 2 /g.
  • the support material On contact with aqueous media, the support material releases silver ions in a controlled way.
  • the support material is a composite comprising titanium dioxide having an average particle size of about 1 to 15 micrometres, preferably about 2 to 5 micrometres, and having from about 10 to 80%, preferably 20 to 60%, by weight (based on the composite) of silver chloride incorporated therein.
  • the compositions according to this invention may comprise one or more surfactants, colourants, binders, fragrances, anti-limescale agents and fillers.
  • reducing agents are excluded, otherwise the silver ion will be reduced to relatively ineffective silver metal.
  • the surfactants may be anionic surfactants, cationic surfactants or non-ionic surfactants.
  • suitable anionic surfactants include alkali metal salts of alkyl substituted benzene sulphonic acids, alkali metal salts of long chain fatty sulphates, alkali metal ether sulphates derived from alcohols and alkyl phenols, alkali metal sulphosuccinates and alkali metal sarcosinates.
  • Cationic surfactants may be exemplified by quaternary ammonium bromides and chlorides containing a long chain alkyl group, of which benzalkonium chloride is a particular example.
  • Non-ionic surfactants may be of the betaine or imidazoline types. Other suitable surfactants will be known to those skilled in the art.
  • the rate of dissolution of the composition may be controlled by the addition of optional solubility control agents.
  • Suitable solubility control agents will usually include materials having a solubility which is lower than the readily soluble components (principally surfactants) of the composition.
  • Such solubility control agents may vary in nature from substantially wholly water-insoluble materials to materials having a low solubility in water.
  • substantially insoluble solubility control agents include paradichlorobenzene, waxes such as beeswax or carnauba wax, petroleum waxes, long chain fatty acids and alcohols, and esters thereof, and fatty alkylamides. Solubility control agents of limited aqueous solubility may also be used, and examples thereof will be known to those skilled in the art.
  • Suitable solubility control agents are those which can withstand the conditions of manufacture (e.g. pressure, temperature) used in processes (such as extrusion processes) ordinarily used to form the bodies of the invention, and are not limited to the above examples.
  • colourants are commercially available colourants such as “Solvent Yellow 98” from Hoechst or “Solvent Blue 70” from BASF. It will be understood, however, that any colourants known to be suitable in the art can be used.
  • Suitable binders are starch, starch derivatives, cellulose ethers and polyethylene glycolethers.
  • fillers are sodium sulphate and silica.
  • Preferred compositions of the present invention which are suitable for use as ITC or ITB toilet blocks comprise:
  • an antimicrobial composition comprising a silver compound deposited on a support material wherein the amount of silver compound is from 1 to 75% w/w of the support material;
  • compositions of the present invention comprise from about
  • an antimicrobial composition comprising a silver salt deposited on particulate titanium dioxide;
  • compositions of the present invention comprise
  • the present invention further provides a process for preparing a composition suitable for use as a toilet block, which process comprises bringing into physical admixture
  • an antimicrobial composition comprising a silver compound deposited on a support material, preferably a physiologically inert oxidic synthetic particulate support material;
  • the process comprises
  • step (d) adding any wet or liquid ingredients of the carrier to the mixture produced by step (c) and; optionally
  • toilet blocks of from about 25 to 75g, such as 40 to 55g, therefrom and; optionally
  • composition of the present invention is particularly suitable for disinfecting the toilet bowl of a water closet and, in a particularly preferred embodiment, the body, preferably of block-like form, is located within a cage-like container adapted to be mounted adjacent to the rim of the toilet bowl.
  • the container is of the siphon type which delivers composition to the toilet bowl at the end of the flushing operation.
  • the majority of the composition is retained in the toilet bowl rather than being lost down the drain.
  • a further aspect of the invention accordingly provides a method of disinfecting water in the toilet bowl of a water closet, which method comprises locating the composition in accordance with the first aspect of the invention in the path followed by the flushing water during flushing of the toilet bowl, and flushing the toilet bowl.
  • composition of the present invention may be located in the cistern supplying the flushing water.
  • the body is preferably encased in a soluble coating material for ease of handling.
  • Figure 1 is an end view of a first type of container, in its closed configuration, for accommodating a body in accordance with the present invention
  • Figure 2 is a top view of the container of Figure 1 in its open configuration
  • Figure 3 is a longitudinal cross section through a part of the container of Figure 2 along line Ill-Ill of Figure 2;
  • Figure 4 is a side view of a second type of container for accommodating a body in accordance with the present invention.
  • Figure 5 is a top view of the container of Figure 4;
  • Figures 6a, 6b and 6c are graphs showing the relationship between the number of flushes and the silver ion content (in parts per billion) of the toilet bowl water after each flush when using an antimicrobial body in accordance with the present invention;
  • Figure 7 is a further graph similar to the graphs of Figures 6a, 6b and 6c;
  • Figures 8a, 8b and 8c are graphs illustrating the relationship between viable test organism count and time in flush water when using different antimicrobial bodies in accordance with the present invention.
  • Figure 9 shows graphs of surviving number of organisms against time in flush water using an antimicrobial body in accordance with the present invention and using a conventional product.
  • the container is in the form of a cage formed of rigid plastics material. It includes an upper wall 1 pivotally mounted at one edge to lower wall 2 via hinge mechanism 3 to define a chamber.
  • the chamber is for accommodating an antimicrobial block-like body of the present invention.
  • the container includes a flexible hanger portion 4 comprising a first end 5 secured to an upper part of the lower wall 2 and a second end 6 adapted to be hooked over the rim of a toilet bowl (not shown).
  • the hanger 4 includes a tongue 7 terminating in a free end including an abutment 8 adapted to engage with an abutment of a catch 9 provided at the top of the upper wall 1 so as to prevent undesired pivotal movement of upper wall 1 and lower wall 2 about hinge mechanism 3.
  • the second end 6 of the hanger 4 includes a protrusion 10 which can be inserted into catch 9 to release the free end of the tongue 7 when it is desired to open the container by relative pivotal movement of upper and lower walls 1 and 2 about hinge 3 in order to fit a new body according to the invention.
  • the upper wall 1 includes a plurality of apertures 11 to enable flushing water to pass through the wall and enter into the chamber.
  • the lower wall 2 is not so provided with apertures.
  • the container includes an upstanding tubular portion 12 at one end and an aperture 13 is provided at the lower part of this tubular portion 12 to provide communication between the interior of the tubular portion 12 and the interior of the chamber.
  • the tubular portion 12 also includes an outlet pipe 14 having an upper first end 15 communicating with the tubular member 12 at a location above the aperture 13 and a lower second end 16 terminating externally of the lower wall 2.
  • the upper end of the tubular portion 12 is effectively sealed by a co-operating part 20 provided on the upper wall 1 .
  • the hanger portion 4 is bent so as to enable the protrusion 10 to be inserted into catch 9 to release the tongue 7 whereby the upper wall 1 can be pivoted, about hinge mechanism 3, with respect to the lower wall 2 to enable a body 19 in accordance with the present invention to be placed in the chamber so that it rests on the uppermost edges of walls 17.
  • the container is then mounted on the rim of the toilet bowl by means of hanger 4 so that it is in a position where it will be in the water flow when the toilet is flushed.
  • the container comprises side walls 31 and 32 of rigid plastics material joined together at their lower parts by means of a hinge mechanism 33.
  • the side wall 32 includes a tongue 34 which engages in a receptor portion 35 on side wall 31 so that the side walls 31 and 32 are ordinarily held together to define a chamber for a block-like body 40 in accordance with the present invention.
  • the container includes a flexible hanger 36 secured to the side wall 31 at one end and having a second end 37 to enable the container to be hung on the rim of a toilet bowl.
  • the end 37 may include a protrusion (not shown) to enable the tongue 34 to be released from the receptor portion 35 when it is desired to open the chamber to insert a fresh anti-microbial body.
  • the side walls 31 and 32 are provided with apertures 38 and the lower part of side wall 32 is provided with apertures 39.
  • the container is suspended on rim of the toilet bowl by the hanger 36 in a position where it will be contacted by the water during flushing.
  • the water enters into the chamber via apertures 38, passes over the body 40 and leaches silver ions therefrom, and then leaves the chamber via bottom apertures 39 to fall into the toilet bowl wherein the silver ions disinfect the toilet bowl water and adjacent surfaces of the bowl.
  • EXAMPLE 1 A free-flowing titanium dioxide/silver chloride composite powder was prepared by reacting silver nitrate with sodium chloride in the presence of titanium dioxide particles having an average size of from about 2 to 3 micrometres so that, after drying, the composite contained 20% by weight silver chloride and 80% by weight titanium dioxide. 2.5% w/w of the composite was then admixed thoroughly with the following ingredients:
  • the efficacy of the blocks for disinfecting toilet bowl water was then ascertained by carrying out tests run in parallel on two different test rigs, each including an automatic flushing toilet. Each block was located in a cage-like container and mounted at the toilet rim. The flush cycle was set at 30 flushes every 24 hours with a uniform time interval between flushes. Generally, about 0.1 gram of the composition was leached away at each flush. After each flush, the degree of silver dosing achieved was determined by collecting a sample of the water from the toilet bowl, fixing the silver present in the water with 1 % nitric acid, and then analyzing it by ICP-MS (Inductively Coupled Plasma Mass Spectrometry).
  • ICP-MS Inductively Coupled Plasma Mass Spectrometry
  • Example 1 was repeated except that in a first experiment the block contained 0.6% w/w of the composite and in a second experiment the block contained 1.25% w/w of the composite. The results obtained in each case are shown in the graph of Figure 7 of the accompanying drawings. Again, an amount of silver ion effective to provide antimicrobial properties was present in the toilet bowl after a large number of flushes.
  • EXAMPLE 3 Example 1 was repeated except that in a first experiment the block contained 0.6% w/w of the composite and in a second experiment the block contained 1.25% w/w of the composite. The results obtained in each case are shown in the graph of Figure 7 of the accompanying drawings. Again, an amount of silver ion effective to provide antimicrobial properties was present in the toilet bowl after a large number of flushes. EXAMPLE 3
  • Lavatory blocks were prepared as described in Example 1 and included respectively 0.625% w/w, 1.25 w/w and 2.5% w/w of the composite. These blocks were mounted in a flushing toilet subjected to normal use and a sample of flush water was collected after the number of flushes indicated in Table 1.
  • Lavatory blocks prepared as described in Example 1 and including 1.25% w/w of the composite were tested for antimicrobial efficacy against Pseudomonas aeruginosa, Enterococcus hirae and Escherichia coli, using the method described in Example 3.
  • Samples of flush water after 50 flushes were taken out, and 1 hour later, were inoculated respectively with approximately 1 ,000,000 cfu/ml of each of the above test organisms.
  • tests were also performed using a lavatory block containing 15-30% of a chlorine-based bleaching agent (sodium dichloroisocyanurate (DCCNa)).
  • lavatory blocks were prepared as described in Example 1 with 1.25% w/w of the composite and tested against Escherichia coli and Pseudomonas aeruginosa. As a comparison, tests were also performed using a lavatory block containing 15-30% sodium dichloroisocyanurate (DCCNa).
  • DCCNa sodium dichloroisocyanurate
  • Each block was located in a siphonic cage and mounted on the toilet rim. After 60 flushes, water samples were taken from the lavatory bowl and also on one occasion from the cistern as a control. The water samples were split into two, and one sample was inoculated with approximately 1.0x10 3 cfu/ml E. coli and the other sample with a similar inoculum of Ps. aeruginosa. Total viable counts (TVC) of the inoculated samples were then measured at various times over a 24 hour period. The organism inoculum was prepared by washing 3 times in distilled water by centrifuging at 3000 ppm in a refrigerated centrifuge. The final pellet of organisms was suspended in distilled water to minimise extraneous organic soiling of the samples.
  • TMC Total viable counts
  • results show that, with the lavatory blocks of the present invention, there is evidence of prolonged antimicrobial activity which is able to resist repeated challenge over a four day period of E. coli and Ps. aeruginosa.
  • the DCCNa-containing block only showed comparable antimicrobial activity for one day with a single inoculation of the challenge organism.
  • results demonstrate that, if lavatory blocks of the present invention are used, the ability of the toilet flush water to resist repeat challenge with typical water-borne and intestinal/food poisoning microorganisms, between flushes, is in the order of 4 to 5 times greater than if a comparative DCCNa-containing block is used.

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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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une composition appropriée à une utilisation comme bloc désinfectant pour toilettes, laquelle composition comprend une composition antimicrobienne renfermant un composé d'argent déposé sur une matière de support particulaire synthétique oxydante physiologiquement inerte, ainsi qu'un support pour la composition antimicrobienne conçu pour permettre l'utilisation de la composition comme bloc désinfectant pour toilettes. De préférence, on donne à cette composition la forme d'un bloc désinfectant pour toilettes placé dans la cuvette à l'intérieur d'une cage à effet siphon.
PCT/GB1998/000719 1997-03-13 1998-03-10 Compositions antimicrobiennes, leur preparation et utilisation WO1998040465A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU64088/98A AU6408898A (en) 1997-03-13 1998-03-10 Antimicrobial compositions, their preparation and use

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9705220.3 1997-03-13
GBGB9705220.3A GB9705220D0 (en) 1997-03-13 1997-03-13 Improvements in or relating to disinfectants

Publications (1)

Publication Number Publication Date
WO1998040465A1 true WO1998040465A1 (fr) 1998-09-17

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ID=10809186

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/000719 WO1998040465A1 (fr) 1997-03-13 1998-03-10 Compositions antimicrobiennes, leur preparation et utilisation

Country Status (5)

Country Link
AR (1) AR011981A1 (fr)
AU (1) AU6408898A (fr)
GB (3) GB9705220D0 (fr)
WO (1) WO1998040465A1 (fr)
ZA (1) ZA982092B (fr)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006026815A1 (fr) * 2004-09-07 2006-03-16 Bacstop Corporation Pty Ltd Procede, materiau et systeme de liberation controlee d'antimicrobiens
EP2688411A2 (fr) * 2011-03-24 2014-01-29 Silver Anti-Bac, LLC Compositions de chlorure d'argent pour la désodorisation et la désinfection
USD752198S1 (en) 2015-03-18 2016-03-22 S.C. Johnson & Son, Inc. Toilet rim block holder
USD752733S1 (en) 2015-03-18 2016-03-29 S.C. Johnson & Son, Inc. Toilet rim block holder
USD784491S1 (en) 2016-05-17 2017-04-18 S. C. Johnson & Son, Inc. Toilet rim block
USD789485S1 (en) 2016-05-17 2017-06-13 S. C. Johnson & Son, Inc. Toilet rim block holder
US10144908B2 (en) 2013-04-16 2018-12-04 Conopco, Inc. Liquid soap having enhanced antibacterial activity
USD841120S1 (en) 2017-01-31 2019-02-19 S. C. Johnson & Son, Inc. Toilet rim-block
USD850578S1 (en) 2017-01-31 2019-06-04 S. C. Johnson & Son, Inc. Toilet rimblock
US10344462B2 (en) 2014-09-08 2019-07-09 S. C. Johnson & Son, Inc. Toilet rimblock and method of making such rimblock
US10370622B2 (en) 2013-04-16 2019-08-06 Conopco, Inc. Soap bar having enhanced antibacterial activity
USD912761S1 (en) 2019-06-07 2021-03-09 S. C. Johnson & Son, Inc. Toilet rim-block
USD914131S1 (en) 2019-06-07 2021-03-23 S. C. Johnson & Son, Inc. Toilet rim-block holder
USD923139S1 (en) 2019-06-07 2021-06-22 S. C. Johnson & Son, Inc. Set of toilet rim-blocks

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BR0214098B1 (pt) * 2001-11-13 2015-01-06 Reckitt Benckiser Llc Aperfeiçoamento relativo a artigos de limpeza para vaso sanitário
DE10312617A1 (de) * 2003-03-21 2004-10-07 Henkel Kgaa Keimreduzierendes Wasch- oder Reinigungsmittel und Verfahren zu seiner Herstellung
CA2585939C (fr) 2004-11-03 2013-06-04 K2 Concepts, Inc. Compositions antimicrobiennes et procedes de fabrication et d'utilisation
US8394420B2 (en) 2005-11-03 2013-03-12 K2 Concepts, Inc. Substrates comprising anti-microbial compositions and methods of making and using the same
DE102009045678A1 (de) * 2009-10-14 2011-04-21 Henkel Ag & Co. Kgaa Hygienewaschmittel

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GB8616294D0 (en) * 1986-07-03 1986-08-13 Johnson Matthey Plc Antimicrobial compositions
US5149354A (en) * 1991-01-10 1992-09-22 Delaney Brendan J Composition for treating swimming pools
GB9713023D0 (en) * 1997-06-20 1997-08-27 Reckitt & Colmann Prod Ltd Improvements in or relating to the cleansing of surfaces

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DATABASE WPI Derwent World Patents Index; *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006026815A1 (fr) * 2004-09-07 2006-03-16 Bacstop Corporation Pty Ltd Procede, materiau et systeme de liberation controlee d'antimicrobiens
US8512725B2 (en) 2004-09-07 2013-08-20 Bacstop Corporation Pty Ltd Method, material and system for controlled release of anti-microbial agents
EP2688411A2 (fr) * 2011-03-24 2014-01-29 Silver Anti-Bac, LLC Compositions de chlorure d'argent pour la désodorisation et la désinfection
EP2688411A4 (fr) * 2011-03-24 2014-08-27 Silver Anti Bac Llc Compositions de chlorure d'argent pour la désodorisation et la désinfection
US10370622B2 (en) 2013-04-16 2019-08-06 Conopco, Inc. Soap bar having enhanced antibacterial activity
US10144908B2 (en) 2013-04-16 2018-12-04 Conopco, Inc. Liquid soap having enhanced antibacterial activity
US10344462B2 (en) 2014-09-08 2019-07-09 S. C. Johnson & Son, Inc. Toilet rimblock and method of making such rimblock
USD752733S1 (en) 2015-03-18 2016-03-29 S.C. Johnson & Son, Inc. Toilet rim block holder
USD752198S1 (en) 2015-03-18 2016-03-22 S.C. Johnson & Son, Inc. Toilet rim block holder
USD784491S1 (en) 2016-05-17 2017-04-18 S. C. Johnson & Son, Inc. Toilet rim block
USD789485S1 (en) 2016-05-17 2017-06-13 S. C. Johnson & Son, Inc. Toilet rim block holder
USD841120S1 (en) 2017-01-31 2019-02-19 S. C. Johnson & Son, Inc. Toilet rim-block
USD850578S1 (en) 2017-01-31 2019-06-04 S. C. Johnson & Son, Inc. Toilet rimblock
USD912761S1 (en) 2019-06-07 2021-03-09 S. C. Johnson & Son, Inc. Toilet rim-block
USD914131S1 (en) 2019-06-07 2021-03-23 S. C. Johnson & Son, Inc. Toilet rim-block holder
USD923139S1 (en) 2019-06-07 2021-06-22 S. C. Johnson & Son, Inc. Set of toilet rim-blocks

Also Published As

Publication number Publication date
ZA982092B (en) 1998-10-09
GB9705220D0 (en) 1997-04-30
GB2324727B (en) 2001-04-11
GB2324727A (en) 1998-11-04
GB9804895D0 (en) 1998-04-29
AU6408898A (en) 1998-09-29
GB9805083D0 (en) 1998-05-06
AR011981A1 (es) 2000-09-13

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