WO2012119838A1 - Composition auto-adhésive de nettoyage de surface dure - Google Patents

Composition auto-adhésive de nettoyage de surface dure Download PDF

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Publication number
WO2012119838A1
WO2012119838A1 PCT/EP2012/052470 EP2012052470W WO2012119838A1 WO 2012119838 A1 WO2012119838 A1 WO 2012119838A1 EP 2012052470 W EP2012052470 W EP 2012052470W WO 2012119838 A1 WO2012119838 A1 WO 2012119838A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
toilet
composition according
anyone
weight
Prior art date
Application number
PCT/EP2012/052470
Other languages
English (en)
Inventor
Luca Ciceri
Daniele Del Fiol
Paolo Mondani
Ivana Trombetta
Original Assignee
Unilever Nv
Unilever Plc
Hindustan Unilever 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 Unilever Nv, Unilever Plc, Hindustan Unilever Limited filed Critical Unilever Nv
Publication of WO2012119838A1 publication Critical patent/WO2012119838A1/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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/43—Solvents
    • 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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; Salts 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • the present invention relates to a hard surface cleaning composition in the form of a toilet block, and its 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
  • 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. Attempts have been made to solve this problem, by various means.
  • 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
  • Hard surface cleaning blocks in different forms are disclosed in the art. Solid blocks in a holder are for instance disclosed in EP-B1 553 162. An alternative to the solid block is a liquid dispenser device, such as the device disclosed in GB2389123. The hard surface cleaning composition can even be applied directly onto the surface as disclosed in EP-Al-1 086 199, where a self adhesive paste is disclosed. Alternatively, WO- 2008/058853 discloses a detergent composition comprising an adhesive phase.
  • Hard surface cleaning blocks optionally comprising biocide are disclosed in the art. However, to be able to dose an effective amount of biocide to provide hygiene from a small hard surface cleaning block over a large number of flushes, requires a high level of biocide. A hard surface cleaning block comprising such a biocide compound in such effective amount to provide hygiene to a hard surface, in particular to a toilet bowl, remains to be desired.
  • US 6,667,287 discloses a light duty liquid cleaning composition comprising a biocide (benzalkonium chloride) for providing hygiene to a toilet.
  • WO-2008/125451 discloses a hard surface cleaning composition in the form of a toilet block that provides hygiene to a hard surface and that can be easily positioned onto said hard surface. Furthermore, the composition disclosed by this document rinses away in a number of flushes while releasing a hygiene agent at a uniform rate.
  • an adhesive layer between one of the sides of the toilet block and the hard surface at which it is to be applied, so as to improve the adhesion of said toilet block.
  • compositions are such that it survives more than 150 flushes after having been positioned in the toilet bowl at a position where the force of water is maximum.
  • said hard surface cleaning composition rinses away in a number of flushes, releases a hygiene agent at a rate sufficient to provide adequate hygiene throughout the operating life of the toilet block, and does not leave behind any residue that cannot be easily removed with e.g. a toilet brush. It is also an object of the invention to provide such a
  • a hard surface cleaning composition in the form of a toilet block and comprising glycerine monoester, biocide material and water, whereby said glycerine monoester forms a cubic or hexagonal phase in the presence of a solvent.
  • the present invention provides a hard surface cleaning composition in the form of a toilet block, wherein said composition comprises:
  • the monoglycerine ester is glycerine monooleate.
  • the invention further provides a method for manufacturing the hard surface cleaning composition of the invention.
  • the invention also provides a method for providing hygiene in a toilet, said method comprising the steps of (a) applying the hard surface cleaning composition of the invention to the toilet surface and (b) flushing the toilet with water.
  • invention comprises a glycerine monoester and biocide material whereby said glycerine monoester, which is a surfactant, forms a cubic or hexagonal phase in contact with a solvent during preparation of the composition.
  • the invention relates to the cleaning formulation and the process for making said
  • composition which may be used to stick directly on a hard surface.
  • the self sticking behaviour is due to the formation of a cubic or hexagonal phase.
  • the solvent present in the composition of the invention and needed for obtaining the cubic or hexagonal phase is preferably selected from the group consisting of glycerine, propylene glycol, ethylene glycol, water and mixtures thereof. More preferably, said solvent contains water. When the solvent contains water, the glycerine monoester present in the
  • composition of the invention will form -at least partly- a cubic phase.
  • Said cubic phase may have different rheological properties depending on whether it is present as bicontinuous phase or discontinuous phase.
  • the phase may have different rheological properties depending on whether it is present as bicontinuous phase or discontinuous phase.
  • the phase is present as bicontinuous phase or discontinuous phase.
  • transition behaviour of the composition in presence of a solvent provides a way to stick the composition in the toilet (i.e. onto the surface of the toilet bowl), thus providing a self adhesive system. It has been found that the cubic phase has good adhesion properties and has got very high viscosity, thus providing the possibility to attach the cleaning
  • composition to a wet surface.
  • composition of the invention gradually erodes or dissolves when contacted or flushed with water, thereby
  • composition of the invention preferably last for at least 100, more preferably at least 150, still more preferably at least 200 flushes.
  • Toilet compositions generally do not last for more than 500 flushes, more preferably not more than 400 flushes and most preferably not more than 300 flushes.
  • the hard surface cleaning composition of the invention may be a solid, semi-solid or gel like composition in the meaning of Rompp Lexicon Chemie, 10 th edition, Stuttgart/New York, 1997.
  • the glycerine monoester present in the cleaning composition of the invention is a nonionic type of surfactant which forms a cubic or hexagonal phase in contact with a solvent.
  • This cubic phase may be a bicontinuous cubic phase or a
  • the glycerine monoester is glycerine monooleate.
  • Preferred types of glycerine monooleate are Monomuls 90-O 18 (ex Cognis) and Cithrol GMO 90 (ex Croda) .
  • the glycerine monoester alone or possibly in contact with small quantity of anionic surfactants gives suitable foaming and adhesion properties to the toilet block product.
  • polysorbates are short chain (C10-C12, saturated or unsaturated) polysorbates, such as Tween 20, or longer chain (up to C18, unsaturated) polysorbates, such as Tween 80.
  • Polysorbate nonionic surfactants were found to have excellent foaming properties.
  • Anionic and amphoteric surfactants may also be present in the surfactant system.
  • the anionic and amphoteric surfactants form liquid crystalline phases above the Krafft point. These liquid crystalline phases may further improve the adhesion properties of the composition to the hard surface.
  • Anionic and amphoteric surfactants with a Krafft Point below 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 may also be used to get similar result.
  • These surfactants can be used in the formulation at a level of 0-10%, more preferably 2-5% by weight. Higher levels have been
  • the glycerine monoester (which forms a cubic or hexagonal phase in the presence of the solvent) is present in the cleaning composition of the invention in a concentration of preferably at least 30%, more preferably at least 40%, most preferably at least 60%.
  • the said monoester is present in the composition in a concentration of not more than 80%, preferably not more than 70%.
  • the biocide material is preferably selected from CTAC (cetyl trimethyl ammonium chloride) , and BAC (benzalkonium chloride) and didecyldimethylammonium chloride, dodecyldipropylene triamine and poly (hexamethylenebiguanide ) hydrochloride.
  • CTAC cetyl trimethyl ammonium chloride
  • BAC benzalkonium chloride
  • BAC is the most preferred type of biocide.
  • the biocide is preferably present in a concentration of from 1 to 15%, more preferably 5 to 15%, by weight.
  • inventions may further comprise detergent active, builders, dyes, perfume, hygiene agents, antioxidants, radical
  • Perfume is preferably present in the cleaning composition of the invention, in a preferred concentration of 3 to 15% by weight .
  • 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
  • composition may optionally comprise humectant.
  • Humectants maintain both structure and clarity. When present, said
  • humectants will enable retention of water within the toilet block formulation of the invention and also increase the stability of said toilet block such that phase transition of the glycerine ester present is prevented.
  • humectants are polyhydroxylated organic compounds, such as sorbitol and sucrose.
  • solvents glycerol and polyethylene glycol (PEG) are also suitable as humectants.
  • 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 other than the solvent needed for forming the cubic or hexagonal phase may also be present in the composition.
  • Preferred -additional- solvents include poly alkylene glycols (e.g. PEG, PPG) and short chain organic solvents (e.g. ethanol or isopropanol) .
  • the additional 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 composition may affect its adhesive properties. It is preferred to have hydrodynamic shapes, which help in better control of the erosion properties of the block which in turn helps in better adhesion to the surface. Thus, round, smooth shapes are preferred over
  • composition life is directly related to its formulation and the size.
  • a normal size toilet block is between about 4 and 50 grams, preferably about 4 to 15 g.
  • a toilet block that is at least partially transparent or translucent.
  • 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.
  • 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
  • composition of the invention may be applied to the internal surface of a toilet bowl from a tube or in a preformed shape so as to be used for toilet cleaning.
  • a method for providing hygiene to a toilet is provided.
  • a hard surface cleaning composition according to the invention is attached to the toilet bowl surface which is preferably a wet surface.
  • the surfactant phase cubic or hexagonal present in the composition ensures good adhesion to the wet toilet bowl surface.
  • the toilet block composition of the invention When the toilet is flushed, the toilet block composition of the invention is wetted and a small portion thereof is dissolved in the flush water, preferably about 0.01% to 2.0% by weight, preferably 0.1% to 1%.
  • the hard surface cleaning composition of the invention may be a solid, semi-solid or gel like composition in the meaning of Rompp Lexicon Chemie, 10 th edition, Stuttgart/New York, 1997
  • 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.
  • Suitable compositions of the invention have a hardness of about 1 to 14 mm, more preferably 1 to 9 mm penetration measured using the method above.
  • the invention provides a method for the manufacturing of a toilet block comprising the cleaning composition of the
  • biocide in the form of a homogeneous liquid containing the solvent needed for forming the cubic or hexagonal phase, and fully dissolving the biocide, optionally adding perfume and colour ingredients at this temperature, and
  • the product in the mould may be kept at room temperature for solidification or it may be passed through a cooling tunnel for quick solidification. Once the product is solidified in the mould it may be packed in any desired packaging.
  • Example 1 The invention is now illustrated by the following non-limiting examples .
  • Example 1 The invention is now illustrated by the following non-limiting examples .
  • compositions of this example each of which are in the form of a toilet block, were attached to the internal surface of a toilet bowl and tested for the number of flushes they lasted while maintaining the right product dosing to the toilet.
  • compositions 1-5 are according to the present invention, whereas composition A is a comparative composition only containing glycerine monooleate and water.
  • Table 1 Cleaning formulations containing glycerine monooleate and water (in % wt)
  • the toilet block with the composition A (which is not according to the present invention) was found to be both insoluble and opaque.

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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)

Abstract

La présente invention concerne une composition de nettoyage de surface dure sous forme d'un bloc pour toilettes, ladite composition comprenant : (a) 20 à 80% en poids de monoester de glycérine formant une phase cubique ou hexagonale en présence de solvant ; (b) 1 à 25% en poids de matériau biocide ; et (c) 15 à 45% en poids dudit solvant. L'invention concerne également un procédé pour la fabrication dudit bloc pour toilettes et un procédé pour assurer l'hygiène des toilettes.
PCT/EP2012/052470 2011-03-04 2012-02-14 Composition auto-adhésive de nettoyage de surface dure WO2012119838A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11156896 2011-03-04
EP11156896.0 2011-03-04

Publications (1)

Publication Number Publication Date
WO2012119838A1 true WO2012119838A1 (fr) 2012-09-13

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/052470 WO2012119838A1 (fr) 2011-03-04 2012-02-14 Composition auto-adhésive de nettoyage de surface dure

Country Status (2)

Country Link
AR (1) AR085604A1 (fr)
WO (1) WO2012119838A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2061313A (en) * 1979-08-06 1981-05-13 Tate & Lyle Ltd Lavatory cleansing compositions
EP0553162B1 (fr) 1990-10-18 1997-05-28 The Victoria University Of Manchester Surveillance de la profondeur d'anesthesie
EP0586137B1 (fr) 1992-08-20 1998-01-07 Unilever Plc Dispositif distributeur
WO2000033816A1 (fr) * 1998-12-10 2000-06-15 The Victoria University Of Manchester Formulations d'administration d'un materiau donne a des membranes de muqueuses
EP1086199A1 (fr) 1998-06-12 2001-03-28 Buck-Chemie GmbH . Produit d'assainissement adhesif
US6569478B1 (en) * 1998-03-13 2003-05-27 Nestec S.A. Food composition containing a monoglyceride memomorphic phase
GB2389123A (en) 2002-05-29 2003-12-03 Unilever Plc Device for dispensing a fluid into a lavatory bowl
US6667287B2 (en) 2000-04-20 2003-12-23 Colgate-Palmolive Company Light duty cleaning composition comprising an amine oxide and polyacrylic acid homopolymer
US20050249665A1 (en) * 2002-09-05 2005-11-10 Dbl Australia Pty Ltd. Urea-, glycerate- and, hydroxyamide-headed hydrocarbon chain lyotropic phases forming surfactants
WO2008058853A1 (fr) 2006-11-16 2008-05-22 Unilever N.V. Bloc de nettoyage pour surface dure auto-adhésif
WO2008125451A1 (fr) 2007-04-16 2008-10-23 Unilever N.V. Bloc de nettoyage pour surface dure auto-adhésif

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2061313A (en) * 1979-08-06 1981-05-13 Tate & Lyle Ltd Lavatory cleansing compositions
EP0553162B1 (fr) 1990-10-18 1997-05-28 The Victoria University Of Manchester Surveillance de la profondeur d'anesthesie
EP0586137B1 (fr) 1992-08-20 1998-01-07 Unilever Plc Dispositif distributeur
US6569478B1 (en) * 1998-03-13 2003-05-27 Nestec S.A. Food composition containing a monoglyceride memomorphic phase
EP1086199A1 (fr) 1998-06-12 2001-03-28 Buck-Chemie GmbH . Produit d'assainissement adhesif
WO2000033816A1 (fr) * 1998-12-10 2000-06-15 The Victoria University Of Manchester Formulations d'administration d'un materiau donne a des membranes de muqueuses
US6667287B2 (en) 2000-04-20 2003-12-23 Colgate-Palmolive Company Light duty cleaning composition comprising an amine oxide and polyacrylic acid homopolymer
GB2389123A (en) 2002-05-29 2003-12-03 Unilever Plc Device for dispensing a fluid into a lavatory bowl
US20050249665A1 (en) * 2002-09-05 2005-11-10 Dbl Australia Pty Ltd. Urea-, glycerate- and, hydroxyamide-headed hydrocarbon chain lyotropic phases forming surfactants
WO2008058853A1 (fr) 2006-11-16 2008-05-22 Unilever N.V. Bloc de nettoyage pour surface dure auto-adhésif
WO2008125451A1 (fr) 2007-04-16 2008-10-23 Unilever N.V. Bloc de nettoyage pour surface dure auto-adhésif

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
"McCutcheon's Emulsifiers and Detergents", MANUFACTURING CONFECTIONERS COMPANY
"Rompp Lexicon Chemie", 1997
H. STACHE: "Tenside-Taschenbuch", 1981, CARL HAUSER VERLAG
SCHWARTZ; PERRY: "Surface Active Agents", vol. 1, 1949, INTERSCIENCE
SCHWARTZ; PERRY; BERCH: "SURFACE ACTIVE AGENTS", vol. 2, 1958, INTERSCIENCE

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