WO2005061689A1 - Composition nettoyante solide pour la fabrication des comprimes - Google Patents

Composition nettoyante solide pour la fabrication des comprimes Download PDF

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Publication number
WO2005061689A1
WO2005061689A1 PCT/DK2004/000901 DK2004000901W WO2005061689A1 WO 2005061689 A1 WO2005061689 A1 WO 2005061689A1 DK 2004000901 W DK2004000901 W DK 2004000901W WO 2005061689 A1 WO2005061689 A1 WO 2005061689A1
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WIPO (PCT)
Prior art keywords
tablet
cleaning composition
weight
composition according
cleaning
Prior art date
Application number
PCT/DK2004/000901
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English (en)
Inventor
Anders Bjerre Kristensen
Jamshid Faramarzi
Thomas Krejberg
Original Assignee
Danlind As
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 Danlind As filed Critical Danlind As
Publication of WO2005061689A1 publication Critical patent/WO2005061689A1/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
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters

Definitions

  • This invention relates to a solid cleaning composition suitable for tabletting and to tablets made from said composition and in particular tablets for use in cleaning hard surfaces such as e.g. windows and tiles.
  • cleaning compositions having specific properties.
  • cleaning compositions should be effective in removing dirt and unwanted stains from surfaces and leaving surfaces with a shiny appearance without streaks.
  • Cleaning compositions in tablet form have several advantages over liquid and powdered cleaning compositions. Thus, because they are compressed and contain no water they are economical for shipping and storage. Furthermore they facilitate an easy and correct dosing and do not cause problems with emission of dust during use.
  • cleaning tablets should disintegrate fairly rapidly.
  • a rapid disintegration may be achieved by chemical means, i.e. an effervescent system or by physical means, i.e. a disintegrant.
  • chemical means i.e. an effervescent system
  • physical means i.e. a disintegrant.
  • an effervescent system in a tablet formulation is often a challenge, since such systems are very sensitive to moist which results in problems during tabletting and storage.
  • US patent No. 6,596,682 discloses a water soluble tablet comprising a cleaning composition.
  • the cleaning composition contains an effervescent system consisting of an organic acid and sodium bicarbonate.
  • the tablet can contain two polymeric disintegrants which help disintegrate the tablet when water is added.
  • the tablet also contains a solubilizing agent in the form of a crosslinked N-2-polyvinyl pyrrolidone having a particle size of 15 to 125 microns.
  • Said tablet has the following composition:
  • an alkali metal salt or an alkaline earth metal of a fatty acid such as magnesium stearate
  • composition also comprises perfume.
  • US patent No. 6,358,911 discloses detergent tablets containing a compressed and a non-compressed portion, where perfume is confined to the non-compressed part of the tablets.
  • a cleaning composition for use in the cleaning of hard surfaces should not only be effective in removing dirt and unwanted stains, but should also, as mentioned above, leave a pleasant smell after use. The latter is of great psychological importance, because a pleasant smell gives an impression of an impression of an cleanliness to the user.
  • perfumes in high concentrations may be a challenge to any formulator.
  • Perfumes are complex blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g. terpenes) where the essential oils also serve to dissolve the other components of the perfume.
  • the organic compounds of a perfume may react with the other components of a cleaning composition thereby impairing the storage stability drastically.
  • perfume due to the oily nature of the perfume, it may also affect the flowability of the powder during the tabletting process resulting in an uneven dosing of the tablet and lot of rejects. In the case of effervescent based cleaning compositions, it may also affect the ability of the effervescent systems to be active upon contact with water. Finally, a high content of perfume may also result in an unacceptable long disintegration time of the tablet as well as reduce the ability of the composition to foam upon contact with water.
  • An object of the present invention is to provide cleaning compositions for the production of tablets having a high concentration of perfume.
  • Another object of the invention is to provide cleaning tablets which maintain their strength and structure over long periods of storage and/or shipping and still have short disintegration times.
  • a further object of the invention is to provide strongly perfumed cleaning compositions which can be tabletised at normal production speed around 500-1000 tablets per minute using standard rotary tabletting machines without production problems such as poor powder flowability and stickiness to die or piston surfaces.
  • the cleaning composition of the invention comprises
  • the invention is based on the discovery that by carefully adjusting the content of solubility intensifier and clay it is possible to manufacture effervescent based solid cleaning compositions with a high content of perfume and which are stable during storage and have short disintegration times, e.g. below 4 minutes in cold water.
  • perfume refers to fragrant or a mixture of substances including natural (i.e. obtained by extraction of flower, herb, blossom or plant), artificial
  • perfumes are complex mixtures of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g. terpenes) such as from 0% to 80%, usually from 10% to 70% by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.
  • essential oils e.g. terpenes
  • the precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of having a pleasant odour.
  • the perfume should be cosmetically acceptable, i.e. non-toxic, hypoallergenic etc.
  • solubility intensifier refers to a solubilizing agent that enhances the disintegration of the tablet in the water when added to water.
  • a solubility intensifier is characterized by having a high solubility in water, thereby facilitating a fast and homogeneous penetration of water into the tablet. This will ensure optimum conditions for the effervescent system and thereby provide for the quickest possible disintegration time.
  • disintegration time refers to the time it takes the tablet to disintegrate in a standard test system: The disintegration time is determined by placing tablets in separate baskets made from a stainless steel net having a mesh size of approximately 5 mm and placing said baskets in beakers containing 1 I of tap water of water hardness 180-250 ppm CaCO3 having a temperature of 20 °C.
  • the time it takes for the tablets to disintegrate without stirring and to leave the basket determines the disintegration time.
  • tablette strength refers to strength of the tablet when an external force is applied onto the tablet in a standard test system:
  • the tablet strength is determined by using a Holland tablet tester CT5.
  • the tablet is placed on a plane surface and under a stainless steel piston having a diameter of 8 mm.
  • the piston is then caused to move downwardly and into the surface of the tablet at a speed of 50 mm/min.
  • the force exerted on the tablet by the piston is determined by a strain gauge and the maximum force detected during the penetration defines the tablet strength.
  • the surfactants of a cleaning composition are active in removing dirt and grease.
  • suitable surfactants according to the invention are liquid, powdered, needle shaped or granular detergents having suitable cleaning properties and being capable of generating a foam during or after the disintegration of the tablets in water without unduly impairing the disintegration process.
  • the surfactants may be nonionic, anionic, cationic or amphoteric.
  • the surfactants may be used alone or in combination.
  • suitable surfactants are aliphatic ethoxylated/ propoxylated non-ionic surfactants, non-ionic surfactants of the alkyl- polyglucoside type, anionic surfactants of the linear alkylbenzene sulphonate type (LAS) and of the fatty alcohol sulphate type (FAS).
  • Co-granulates of suitable surfactants and builder/binder components are also applicable to use as surfactants.
  • An example of an amphoteric surfactant is Ampholak® X07- SD80 from Akzo Nobel in Sweden.
  • Benzalconium chloride BTC824P100 powder from Stepan in France is an example of a cationic surfactant.
  • Particularly preferred are anionic surfactants of granular form such as Sulfopon® 1216 G, a C12-C16 fatty alcohol sulphate, from Cognis in Germany.
  • the surfactants are used in a concentration of 0.1-25% by weight.
  • concentration of surfactant is 1-15% by weight, more preferably 2-10% by weight.
  • a part of the surfactant used may be added in the form of a foam booster.
  • Foam boosters can be many different types of ingredients which stabilize the foam.
  • An example is a coconut fatty acid diethanolamide such as Ufanon KDS from Unger.
  • a preferred foam booster is an alkyl sulfo acetate in the form of a coarse granulate or in small flakes such as Lathanol® LAL from Stepan in France.
  • the foam booster preferably constitutes from 0.1-5% by weight of the cleaning composition, more preferable from 0.5-2% by weight of the cleaning composition.
  • effervescent agent means a compound or composition which in the presence of water reacts with the acid compound of the cleaning composition so as to generate a gas, e.g. carbon dioxide.
  • suitable effervescent agents are percarbonates, bicarbonates, carbonates, bicarbonates, co-granulates of silicates and sodium carbonate like Nabion® 15 from Rhone Poulenc.
  • Preferred effervescent agents are alkali metal bicarbonates or carbonates such as sodium and potassium carbonate and/or sodium and potassium bicarbonate. The most preferred alkali metal carbonate is sodium carbonate.
  • the effervescent agent is preferably present in an amount of from 25-45% by weight.
  • the cleaning composition comprises an acid which reacts with the effervescent agent in the formulation and forms a gas, e.g. carbon dioxide.
  • a gas e.g. carbon dioxide.
  • Suitable examples of acids are organic acids such as carboxylic acids and/or inorganic acids such as sulphamic acid.
  • Preferred acids are organic acids such as citric acid, malic acid and adipic acid.
  • the most preferred organic acid is anhydrous citric acid with an average grain size of 300 micron.
  • the acid preferably constitutes from 30 to 50% by weight of the composition.
  • the ratio of effervescent agent to acid in the composition may be varied in order to obtain a higher or lower pH of the composition in use.
  • a low pH of the cleaning composition is preferred for cleaning ceramics and porcelain surfaces such as toilets bowls and cisterns.
  • a pH of 6-8 is preferred for cleaning hard surfaces such as windows.
  • the sodium carbonate used in the compositions according to the present invention can be either a light density sodium carbonate (density 400-580 g/l), a dense density sodium carbonate (density 10OOg/l - 1100 g/l), or mixtures of light density sodium carbonate and dense density sodium carbonate in a weight ratio of 5:1 to 1 :5.
  • a solubility intensifier which primarily dissolves quickly in water, a rapid transport of water throughout the entire tablet is facilitated.
  • a high solubility in cold water is not the only parameter which can promote a rapid transport of water throughout the entire tablet for shortest possible dissolution time.
  • the actual grain size of the solubility intensifier and the physical structure of the individual crystals are affecting the ability of the solubility intensifier to maximize the degree of water transport throughout the tablet interior.
  • Suitable ingredients are characterized by having a solubility in cold water higher than 10 g pr. 100 ml water at 20°C or more preferable higher than 50 g pr. 100 ml water at 20°C and even more preferable higher than 75 g/100 ml.
  • Non limiting examples are sodium gluconate, sodium citrate, sodium acetate, urea and sorbitol.
  • the preferred solubility intensifier is sodium acetate.
  • solubility levels for different ingredients are shown in the table below:
  • the solubility intensifier preferably constitutes 2-20% by weight, and more preferred 5-15% by weight of the composition.
  • the clay which as mentioned above is present in an amount of from 0.1 to 20% by weight of the cleaning composition exerts a stabilising effect on the cleaning composition and reduces the disintegration time after long term storage at the warehouse, in the supermarket or with the consumer.
  • Suitable clays are both naturally occurring and synthetic colloid-forming clays.
  • Suitable clays can be smectite clays including montmorillonite (bentonite), hecto te, saponite and the like. Available bentonite clays are the Laundrosil® types from Sud-Chemie AG in Germany or Detercal® / Detersoft® types from Laviosa Chimica Mineraria S.p.A. in Italy. Attapulgite clays include the materials commercially available under the tradename Attagel, e.g. Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporartion in USA. Mixtures of smectite and attapulgite types in weight ratios of 4:1 to 1 :5 are also useful herein.
  • Clays of the laponite type are synthetic layered silicates.
  • a preferred clay is Laponite RD.
  • Laponite RD is a synthetic hydrous sodium lithium magnesium silicate consisting of colloid or macromolecular layered silicates in the form of amorphous disc-shaped crystals.
  • Natural clay such as Bentonite and Hectohte have a similar disc- shaped crystal structure.
  • the clay preferably constitutes 0.5-15% by weight, more preferred 1-10% by weight of the composition.
  • solubility intensifier it is known to the person skilled in the art that if a certain type of clay is replaced by another type of clay, it may be necessary to adjust the content of the solubility intensifier accordingly. It should also be appreciated that the clay as well as the solubility intensifier may be used alone or in combination with other clays and solubility intensifiers, respectively.
  • the perfume preferably constitutes 1-10% by weight of the composition, more preferred 2-9% by weight of the composition and most preferred 3-8% by weight of the composition.
  • the perfume preferably constitutes 3.5-10% by weight of the composition, more preferred 4.0-10% by weight of the composition, even more preferred 4.5-10% by weight of the composition and most preferred 5.0-10% by weight of the composition.
  • the perfume used according to the invention may be incorporated directly into the powder, in a carrier associated form by using a highly absorbing substrate or in an encapsulated form.
  • the perfume is used directly in the cleaning composition.
  • the cleaning composition of the invention may contain up to 10% by weight of conventional cleaning composition additives to improve the general appearance, detergency and produceability.
  • the cleaning composition may contain phosphates to support the cleaning performance. All types of phosphates can be used in powder or granular form.
  • Non limiting examples of phosphate salts are builders such as the alkali metal thpolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophoshate, sodium polymeta/phosphate. Most preferred are sodium thpolyphosphates in granular form with an average grain size of 200-800 micron, even more preferred are sodium thpolyphosphates in granular form with an average grain size of 400-800 micron.
  • the cleaning composition according to the invention is phosphate free.
  • the composition comprises 40 % by weight of citric acid, 35 % by weight of sodium carbonate, 10 % by weight of sodium acetate, 5 % by weight of Laponite RD, 5 % by weight of anionic surfactant, 1 % by weight of non-ionic surfactant, 1 % by weight of tabletting additives and 3 % by weight of perfume.
  • the disintegration may be determined by placing tablets in separate baskets made from a stainless steel net having a mesh size of approximately 5 mm and placing said baskets in beakers containing 1 I of tap water of water hardness 180-250 ppm CaCO3 having a temperature of 20 °C. The time it takes for the tablets to disintegrate without stirring and to leave the basket determines the disintegration time.
  • the tablets according to the present invention has a disintegration time of less than four minutes, more preferred the disintegration time of the tablets is less than three minutes.
  • the invention also relates to a method for preparing a cleaning composition according to the present invention comprising mixing the ingredients.
  • the mixing of the ingredients according to the present invention is carried out using conventional mixing equipment known to the person skilled in the art, e.g. Nauta mixer.
  • Liquid ingredients may be added by spraying them on the other ingredients through a spraying device, e.g. a nozzle.
  • the ingredients are added one by one and mixed until a homogenous mixture is obtained, preferably the ingredients are mixed for 1-3 minutes between each addition.
  • the cleaning composition ingredients are mixed, it is an advantage to add the surfactants and the foam boosters in granular or powder form in the end of the mixing process in order to avoid the powder becoming sticky, which may eventually prolong the final disintegration time of the tablet.
  • the clay is added before adding the surfactants and foam boosters, which are added in the end of the mixing step.
  • the solid cleaning composition is compressed into tablets.
  • the tabletting of the powder according to the present invention is carried out using conventional tabletting equipment known to the person skilled in the art, e.g. a rotary tabletting press Model PH 423 from Korsch AG in Germany equipped with a conventional die and piston known to the person skilled in the art.
  • An appropriate tablet weight is achieved by adjusting the filling depth of the die in a manner known to the person skilled in the art.
  • the press force is also adjusted in a manner known to the person skilled in the art.
  • the tabletting speed is around 100-2500 tablets per minute, preferably around 250-1500 tablets per minute, most preferably around 500-1000 tablets per minute.
  • the tablets are packed using conventional packing equipment known to the person skilled in the art.
  • the packing is an in line packing process.
  • the invention also relates to tablets prepared from a cleaning composition as described above.
  • the tablets of the invention may have any suitable shape and size and may be composed of more than one layer, e.g. 2-3 or even more layers.
  • the cleaning tablets according to the invention can be made either as a single layer tablet or a multi-layer tablet, in a preferred embodiment the tablet is a single layer tablet.
  • Cleaning tablets for all purpose cleaning are of rectangular form having the dimensions 26 x 36 mm with a tablet weight of from 6 to 20 g and a tablet height of 5 to 18 mm.
  • Preferably all purpose cleaning tablets are cylindrical and have a diameter of from 12 mm to 50 mm with a tablet weight of from 1 to 40 g and a tablet height of from 12 mm to 18 mm.
  • Particularly preferred is 0 20 mm for a tablet weight of 4 g and a tablet height of 11 mm or 0 22,5 mm for a tablet weight of 5 g and a tablet height of 9 mm.
  • the tablets are packed into their final container. They may be packed together in any conceivable number directly into a suitable container, together in a bag using a vertical bag filler, packing a certain amount of tablets into a blister packing, preferably two tablets are packed together, more preferably each tablet is packed separately. Most preferred the tablets are flow packed separately in a suitable foil using hot or cold seal techniques.
  • the packing material can be made from polypropylene (PP) with a metalised layer for improved barrier properties against moisture and oxygen.
  • Example 1 In line manufacture and packing of cleaning tablets: Mixing Mixing was performed in a 1200 L conical Nauta mixer, in which a rotating screw is moving around the periphery of the mixer driving the powder from the bottom and up toward the top. Liquids were pumped through a mono pump via 1/2 inch steel tubes ending inside the Nauta mixer, spraying directly the liquids unto the powder via a special nozzle.
  • the powdered dye was dissolved and thoroughly dispersed in the liquid polyethylene glycol (PEG).
  • PEG liquid polyethylene glycol
  • the dye solution was sprayed unto the organic acid during mixing and mixed further for 2-3 minutes.
  • STEP 3 Sodium carbonate, sodium acetate and clay were added and mixed for 2 - 3 minutes whereafter the liquid perfume was sprayed directly unto the ingredients and mixed further 1-2 minutes.
  • STEP 4 Surfactants in powder or granular form (including the foam booster surfactant) were added and the mixing was continued for another 1 - 2 minutes and the batch was then discarded into a stainless steel transport silo. Tabletting
  • the tabletting step was carried out on a standard rotary tabletting press Model PH 423 from Korsch AG in Germany.
  • the transport silo was placed on top of the tabletting press allowing the powder to flow by gravity through the powder feeding tubes via the feed frame into the die of the press.
  • the wanted tablet weight is achieved by adjusting the filling depth of the die.
  • the press force was adjusted to around 5-35 kN.
  • the tabletting speed was around 500-1000 tablets pr. minute.
  • Example 2 Stability testing of tablets containing 2.5%, 5.0% and 7.5% clay, 10% sodium acetate and 3% perfume (by weight)
  • composition of these cleaning agents and the properties of the cleaning tablets are set forth in the following table.
  • Example 3 Stability testing of tablets containing varying amounts of clay, sodium acetate and perfume
  • composition of these cleaning agents and the properties of the cleaning tablets are set forth in the following table.
  • composition of these cleaning agents and the properties of the cleaning tablets are set forth in the following table.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une composition nettoyante à base effervescente solide convenant à la fabrication de comprimés, comprenant un composant de parfum ainsi qu'un intensificateur de solubilité et une argile. Un procédé de préparation de la composition nettoyante est également décrit.
PCT/DK2004/000901 2003-12-22 2004-12-22 Composition nettoyante solide pour la fabrication des comprimes WO2005061689A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US53232803P 2003-12-22 2003-12-22
DKPA200301907 2003-12-22
DKPA200301907 2003-12-22
US60/532,328 2003-12-22

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WO2005061689A1 true WO2005061689A1 (fr) 2005-07-07

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007007035A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Articles
WO2007007030A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article et procédé
WO2007007034A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article de nettoyage et procédé de nettoyage
WO2007007032A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article et procédé
WO2007007037A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article et procédé
WO2007007036A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article de nettoyage et procédé de nettoyage
WO2010017361A1 (fr) * 2008-08-07 2010-02-11 Phyzz, Inc. Comprimés/granules effervescents
WO2016142565A1 (fr) * 2015-03-12 2016-09-15 MARTÍ COMA, Lorena Composition détergente se présentant sous forme de pastille effervescente
WO2020264234A1 (fr) * 2019-06-28 2020-12-30 Ecolab Usa Inc. Stabilisation par tensioactif d'espèces hygroscopiques
CN114350448A (zh) * 2022-01-05 2022-04-15 广东一芙化妆品有限公司 富泡沫速溶清洁块及其方法
US20220186160A1 (en) * 2020-12-16 2022-06-16 Linkage Technology Development Switzerland SA Cleaning formulation
US20230042815A1 (en) * 2021-07-29 2023-02-09 Henkel IP & Holding GmbH Powdered Cleaning Composition Having Improved Dissolution
US20230046332A1 (en) * 2021-08-06 2023-02-16 Henkel IP & Holding GmbH Toilet Cleaning Product Containing Aqueous Crystalline Material
US20230049070A1 (en) * 2021-07-29 2023-02-16 Henkel IP & Holding GmbH Dissolvable Toilet Brush Formulations
US20230053756A1 (en) * 2021-08-06 2023-02-23 Henkel IP & Holding GmbH Dissolvable Toilet Brush - Low pH Formulations For Antibacterial And Antiviral Benefits

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2549723A1 (fr) * 1983-07-26 1985-02-01 Alain Beaujean Compositions effervescentes pour le bain
EP0537584A1 (fr) * 1991-10-12 1993-04-21 Henkel KGaA Tablette contenant des parfums
US6596682B1 (en) * 2002-04-16 2003-07-22 Colgate-Palmolive Company Cleaning compositions in the form of a tablet
US6608022B1 (en) * 2003-01-27 2003-08-19 Colgate-Palmolive Company Cleaning compositions in the form of a tablet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2549723A1 (fr) * 1983-07-26 1985-02-01 Alain Beaujean Compositions effervescentes pour le bain
EP0537584A1 (fr) * 1991-10-12 1993-04-21 Henkel KGaA Tablette contenant des parfums
US6596682B1 (en) * 2002-04-16 2003-07-22 Colgate-Palmolive Company Cleaning compositions in the form of a tablet
US6608022B1 (en) * 2003-01-27 2003-08-19 Colgate-Palmolive Company Cleaning compositions in the form of a tablet

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007007035A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Articles
WO2007007030A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article et procédé
WO2007007034A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article de nettoyage et procédé de nettoyage
WO2007007032A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article et procédé
WO2007007037A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article et procédé
WO2007007036A1 (fr) * 2005-07-08 2007-01-18 Reckitt Benckiser N.V. Article de nettoyage et procédé de nettoyage
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