EP2134829B1 - Bloc de nettoyage pour surface dure auto-adhésif - Google Patents

Bloc de nettoyage pour surface dure auto-adhésif Download PDF

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Publication number
EP2134829B1
EP2134829B1 EP08735463A EP08735463A EP2134829B1 EP 2134829 B1 EP2134829 B1 EP 2134829B1 EP 08735463 A EP08735463 A EP 08735463A EP 08735463 A EP08735463 A EP 08735463A EP 2134829 B1 EP2134829 B1 EP 2134829B1
Authority
EP
European Patent Office
Prior art keywords
hard surface
cleaning block
surfactant
surface cleaning
toilet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP08735463A
Other languages
German (de)
English (en)
Other versions
EP2134829A1 (fr
Inventor
Syed Husain Abbas
Daniele Del Fiol
Paolo Mondani
Serena Pezzia
Ivana Trombetta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to PL08735463T priority Critical patent/PL2134829T3/pl
Priority to EP08735463A priority patent/EP2134829B1/fr
Publication of EP2134829A1 publication Critical patent/EP2134829A1/fr
Application granted granted Critical
Publication of EP2134829B1 publication Critical patent/EP2134829B1/fr
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
    • C11D17/0095—Solid transparent soaps or detergents
    • 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
    • C11D3/50—Perfumes

Definitions

  • the present invention relates to the use of self adhesive hard surface cleaning blocks, and to a method for providing hygiene in a toilet.
  • Hard surface cleaning blocks such as lavatory blocks are known in the art and are typically configured to provide an automatic and sustained release of active ingredients to a liquid passing the block and/or the release of perfume to the air.
  • they may be suspended in a container under the rim of a lavatory bowl or urinal such that, during a flushing cycle, water from the cistern flows over the block thereby dissolving a portion of the block and releasing active ingredients of the block into the lavatory bowl. They may also be used inside a dish washing machine or even for the purpose of manual dishwashing.
  • Holders for solid detergent blocks are for instance disclosed in EP-B1-586 137 .
  • An alternative to the lavatory block is a liquid dispenser device, such as the device disclosed in GB2389123 .
  • Both the liquid and the solid rim device require a holder connecting the lavatory block to the toilet rim.
  • Present day consumers do not like the idea of having to touch and handle a device that has been in the toilet for weeks, when refilling or replacement is required. Due to environmental reasons, disposal of such devices is also not appreciated by the consumers.
  • One such alternative is a tablet for use in the water cistern.
  • this kind of device cannot be used in built-in water cisterns that are becoming more and more popular.
  • Another alternative is a pump device having a dispenser at the toilet rim and a separate bottle with cleaning liquid outside the toilet. This option has the disadvantage of a tube connecting the rim device to the bottle with cleaning liquid.
  • GB-1364460 discloses a method for cleaning or disinfecting lavatory bowls by introducing into the flushing system a composition shaped to a tablet comprising detergent, disinfectant, hydrophobic material and perfume.
  • GB-2061996 discloses a lavatory cleansing block comprising surfactant and optionally perfume which is to be used in the flush-water cistern of a lavatory bowl.
  • US-A-4,308,625 discloses a sanitizing agent with a dye to be used in the toilet flush water.
  • US-A-2002/035049 discloses compositions suitable for use as a toilet cleanser block by use in toilet cisterns.
  • EP-A-619,366 discloses solid cleaning blocks which may be used as in-rim lavatory blocks, whereby the blocks are to be hung from the rim of a lavatory bowl in a convenient type rim cage.
  • GB 2061313 discloses lavatory cleansing blocks for immersion in the flushing system.
  • DE 2602514 discloses a self-supporting toilet cleaning block including a plastic net which contains the active composition, which block may be placed on the rim of a toilet bowl with a holder.
  • the hard surface cleaning composition can even be applied directly onto the surface as disclosed in EP-A1-1 086 199 , where a self adhesive paste is disclosed.
  • copending European application nr 2,082,020 discloses a detergent composition comprising an adhesive phase.
  • a detergent block that can be easily positioned on a hard surface remains to be desired.
  • a hard surface cleaning block comprising an adhesive phase meets at least one of these objects.
  • the invention provides a method for providing hygiene in a toilet, as specified in claim 1.
  • the invention further provides a use of a self sticking hard surface cleaning block, as specified in claim 7.
  • the hard surface cleaning block used according to the invention comprises
  • the invention relates to a method including the step of providing a self sticking block which is used to directly stick on a toilet surface.
  • the self sticking behaviour is due to the formation of liquid crystalline phase in presence of water.
  • Said liquid crystalline phases have different rheological properties.
  • the phase transition behaviour of the composition in presence of water provides a way to stick the block in toilet, thus providing a self adhesive system. It has been found that cubic and hexagonal phases have good adhesion properties and have got very high viscosity. It is possible to have lamellar liquid phase in the composition which in contact with water forms hexagonal phase and gives adhesion properties to the block, thus providing the possibility to attach the composition to a wet surface.
  • the hard surface cleaning composition of the invention is intended to gradually release active ingredients, in particular perfume. This is achieved by providing a block that gradually erodes or dissolves when contacted or flushed with water.
  • Toilet blocks preferably last for at least 50 flushes, more preferably at least 200 flushes, but not more than 300 flushes
  • the hard surface cleaning composition of the invention may be a solid, or semi-solid composition in the meaning of Römpp Lexicon Chemie, 10 th edition, Stuttgart/New York, 1997.
  • the surfactant forms a liquid crystalline phase in contact with water. These liquid crystalline phases help in the adhesive properties of the block. Besides adhesion properties these surfactants provide sufficient foam during use.
  • Suitable surfactants are non ionic surfactants. Suitable non ionic surfactants are alcohol ethoxylates with a high degree of ethoxylation, such as C14 to C24 fatty alcohols with 20 to 60 ethylene oxide groups, more preferably C16 to C20 fatty alcohols with 20 to 60 ethylene oxide groups.
  • the composition may contain 0-15% of C10-C12 fatty alcohol ethoxylates with ethoxylation value of 2-10 for getting acceptable foaming properties.
  • 10-80% of long chain fatty alcohol ethoxylates may be used to give some foaming properties but mainly for giving body or structure to the block.
  • the chain length and the ethoxylation values are selected based on the melting point of the fatty alcohol ethoxylate.
  • the preferred melting point for the ethoxylate is from 40°C to 65°C. More preferred melting point is 45°C to 60°C and the most preferred range is 50°C to 58°C
  • polysorbate nonionic surfactants may also be used. More preferably the polysorbate is a short chain (C10-C12) polysorbate, such as Tween 20, or longer chain (up to C18) unsaturated polysorbate, such as Tween 80. Polysorbate nonionic surfactants are found to have excellent foaming properties.
  • fragrance in the composition it is possible to use soap with a suitable chain distribution of C8-18 with at least 5-25% of C16-C18 saturated soap. Small levels of other anionic and amphoteric surfactants may also be used to give good foaming properties.
  • the anionic and amphoteric surfactants form liquid crystalline phases above Krafft point. These liquid crystalline phases help in the adhesion properties of the product to the hard surface.
  • the surfactants with Krafft Point less than room temperature are suitable for this application.
  • Anionic surfactants such as alfa olefin sulfonate, sodium lauryl ether sulphate and sodium lauryl sulphate are suitable for this application.
  • CMEA, CDEA and the amphoteric surfactants such as CAP Betaine can also be used to get similar result. These surfactants can be used at 2-10% level in the formulation. The most preferred level can be 2-5%. Higher levels have been observed to give softer product.
  • the surfactant forming a liquid crystalline phase in the presence of water is present in the composition in a concentration of at least 50%, preferably at least 60% by weight.
  • the surfactant is present in the block in a concentration of not more than 80%, preferably not more than 75%, more preferably not more than 65% by weight.
  • the composition also comprises perfume to provide constant room scenting.
  • the perfume may be a single discrete ingredient, but more typically will be a complex blend of volatile liquid (and some solid) ingredients of natural and/or synthetic origin.
  • the perfume is present in the composition in a concentration of 1-50% by weight. More preferably, the composition comprises at least 4% of perfume.
  • the composition preferably comprises not more than 40%, more preferably not more than 30%, still more preferably not more than 30%, even more preferably not more than 20%, or even less than 10% by weight of perfume.
  • the hard surface cleaning composition according to the invention may further comprise detergent active, builders, dyes, perfume, hygiene agents, antioxidants, radical scavengers, chelating agents, hydrotropes, anticorrosion agents, opacifiers, brighteners, preservatives and/or abrasives.
  • detergent active builders, dyes, perfume, hygiene agents, antioxidants, radical scavengers, chelating agents, hydrotropes, anticorrosion agents, opacifiers, brighteners, preservatives and/or abrasives.
  • further ingredient that compromise the transparent or translucent character of the composition are not preferred.
  • Suitable detergent active are e.g. described in " Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949 , Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 , in the current edition of " McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in " Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
  • the composition may optionally comprise humectant.
  • Humectants maintain both structure and clarity, enabling salvation of the soap chains/ribbons to maintain microcrystalline domains. If these domains are kept small and prevent further crystal nucleation, then the resultant structure is transparent.
  • Preferred humectants are polyhydroxylated organic compounds, such as sorbitol and sucrose.
  • the humectant may be present in a concentration of 0 to 40% by weight of the composition.
  • the humectant is preferably present in a concentration of at least 5%, but preferably not more than 20%, more preferably not more than 10%.
  • Solvents may also be present in the composition.
  • Preferred solvents include glycols, (e.g. monopropylene glycol/propane-1,2-diol), poly alkylene glycols (e.g. PEG, PPG), water and short chain organic solvents (e.g. ethanol or isopropanol) and perfumes.
  • the solvent may be present in the composition in a concentration of 0 to 10%, preferably 1-10% by weight of the composition.
  • the shape of the hard surface cleaning block may affect the adhesive properties of the block. It is preferred that the blocks have a hydrodynamic shape, to improve the erosion properties of the block which in turn helps in lasting adhesion of the block to the surface. Thus, round, smooth shapes are preferred over square/rectangular blocks with sharp edges, due to superior hydrodynamic behaviour.
  • a normal size toilet block is between 30 and 50 grams, usually about 40 grams. This sort of block typically lasts for at least 100 flushes, preferably more than 200 flushes. The blocks preferably last for up to about 300 flushes.
  • At least partially transparent or translucent is meant that a 1 cm thick sample of the material transmits at least 5% of visible light, preferably at least 20% of visible light, more preferably at least 50% of visible light. More preferably the block is transparent. By transparent is meant that a 1 cm thick sample of the block transmits at least 70% of visible light, preferably at least 90%. Due to the presence of a dye, and almost inevitable absorption and/or scattering of some of the light, the transmission is generally below 95% of visible light.
  • the hard surface cleaning block are used for cleaning toilet surfaces, i.e. hard surfaces that are regularly contacted with water.
  • the present invention provides a method for providing hygiene in a toilet comprising the step of applying the block according to the invention to the toilet surface.
  • the detergent phase is spent, the remains of the adhesive phase are preferably brushed or flushed away.
  • the block according to the invention may optionally comprise an adhesive layer as disclosed in co-pending European patent application 2,082,020 .
  • Such adhesive phase may be preferred for attaching the hard surface cleaning composition according to the invention directly to a hard surface.
  • the adhesive phase comprises a hydrophobic adhesive material and optionally a hydrophilic adhesive material.
  • the hydrophobic adhesive material is required for the invention to obtain suitable resistance to water.
  • the composition may further comprise a hydrophilic adhesive material.
  • the hydrophobic adhesive material comprises at least one of a hydrophobic compound with an aggregate melting point of 30 to 60 °C, preferably 45 to 55 °C and a polymer.
  • the hydrophobic compound is present in the hydrophobic adhesive material in a concentration of 25-60%, preferably 35-55%, more preferably 40-50% by weight based the hydrophobic adhesive material.
  • the adhesive phase further comprises a polymer in a concentration of 5-75%, preferably 20-70%, more preferably 40-65%, most preferably 50-60% by weight based on the hydrophobic adhesive material.
  • the hydrophobic compound is preferably selected from natural or mineral oils, petrolatum, thickened oils, partially hydrogenated oils or fats, silicon oils and derivatives, thickened non polar solvent or low HLB non ionic surfactant and combinations thereof.
  • Low HLB as defined herein means preferably less than 12, more preferably less than 10.
  • the polymer is preferably selected from natural and synthetic cellulosic polymers, such as carboxymethyl cellulose, polyacrylates, polyvinyl pyrolidone, maleic/vinyl copolymers, silicon based polymers and mixtures thereof.
  • the polymers in the hydrophobic adhesive material are preferably water insoluble and preferably swell in contact with water.
  • the adhesive phase optionally comprises a hydrophilic adhesive material.
  • the hydrophilic adhesive material if present, is preferably positioned in such a way that it is connected to both the hard surface and the detergent phase or an intermediate phase between the detergent phase and the adhesive phase, while it is surrounded by the hydrophobic adhesive material on all other sides.
  • the hydrophilic adhesive material is postulated, without wishing to be bound by a theory, that it is possible to obtain said further improved adhesion by the combination of hydrophobic adhesive material surrounding hydrophilic adhesive material, because the hydrophobic adhesive material stops the penetration of water while the hydrophilic adhesion material further improves the adhesive strength to the block.
  • the hydrophilic adhesive phase is preferably selected from starch based adhesive materials, hydrophilic polymers, fatty acid salts and/or mixtures thereof.
  • a hydrophilic adhesive is a mixture comprising PVP polymer and sodium stearate.
  • the hydrophilic adhesive material is present in an amount of 0-60% by weight of the total adhesive phase.
  • the ratio of hydrophobic:hydrophilic adhesive material is between 10:1 and 1:10, more preferably, between 5:1 and 1:5, still more preferably 4:1 and 1:2, most preferably between 2:1 and 1:1.
  • Either one or both of the adhesive materials may further comprise a suitable rheology modifier.
  • the rheology modifier is present in a concentration of 0-10%.
  • Polymeric thickeners are an example of suitable rheology modifiers for fumed silica or silica oil; hydrogenated triglycerides or fatty acids are an example of suitable rheology modifiers for fatty acids and triglycerided; and an example of a suitable rheology modifier for anhydrous, hydrophobic oils is 12-Hydroxy stearic acid.
  • the hard surface cleaning composition of the invention may be a solid, or semi-solid composition in the meaning of Römpp Lexicon Chemie, 10th edition, Stuttgart/New York, 1997 .
  • composition hardness is measured by the method given below.
  • the composition hardness may be analysed using a Penetrometer PNR10 (ex SUR Berlin).
  • the method involves using a probe to mechanically penetrate the sample of interest using a known force.
  • the penetrometer needle is positioned manually close to the surface of sample under test and impact measurement carried out. The result is displayed in 'mm' penetration depth into the sample and replicate readings carried out on a different part of the composition. Low values correlate to hard samples, while higher values correspond to softer materials.
  • a somewhat flexible composition with a hardness of about 1 to 14 mm penetration, more preferably 3 to 12 mm, most preferably 4 to 9 mm is preferred.
  • composition according to the invention is a solid or semi-solid in anhydrous form or at low level of water, and when contacted with water, it forms a cubic phase or hexagonal liquid crystalline phase, providing adhesion properties of the composition to the surface.
  • melt casting which is a widely used method in the field.
  • composition according to the invention may be formed into blocks by other traditional methods such as injection moulding or conventional extrusion processes.
  • Example 1 Formulations using soap base of 85 Tallow/15 Coco
  • Example 2 Non Soap formulations using non ionic surfactants.
  • the blocks in various compositions last for at least 150 flushes and up to 300 flushes.

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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)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Cosmetics (AREA)

Claims (13)

  1. Procédé pour assurer l'hygiène dans des toilettes comprenant les étapes consistant à :
    a. fournir un bloc nettoyant de surface dure autocollant qui est au moins partiellement transparent ou translucide comprenant 50 à 80 % en poids d'un agent tensioactif formant une phase à cristaux liquides en présence d'eau et 1 à 50 % en poids d'une substance de parfum
    b. appliquer le bloc nettoyant à la surface des toilettes
    c. tirer la chasse d'eau des toilettes.
  2. Procédé selon la revendication 1, dans lequel le bloc nettoyant comprend en outre une couche adhésive, où la couche adhésive comprend une matière adhésive hydrophobe comprenant :
    a. 25 à 60 % d'au moins un composé hydrophobe, ayant un point de fusion global de 30 à 60 % ; et
    b. 5 à 75 % d'un polymère.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, dans lequel l'agent tensioactif est un agent tensioactif non ionique.
  4. Procédé selon la revendication 3, dans lequel l'agent tensioactif non ionique est choisi parmi les éthoxylats d'alcool ayant un degré élevé d'éthoxylation et/ou les agents tensioactifs non ioniques polysorbate.
  5. Procédé selon l'une quelconque des revendications 1 ou 2, dans lequel l'agent tensioactif est un agent tensioactif anionique ou amphotère, ayant un point de Krafft en dessous de la température ambiante.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel la dureté du bloc est de 1 à 14 mm.
  7. Utilisation d'un bloc nettoyant de surface dure autocollant qui est au moins partiellement transparent ou translucide comprenant
    ■ 50 à 80 % en poids d'un agent tensioactif formant une phase à cristaux liquides en présence d'eau et 1 à 50 % en poids d'une substance de parfum
    ■ par application à une surface de toilettes pour parfumer les toilettes.
  8. Utilisation d'un bloc nettoyant de surface dure autocollant selon la revendication 7, dans laquelle le bloc nettoyant comprend en outre une couche adhésive, où la couche adhésive comprend une matière adhésive hydrophobe comprenant :
    a. 25 à 60 % d'au moins un composé hydrophobe, ayant un point de fusion global de 30 à 60 % ; et
    b. 5 à 75 % d'un polymère.
  9. Utilisation d'un bloc nettoyant de surface dure autocollant selon l'une quelconque des revendications 7 ou 8, dans laquelle l'agent tensioactif est un agent tensioactif non ionique.
  10. Utilisation d'un bloc nettoyant de surface dure autocollant selon la revendication 9, dans laquelle l'agent tensioactif non ionique est choisi parmi les éthoxylats d'alcool ayant un degré élevé d'éthoxylation et/ou les agents tensioactifs non ioniques polysorbate.
  11. Utilisation d'un bloc nettoyant de surface dure autocollant selon l'une quelconque des revendications 7 ou 8, dans laquelle l'agent tensioactif est un agent tensioactif anionique ou amphotère, ayant un point de Krafft en dessous de la température ambiante.
  12. Utilisation d'un bloc nettoyant de surface dure autocollant selon l'une quelconque des revendications 7 à 11, dans laquelle la dureté du bloc est de 1 à 14 mm.
  13. Utilisation d'un bloc nettoyant de surface dure autocollant selon l'une quelconque des revendications 7 à 12, comprenant au moins 4 % en poids de parfum.
EP08735463A 2007-04-16 2008-03-25 Bloc de nettoyage pour surface dure auto-adhésif Revoked EP2134829B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL08735463T PL2134829T3 (pl) 2007-04-16 2008-03-25 Samoprzylepna kostka do mycia twardych powierzchni
EP08735463A EP2134829B1 (fr) 2007-04-16 2008-03-25 Bloc de nettoyage pour surface dure auto-adhésif

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07106223 2007-04-16
PCT/EP2008/053463 WO2008125425A1 (fr) 2007-04-16 2008-03-25 Bloc de nettoyage pour surface dure auto-adhésif
EP08735463A EP2134829B1 (fr) 2007-04-16 2008-03-25 Bloc de nettoyage pour surface dure auto-adhésif

Publications (2)

Publication Number Publication Date
EP2134829A1 EP2134829A1 (fr) 2009-12-23
EP2134829B1 true EP2134829B1 (fr) 2010-10-13

Family

ID=38459834

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08735463A Revoked EP2134829B1 (fr) 2007-04-16 2008-03-25 Bloc de nettoyage pour surface dure auto-adhésif

Country Status (16)

Country Link
US (1) US20100162474A1 (fr)
EP (1) EP2134829B1 (fr)
CN (1) CN101663385B (fr)
AR (1) AR066072A1 (fr)
AT (1) ATE484570T1 (fr)
AU (1) AU2008238156B2 (fr)
BR (1) BRPI0810493A2 (fr)
CL (1) CL2008001059A1 (fr)
DE (1) DE602008003016D1 (fr)
EA (1) EA020185B1 (fr)
MX (1) MX2009010979A (fr)
MY (1) MY146732A (fr)
PL (1) PL2134829T3 (fr)
UA (1) UA99616C2 (fr)
WO (1) WO2008125425A1 (fr)
ZA (1) ZA200906454B (fr)

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DE102012224159A1 (de) * 2012-12-21 2014-06-26 Henkel Ag & Co. Kgaa Selbsthaftender Reinigungsmittelstreifen für harte Oberflächen
EP2770045A1 (fr) * 2013-02-25 2014-08-27 Eurvest S.A. Applicateur hygiénique
DE102013226523A1 (de) * 2013-12-18 2015-06-18 Henkel Ag & Co. Kgaa Reinigungsmittelblock für harte Oberflächen
US10196591B2 (en) * 2015-07-10 2019-02-05 S. C. Johnson & Sons, Inc. Gel cleaning composition
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JP3609768B2 (ja) * 2000-12-25 2005-01-12 資生堂ホネケーキ工業株式会社 透明固形石鹸組成物
BRPI0211039B1 (pt) * 2001-06-22 2015-07-14 Unilever Nv Composição condicionadora sólida para os cabelos e uso de uma composição condicionadora sólida para os cabelos
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US7709433B2 (en) * 2007-02-12 2010-05-04 S.C. Johnson & Son, Inc. Self-sticking disintegrating block for toilet or urinal

Also Published As

Publication number Publication date
BRPI0810493A2 (pt) 2015-07-28
MX2009010979A (es) 2009-10-30
CL2008001059A1 (es) 2009-01-16
CN101663385B (zh) 2012-01-11
AR066072A1 (es) 2009-07-22
MY146732A (en) 2012-09-14
EP2134829A1 (fr) 2009-12-23
PL2134829T3 (pl) 2011-04-29
DE602008003016D1 (de) 2010-11-25
US20100162474A1 (en) 2010-07-01
WO2008125425A1 (fr) 2008-10-23
AU2008238156A1 (en) 2008-10-23
ATE484570T1 (de) 2010-10-15
UA99616C2 (ru) 2012-09-10
ZA200906454B (en) 2010-11-24
CN101663385A (zh) 2010-03-03
EA020185B1 (ru) 2014-09-30
EA200901404A1 (ru) 2010-02-26
AU2008238156B2 (en) 2011-05-19

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