EP2082020A1 - Bloc de nettoyage pour surface dure auto-adhésif - Google Patents

Bloc de nettoyage pour surface dure auto-adhésif

Info

Publication number
EP2082020A1
EP2082020A1 EP07847106A EP07847106A EP2082020A1 EP 2082020 A1 EP2082020 A1 EP 2082020A1 EP 07847106 A EP07847106 A EP 07847106A EP 07847106 A EP07847106 A EP 07847106A EP 2082020 A1 EP2082020 A1 EP 2082020A1
Authority
EP
European Patent Office
Prior art keywords
phase
adhesive
block according
block
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP07847106A
Other languages
German (de)
English (en)
Other versions
EP2082020B1 (fr
Inventor
Giuseppe Vincenzo Bolzoni
Ivan Valcarenghi
Daniele Del Fiol
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
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to PL07847106T priority Critical patent/PL2082020T3/pl
Priority to EP07847106A priority patent/EP2082020B1/fr
Publication of EP2082020A1 publication Critical patent/EP2082020A1/fr
Application granted granted Critical
Publication of EP2082020B1 publication Critical patent/EP2082020B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • 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
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to self adhesive hard surface cleaning blocks, and their use.
  • 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.
  • a hard surface cleaning block comprising an adhesive phase meets at least one of these objects.
  • the invention provides a hard surface cleaning block, comprising
  • a detergent phase - An adhesive phase; wherein the adhesive phase comprises a hydrophobic adhesive material comprising: 25-60% of at least one hydrophobic compound, having an aggregate melting point of 30-60 0 C; and 5-75% of a polymer.
  • the invention further provides methods for providing hygiene to a toilet and methods for washing dishes with the hard surface cleaning block of the invention as further explained herein below.
  • the hard surface cleaning block according to the invention comprises of an adhesive phase and a detergent phase.
  • the purpose of the adhesive phase is to apply the detergent phase to a hard surface.
  • the purpose of the detergent phase is to release detergent material and other components incorporated in the detergent phase to the hard surface for treatment thereof. This normally happens when the block comes in contact with water, e.g. by flushing of a toilet in application as a toilet block, or by wetting the block before use in dishwashing applications. The block is then partially dissolved upon each contact with water.
  • composition of the block is preferably selected in such a way that there is a balanced level of surfactant and structurant to give proper foam and strength to the block.
  • One of the aspects of the invention is to develop an adhesive system which can easily be washed away by gentle rubbing of the surface on which the block is applied.
  • the block is adhered sufficiently strong to take the pressure of passing water in a toilet, sink or shower, while on the other hand the adhesion is not so strong that it is difficult to remove the adhesive material from the surface after the product is used up.
  • the detergent phase may be any kind of detergent phase. It may for instance be a solid, a semi solid or a gel.
  • the detergent phase may be transparent, translucent, opaque, or not transparent at all.
  • the detergent phase may be directly attached to the adhesive phase or indirectly, e.g. in a cage or with a separation layer between the phases.
  • the detergent phase comprises surfactants. Suitable surfactants are described in "Surface Active Agents” Vol. 1 , by Schwartz & Perry, lnterscience 1949, Vol. 2 by Schwartz, Perry & Berch, lnterscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing
  • Adhesive phase is preferably suitable for attaching the detergent phase to the hard surface.
  • the self adhesive detergent blocks of the invention are challenged by the flow of water, whether the block is adhered to a sink, dishwashing machine, or toilet.
  • the force that water applies to a toilet block, with a frontal surface of 10cm 2 is 0.3 N at an average flush. Therefore, the force required to release the block from the surface is preferably more than said 0.3 N.
  • 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 0 C, preferably 45 to 55 0 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 block according to the invention may further comprise builders, dyes, perfume, hygiene agents, antioxidants, radical scavengers, chelating agents, hydrotropes, anticorrosion agents, opacifiers, bhghteners, preservatives and/or abrasives.
  • Each of the optional components may be included in the detergent phase, in the adhesive phase or in both phases
  • an intermediate phase may for instance be present to prevent interaction between phases or to improve the adhesion between the phases.
  • the intermediate phase is preferably a water resistant film.
  • the intermeditate layer when present, acts as a protective layer that does not allow water to penetrate between the adhesive phase and the detergent phase, thus providing additional protection to the adhesive phase.
  • the intermediate phase may be a polymer film, a solid barrier, or any other known barrier layer.
  • Suitable polymer films are described in co-pending applications WO-02/090475 or WO-03/046119.
  • Suitable non-polymer based barrier layers may be found in e.g. EP-B-1 491 622, EP-B-1 522 575 or
  • the thickness of the intermediate layer is at least 50 microns, an preferably less than 500 microns. The most preferred range is 100-200 microns. If the thickness is less than about 50 microns, the strength of the coating is not sufficient to protect the glue. More than 500 micron is uselessly expensive.
  • the detergent phase may also be surrounded by a casing, to which the adhesive phase is attached.
  • a casing may be similar to the commonly used types in most housing cages for solid toilet blocks.
  • Block size and shape The shape of the hard surface cleaning block may affect the adhesive properties of the block. It is preferred to have hydrodynamic shapes of the block, which help in better control of the erosion properties of the block which in turn helps in better 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.
  • the required amount of the adhesive phase is determined by the surface of the detergent block.
  • the amount of adhesive phase material is preferably at least 0.01 g/cm 2 , more preferably at least 0.05 g/cm 2 , still more preferably at least 0.1 g/cm 2 , but preferably not more than 1.5 g/cm 2 , more preferably not more than 0.3 g/cm 2 , still more preferably not more than 0.2 g/cm 2 .
  • the hard surface cleaning block may be used for cleaning hard surfaces of any kind.
  • the most suitable surfaces are those that are regularly contacted with water, such as toilet surfaces, kitchen sinks and showers.
  • 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 present invention further provides a method for washing dishes comprising the steps of applying the block according to the invention to a kitchen sink and filling the sink with water. Thereby the water comes in contact with the block and releases part of the detergent phase to the water.
  • the present invention further provides a method for washing dishes, the method comprising the step of applying the block according to the invention to the inside of a dishwashing machine.
  • the adhesive layer of the present invention preferably adheres the detergent phase to a hard surface hard surface directly.
  • the detergent phase is held by a cage and the cage be adhered to the surface.
  • Example 1 Four examples of compositions for the adhesive phase (Adh 1 -4) are given in Table 1 below. Table 1 : Adhesive phase composition in %
  • the adhesive phases of the example are made by the following process.
  • Petrolatum and Vaseline® are melted in a mixer by heating it at about 60 0 C (sunflower seed oil was suitable for processing as is). Polymers and other ingredients are added in the clear melt and mixed slowly to avoid any aeration. If aeration takes place during the mixing then it is necessary to apply vacuum to de-aerate the mix before cooling. The de-aerated mass can be poured in an application tank from where it is directly pumped on the surface of the product. Colour and fragrance components may be added to the adhesive phase to give better performance of the product.
  • the detergent phases of the example are made by the following process.
  • the detergent block can be made by conventional extrusion or melt cast processes, depending upon the type of formulation.
  • extrusion process the ingredients are mixed together and then extruded in the form of billets. These billets are then cut in desired size of the blocks and the adhesive phase is applied.
  • melt cast process the ingredients are mixed and melted by heating at elevated temperature. Additional ingredients, such as colour and fragrance components may be added to the detergent phase in this stage to give better performance of the product.
  • the homogeneous mass is then poured in molds and cooled to room temperature to solidify. Once the block is solidified, the adhesive phase is applied to the block.
  • the amount of adhesive phase used is about 100 mg/cm2.
  • any combination of adhesive phase (100 mg/cm2, from Table 1 ) and detergent phase (40 grams, from Table 1 ) was found remain firmly attached to the toilet bowl for at least 100 flushes.
  • the thin layer of the adhesive phase is removed by gentle rubbing of the surface using a toilet brush. There is no residue left on the surface after brushing.
  • the intermediate layer in this example consisted of epoxy acrylate based uv- cured material as disclosed in WO03/046119 with a layer thickness of about 100 microns.
  • any combination of adhesive phase from Table 1
  • intermediate phase from Table 2
  • detergent phase from Table 2
  • the thin layer of the adhesive phase is removed by gentle rubbing of the surface using a toilet brush. There is no residue left on the surface after brushing.
  • Example 3 Determination of Adhesive Force is done with a Texture Analyser, rigged for the determination of horizontal force.
  • a Texture Analyser rigged for the determination of horizontal force.
  • the a Lloyd lntruments LRX Plus texture analyser was used.
  • similar texture analysers are available from for instance Instron.
  • the texture analyser rigged for measuring horizontal force, was used to determine the adhesive forces of different adhesive phase systems. 2 g of adhesive material was applied on the (flat) bottom surface (15 cm2) of a detergent block. The surface with the adhesive layer was pressed on a ceramic surface attached to the texture analyser. The block is moved horizontally, parallel to the ceramic surface, and the data for the applied force (N) is recorded. The force (in N) that is required to move the detergent block is given in the table below.
  • the viscosity of the adhesive phase was measured with a Brookfield (RVT), using a TD-20.4 mm spindle, at a temperature TR of 25°C, at a rotation speed of 5 rpm.
  • the unit for viscosity is in cps (mPa.s).
  • a detergent block, adhered to the bowl of a toilet, is challenged by the flow of water at every flush.
  • the force that the water applies to such a toilet block, with a frontal surface of 10cm 2 is 0.3 N.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne des blocs de nettoyage pour surface dure auto-adhésifs, et leur utilisation. La présente invention a pour objectif de proposer un bloc détergent pouvant facilement être positionné sur une surface dure ; même une surface humide. L'invention a également pour objectif de proposer un bloc détergent qui s'élimine par rinçage en un certain nombre de rinçages, et ne laisse aucun résidu ne pouvant pas être facilement retiré avec p. ex. une brosse pour toilettes. Le bloc de nettoyage pour surface dure selon l'invention comprend une phase adhésive et satisfait au moins un de ces objectifs. L'invention concerne également des procédés de nettoyage d'assiettes dans un évier ou dans un lave-vaisselle.
EP07847106A 2006-11-16 2007-11-02 Bloc de nettoyage pour surface dure auto-adhésif Active EP2082020B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL07847106T PL2082020T3 (pl) 2006-11-16 2007-11-02 Samoprzylepna kostka czyszcząca do twardych powierzchni
EP07847106A EP2082020B1 (fr) 2006-11-16 2007-11-02 Bloc de nettoyage pour surface dure auto-adhésif

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06124234 2006-11-16
PCT/EP2007/061823 WO2008058853A1 (fr) 2006-11-16 2007-11-02 Bloc de nettoyage pour surface dure auto-adhésif
EP07847106A EP2082020B1 (fr) 2006-11-16 2007-11-02 Bloc de nettoyage pour surface dure auto-adhésif

Publications (2)

Publication Number Publication Date
EP2082020A1 true EP2082020A1 (fr) 2009-07-29
EP2082020B1 EP2082020B1 (fr) 2012-08-22

Family

ID=37965037

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07847106A Active EP2082020B1 (fr) 2006-11-16 2007-11-02 Bloc de nettoyage pour surface dure auto-adhésif

Country Status (14)

Country Link
EP (1) EP2082020B1 (fr)
CN (1) CN101535463B (fr)
AR (1) AR063824A1 (fr)
AU (1) AU2007321362B2 (fr)
BR (1) BRPI0718778B1 (fr)
CL (1) CL2007003287A1 (fr)
HK (1) HK1134517A1 (fr)
MX (1) MX2009005178A (fr)
MY (1) MY153644A (fr)
PL (1) PL2082020T3 (fr)
RU (1) RU2443770C2 (fr)
UA (1) UA97967C2 (fr)
WO (1) WO2008058853A1 (fr)
ZA (1) ZA200902458B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014072677A1 (fr) 2012-11-09 2014-05-15 Reckitt Benckiser Llc Distributeur pliable à usage unique pour une composition de traitement de toilettes adhésive
DE102012224159A1 (de) 2012-12-21 2014-06-26 Henkel Ag & Co. Kgaa Selbsthaftender Reinigungsmittelstreifen für harte Oberflächen

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7709433B2 (en) 2007-02-12 2010-05-04 S.C. Johnson & Son, Inc. Self-sticking disintegrating block for toilet or urinal
EA019083B1 (ru) * 2007-04-16 2014-01-30 Юнилевер Н.В. Чистящий блок для туалета
CN101945987B (zh) 2008-02-21 2014-01-22 约翰逊父子公司 自粘合性高且提供残留益处的清洁组合物
US9481854B2 (en) 2008-02-21 2016-11-01 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
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
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
US8835371B2 (en) 2008-02-29 2014-09-16 Buck-Chemie Gmbh Adhesive agent for application on a sanitary object
US8444771B2 (en) 2008-02-29 2013-05-21 Buck-Chemie Gmbh Method for cleaning and/or deodorizing toilet bowl or urinal using an adhesive agent
CA2740067C (fr) 2008-02-29 2014-04-08 Buck-Chemie Gmbh Agent collant pour l'application sur un objet sanitaire
DE102008012092A1 (de) * 2008-02-29 2009-09-10 Buck- Chemie Gmbh Haftendes Mittel zur Applikation auf einem Sanitärgegenstand
ITMI20081202A1 (it) * 2008-06-30 2010-01-01 Bolton Manitoba S P A Prodotto detergente adesivo e dispositivo contenitore ed applicatore per tale prodotto
US7919447B1 (en) 2010-03-12 2011-04-05 S.C. Johnson, Inc Array of self-adhesive cleaning products
WO2012119838A1 (fr) 2011-03-04 2012-09-13 Unilever Nv Composition auto-adhésive de nettoyage de surface dure
GB2502763B (en) 2011-10-14 2016-09-28 Jeyes Group Ltd An Applicator for a sanitary ware surface
WO2013107576A1 (fr) 2012-01-20 2013-07-25 Unilever N.V. Composition de nettoyage de surfaces dures renfermant un renforçateur de mousse
AU2013291737B2 (en) * 2012-07-16 2015-06-25 Reckitt Benckiser Llc Self-adhesive lavatory treatment compositions
DE102012106742A1 (de) 2012-07-25 2014-01-30 Geting Solutions Gmbh Stückförmiges Mittel zur Applikation auf einem Sanitärgegenstand
DE102013108019B3 (de) * 2013-07-26 2014-08-28 Buck-Chemie Gmbh Haftendes Mittel zur Applikation auf einem Sanitärgegenstand
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

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9217715D0 (en) * 1992-08-20 1992-09-30 Unilever Plc Dispensing device
US5759974A (en) * 1994-11-07 1998-06-02 Henkel Kommanditgesellschaft Auf Aktien Block-form cleaners for flush toilets
JP3743864B2 (ja) * 1995-04-03 2006-02-08 小林製薬株式会社 トイレ便器用洗浄剤
DE19758178A1 (de) * 1997-12-30 1999-07-01 Henkel Kgaa Geschirrspülmittelformkörper mit Chlorbleichmitteln
PT979865E (pt) * 1998-07-17 2002-09-30 Procter & Gamble Pastilhas detergentes
CN1230503C (zh) * 2000-11-22 2005-12-07 上海白猫有限公司 一种厕盆保洁剂
PL199102B1 (pl) * 2001-05-03 2008-08-29 Unilever Nv Ukształtowana detergentowa kompozycja i sposób jej wytwarzania
DE10336796B4 (de) * 2003-08-08 2005-05-19 Henkel Kgaa Wasch- oder Reinigungsmittel
ES2285350T5 (es) * 2004-01-08 2011-06-17 Unilever N.V. Pastillas para inodoros.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008058853A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014072677A1 (fr) 2012-11-09 2014-05-15 Reckitt Benckiser Llc Distributeur pliable à usage unique pour une composition de traitement de toilettes adhésive
DE102012224159A1 (de) 2012-12-21 2014-06-26 Henkel Ag & Co. Kgaa Selbsthaftender Reinigungsmittelstreifen für harte Oberflächen

Also Published As

Publication number Publication date
HK1134517A1 (en) 2010-04-30
AU2007321362A1 (en) 2008-05-22
UA97967C2 (ru) 2012-04-10
EP2082020B1 (fr) 2012-08-22
AU2007321362B2 (en) 2010-09-02
WO2008058853A1 (fr) 2008-05-22
CN101535463A (zh) 2009-09-16
RU2443770C2 (ru) 2012-02-27
RU2009122702A (ru) 2010-12-27
BRPI0718778B1 (pt) 2017-11-21
AR063824A1 (es) 2009-02-18
PL2082020T3 (pl) 2012-11-30
MX2009005178A (es) 2009-05-25
BRPI0718778A2 (pt) 2015-01-06
CL2007003287A1 (es) 2008-06-20
CN101535463B (zh) 2013-07-17
MY153644A (en) 2015-03-13
ZA200902458B (en) 2010-07-28

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