EP0975721A1 - Produit gelifie de nettoyage de toilettes a chasse d'eau - Google Patents

Produit gelifie de nettoyage de toilettes a chasse d'eau

Info

Publication number
EP0975721A1
EP0975721A1 EP98921455A EP98921455A EP0975721A1 EP 0975721 A1 EP0975721 A1 EP 0975721A1 EP 98921455 A EP98921455 A EP 98921455A EP 98921455 A EP98921455 A EP 98921455A EP 0975721 A1 EP0975721 A1 EP 0975721A1
Authority
EP
European Patent Office
Prior art keywords
weight
amounts
particularly preferably
agents
composition according
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
EP98921455A
Other languages
German (de)
English (en)
Other versions
EP0975721B1 (fr
Inventor
Ronald Menke
Alexander Ditze
Frank Pessel
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to DK98921455T priority Critical patent/DK0975721T3/da
Publication of EP0975721A1 publication Critical patent/EP0975721A1/fr
Application granted granted Critical
Publication of EP0975721B1 publication Critical patent/EP0975721B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D3/48—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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/50—Perfumes
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the present invention relates to a gel-type cleaning agent which can preferably be used in flush toilets.
  • solid cleaning agents are used in piece form for automatically keeping toilets clean. These are either installed in the toilet bowl or in the water tank.
  • the moldings are overflowed with water during each rinsing process, whereby they gradually dissolve and release their active cleaning ingredients during this time.
  • These cleaning moldings usually contain additional perfume for room scenting or disinfectant agents for hygiene optimization.
  • the piece-shaped detergent tablets described are partially applied in suitable containers with special refill options.
  • the moldings described are generally produced by casting, pressing, extruding or granulating processes, which require a high level of technical outlay and frequently suffer undesirable perfume losses due to the temperature load (casting / extruding process) that occurs.
  • the object of the invention was to develop a system which does not have the disadvantages described. Surprisingly, it was found that special gel-like preparations with pseudoplastic properties significantly reduce the outlay for production and, because of the simple technique, are more cost-effective are to be produced. The problem of the individual refill possibility can also be solved by such pseudoplastic active substance preparations.
  • a special container which is particularly suitable for the gel-form cleaning agents according to the invention is described in DE-A-195 201 45.
  • the invention relates to a stable, gel-like and shear-thinning cleaning agent which, in addition to a polysaccharide, contains a C 8 to C 22 alkyl polyglycoside as a surfactant system and perfume components, the agent containing a polysaccharide in amounts of between 1 and 5% by weight as a component of the A C 8 to C 22 alkyl polyglucoside in amounts of between 3 and 25% by weight, the perfume component (s) in amounts of 2 to 15% by weight and possibly further ingredients such as cosurfactants, descaling agents, dyes, germ-inhibiting agents Contains agents, pearlescent agents, stabilizers, cleaning enhancers and odor absorbers and has a viscosity of 30,000 to 150,000 mPas; the viscosity was measured using a Brookfield rotary viscometer, type RVT with Helipath device and the spindle TA at 1 rpm and 23 ° C.
  • Another advantage is that the viscosity decreases with increasing shear rate, resulting in filling in the production process and easy handling by the consumer during metering / refilling.
  • the size of the air bubbles that z. B. on the stirring speed in the production process and the viscosity of the agent can be neither too large nor too small; in addition, the amount of air bubbles should also only be selected in a preferred range. If the presence of air bubbles is desired, it should not contain more than 30% by volume of air, preferably between 2 and 25% by volume of air and very particularly preferably between 5 and 20% by volume of air.
  • the most preferred embodiments contain air bubbles between 0.1 mm and 20 mm in diameter, most preferably between 1 mm and 15 mm in diameter.
  • the viscosity of the agents according to the invention also allows the air bubbles already entered in the production process by briefly applying a negative pressure which can be in a range just below room pressure to close to a vacuum.
  • the duration of the vacuum treatment depends on the strength of the vacuum. With a stronger negative pressure, the treatment does not have to be carried out as long.
  • the person skilled in the art also knows that if the negative pressure is too strong, undesirable side effects can occur, such as, for. B. the increased evaporation of volatile perfume components and u. U. Problems with the stirrability of the system. Degassing of the agents according to the invention by treatment in a centrifuge or by ultrafast stirring is possible, but less preferred.
  • the person skilled in the art according to the present invention avoids excessive action of shear forces on the agents according to the invention during and after the production process, since otherwise the properties according to the invention are often lost in the short to medium term and can only be recovered after longer waiting times.
  • water is in a commercial mixer, such as. B. a Beco mix system, submitted and the dye stirred.
  • a commercial mixer such as. B. a Beco mix system
  • the xanthan gum which is preferably used as the polysaccharide is preferred with solvent
  • Suspension is added to the initial charge and stirred at low speeds, for example 30 rpm.
  • the mixture is generally to be placed in a suitable container, depending on the viscosity, for a short time, for example 15 minutes, under reduced pressure or under a vacuum.
  • the disinfectant is then added, preferably selected from the group of isothiazolines, benzoates or salicylic acid or salicylates.
  • the filling can in this case, for. B. done in a commercial dosing bottle via a rotary bottle.
  • Brookfield viscometers were used, which are a spindle intended for gels have ready.
  • the viscosities according to the invention were measured with this Helipath spindle.
  • formulations according to the invention can contain the following components in a frame formulation:
  • complexing agent 2 0 to 5.0% by weight of complexing agent 2 to 15% by weight, preferably 2 to 12% by weight and in particular 3 to 8% by weight of perfume to 5.0% by weight, preferably 0.01 to 4 wt .-% solvent, such as Ethanol
  • Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate.
  • Xanthomonas campestris produces xanthan under aerobic conditions with a molecular weight of 2-15 X 10 6 .
  • Xanthan is produced in batch cultures and dried and ground with propanol after killing the culture and cases. Other suitable methods are also described in the literature.
  • the polysaccharide in particular xanthan gum, is preferably present in the compositions in amounts of between 1 and 4% by weight, in particular between 1.5 and 3.5% by weight and most preferably between 1, 8 and 3% by weight .
  • Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols using the relevant methods of preparative organic chemistry, with a mixture of monoalkylated, oligomeric or polymeric sugars depending on the type of preparation.
  • Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol with alkyl chain lengths between C 8 and C 22 , preferably between C 8 and C ⁇ and particularly preferably between C 8 and C 12 or a mixture of long-chain fatty alcohols.
  • the degree of oligomerization of the sugars which is a calculated and therefore generally not an integer size, is between 1 and 10, preferably between 1, 1 and 5 and very particularly preferably between 1, 2 and 3 and extremely preferably between 1, 3 and 2 , 5th
  • the agents contain C 8 to C 22 alkyl polyglycosides, preferably in amounts of 4 to 20% by weight, in particular 5 to 17% by weight and extremely preferably 5 to 15% by weight, with amounts of up to 12% by weight also .-% can be advantageous.
  • Anionic co-surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lignin sulfonates.
  • aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether
  • Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates are also usable within the scope of the present invention, but are not preferred.
  • Fatty alcohol sulfates and fatty alcohol ether sulfates are preferably used. So far, less good results have been achieved with alkylbenzenesulfonates.
  • the weight ratio of alkyl polyglycoside to cosurfactants is at least 1, ratios between 50: 1 and 1: 1, particularly preferably between 10: 1 and 1.5: 1 and very particularly preferably between 5: 1 and 1.8: 1, are particularly advantageous.
  • Nonionic co-surfactants can also be used.
  • Nonionic surfactants in the context of the present invention can be alkoxylated alcohols, such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters.
  • alkoxylated alcohols such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters.
  • Ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides can also be used
  • alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably the longer-chain alcohols in the sense of the present invention.
  • n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • final etherification with short-chain alkyl groups such as preferably the butyl group, can also give the substance class of the “closed” alcohol ethoxylates, which can also be used for the purposes of the invention.
  • Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.
  • the formulations described can preferably contain inorganic or organic acids such as citric acid, acetic acid, lactic acid or their water-soluble salts in an amount of 1-12% by weight as descaling agents. Contents of 2-5% by weight are particularly preferred.
  • the agents according to the invention preferably contain dye, either for the coloring of the product or for the coloring of the liquid surrounding the container.
  • the content of water-soluble dyes is preferably ⁇ 1% by weight and serves to improve the appearance of the product. If an additional color signal is required during the flushing process, the content of water-soluble dyes can be up to 5% by weight.
  • the content is preferably in amounts of up to 3% by weight, in particular up to 2% by weight and very preferably up to 1% by weight.
  • the gels according to the invention already have an excellent cleaning action without this component, the hygienic action can be enhanced by the addition of germ-inhibiting agents.
  • the amount of these agents depends strongly on the effectiveness of the particular compound and can be up to 5% by weight. At least 0.01% by weight is preferably incorporated into the gels. The range between 0.01% by weight and 3% by weight is particularly preferred. Isothiazoline mixtures, sodium benzoate or salicylic acid or salicylates are particularly suitable. Further preferred amounts are from 0.01 to 2% by weight, in particular from 0.01 to 1% by weight.
  • Solubilizers for example for dyes and perfume oils, can be used, for example, as alkanolamines, polyols such as ethylene glycol, representatives of the lower alcohols such as propylene glycol, glycerol and other mono- and polyhydric alcohols, and also alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical.
  • Preferred amounts are up to 5% by weight, in particular 0.01 to 4% by weight, advantageously 0.1 to 4% by weight and very particularly preferably 0.5 to 3% by weight.
  • the usual thickeners which could also be used if required, include urea, sodium chloride, sodium sulfate, magnesium sulfate, ammonium chloride and magnesium chloride and the combination of these thickeners. However, the use of these additional thickeners is not preferred.
  • Water-soluble and water-insoluble builders may be present in the cleaning agents according to the invention. Then there are water-soluble builders preferred because they tend to have less tendency to form insoluble residues on hard surfaces.
  • Customary builders or complexing agents which can be present in the context of the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the citric acid and their salts, the carbonates, phosphates and silicates.
  • Water-insoluble builders include the zeolites, which can also be used, as well as mixtures of the abovementioned builder substances. The group of citrates is particularly preferred.
  • the agents according to the invention preferably contain builders or complexing agents in amounts of up to 10% by weight, in particular 0.1 to 8% by weight, particularly preferably 1 to 6% by weight and very particularly preferably 2 to 5% by weight.
  • the viscosity in the examples listed was measured using a Brookfield Roto viscometer, rotary viscometer, type RVT with Helipath device and the spindle TA at 1 rpm and 23 ° C.
  • 0.1 g of gel are foamed in 500 ml of tap water at 17 ° d in a 1000 ml measuring cylinder with 40 strokes at a rotation speed of 100 rpm.
  • the structure of the foam volume is read after 1, 3 and 10 min.
  • the measurement is carried out on an automatically controlled toilet system, which dispenses the contents of the water tank every 1 hour and refills the tank with 9 liters of tap water at 17 ° d and a water temperature of 15 - 16 ° C.
  • an automatically controlled toilet system which dispenses the contents of the water tank every 1 hour and refills the tank with 9 liters of tap water at 17 ° d and a water temperature of 15 - 16 ° C.
  • 1 filling of a vessel according to DE 195 201 45 is hung in the toilets and it is determined how many flushes are possible until it is completely used up.
  • the average results are determined from 5 parallel tests.
  • Pre-weighed white Carrara marble slabs measuring 75 x 150 x 5 mm are completely immersed in the gel in a plexiglass cell. This is done for a time of 10 seconds.
  • the plate is then removed and placed vertically in a stand provided for this purpose. This has to be done in such a way that adhering product can run off.
  • the exposure time of the adhesive Product is another 10 min.
  • the plate is then rinsed with water and the weight loss is determined after drying at 105 ° C.
  • the measurement was carried out electrochemically in the concentrate.
  • the storage took place in electrically controlled heat chambers.
  • the storage time at 40 ° C is 3 and 4 weeks, at 23 ° C 12 weeks. This was followed by a visual inspection of the stored goods.
  • Xanthan gum granulated e.g. Keltrol® RD 2.3
  • Rinsing behavior 220 rinses at 21 rinses / day
  • the production can be in a wide variety of batch sizes up to
  • Tone scale can be carried out.
  • water is in a commercial mixer, such as. B. submitted to a Beco mix system, and the dye stirred.
  • the xanthan gum used is slurried separately with solvent, preferably ethanol and the desired perfume oil.
  • Suspension is added to the aqueous template and with small
  • the mixture should, as a rule, be placed in a suitable container depending on the viscosity for a short time, for example 15 minutes under reduced pressure or under a vacuum.
  • the filling in the appropriate storage container can then, for. B. via a suitable commercially available tube filler.
  • Rinsing behavior 250 rinses at 21 rinses / day
  • Tone scale can be carried out.
  • the suspension is added to the template and with low
  • the filling can in this case, for. B. done in a commercial dosing bottle via a rotary bottle.
  • Rinsing behavior 230 rinses at 21 rinses / day
  • TTF Perfume oil apple note
  • TTF Perfume oil apple note
  • Rinsing behavior 300 rinses at 21 rinses / day
  • Foaming behavior 100 ml 1 min; 80 ml 3 min; 50 ml 10 min.
  • TTF Perfume oil apple note
  • Rinsing behavior 500 rinses at 21 rinses / day
  • Rinsing behavior 280 rinses at 21 rinses / day
  • TTF Perfume oil Cool water

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

L'objet de l'invention est d'améliorer la stabilité, le pouvoir odorant et nettoyant et la capacité de recharge d'un produit gélifié de nettoyage, de préférence de toilettes à chasse d'eau. A cet effet, on prépare un produit gélifié de nettoyage diluant qui contient entre 1 et 5 % en poids d'un polysaccharide, 3 à 25 % en poids d'un alkylpolyglycoside en C8 à C22 comme élément constitutif du système tensioactif, jusqu'à 15 % en poids d'un élément odoriférant, ainsi que d'autres ingrédients tels que des antitartres, des colorants, des agents bactéricides, des agents lustrants, des stabilisateurs, des renforçateurs du pouvoir de nettoyage et des absorbants d'odeurs. Ces produits gélifiés ont une viscosité comprise entre 30.000 et 150.000 mPas.
EP98921455A 1997-04-16 1998-04-11 Produit gelifie de nettoyage de toilettes a chasse d'eau Expired - Lifetime EP0975721B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DK98921455T DK0975721T3 (da) 1997-04-16 1998-04-11 Gelformigt rengöringsmiddel til skylletoiletter

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19715872A DE19715872C2 (de) 1997-04-16 1997-04-16 Gelförmiges Reinigungsmittel für Spültoiletten
DE19715872 1997-04-16
PCT/EP1998/002123 WO1998046712A1 (fr) 1997-04-16 1998-04-11 Produit gelifie de nettoyage de toilettes a chasse d'eau

Publications (2)

Publication Number Publication Date
EP0975721A1 true EP0975721A1 (fr) 2000-02-02
EP0975721B1 EP0975721B1 (fr) 2004-06-16

Family

ID=7826682

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98921455A Expired - Lifetime EP0975721B1 (fr) 1997-04-16 1998-04-11 Produit gelifie de nettoyage de toilettes a chasse d'eau

Country Status (9)

Country Link
EP (1) EP0975721B1 (fr)
JP (1) JP2001518969A (fr)
AT (1) ATE269389T1 (fr)
BR (1) BR9811461A (fr)
CA (1) CA2287449A1 (fr)
DE (2) DE19715872C2 (fr)
DK (1) DK0975721T3 (fr)
ES (1) ES2224390T3 (fr)
WO (1) WO1998046712A1 (fr)

Families Citing this family (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19826293A1 (de) * 1998-06-12 2000-03-23 Buck Chemie Gmbh Sanitärmittel
DE19853110A1 (de) * 1998-11-18 2000-05-25 Cognis Deutschland Gmbh Gelförmiges Reinigungsmittel für Spültoiletten
DE19906481A1 (de) * 1999-02-17 2000-08-24 Cognis Deutschland Gmbh Gelförmige Reinigungsmittel für Spültoiletten
DE19910788A1 (de) * 1999-03-11 2000-09-14 Cognis Deutschland Gmbh Gelförmiges Reinigungsmittel für Spültoiletten
DE19918186A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
DE19918184A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
DE19918192A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
DE19918182A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
DE19918185A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
DE19918189A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
DE19918191A1 (de) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
DE19918188A1 (de) 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Reinigungsmittel für harte Oberflächen
DE19924368A1 (de) * 1999-05-27 2000-11-30 Henkel Ecolab Gmbh & Co Ohg Tensidhaltige Reinigungsformkörper
GB2360293A (en) * 2000-03-14 2001-09-19 Procter & Gamble Detergent compositions
DE10012949A1 (de) 2000-03-16 2001-09-27 Henkel Kgaa Kieselsäureester-Mischungen
US7048205B2 (en) 2000-07-12 2006-05-23 S.C. Johnson & Son, Inc. Lavatory freshening and/or cleaning system and method
GB2364710B (en) * 2000-07-12 2003-01-15 Johnson & Son Inc S C Lavatory freshening and/or cleaning system and method
GB2364709B (en) * 2000-07-12 2004-12-22 Johnson & Son Inc S C Lavatory freshening and/or cleaning system and method
DE10048887A1 (de) * 2000-09-29 2002-04-18 Buck Chemie Gmbh Haftendes Sanitärreinigungs- und Beduftungsmittel
US7541325B2 (en) * 2001-01-11 2009-06-02 Joker Ag Agent for removing solid particles
JP4541076B2 (ja) * 2004-09-07 2010-09-08 京都リフレ新薬株式会社 尿石付着防止剤
DE102004056554A1 (de) * 2004-11-23 2006-05-24 Buck-Chemie Gmbh Haftendes Sanitärreinigungs- und Beduftungsmittel
JP2005330498A (ja) * 2005-05-09 2005-12-02 Sara Lee De Nv ラバトリー用フレッシュナー／クリーナーシステム
EP1894989A1 (fr) * 2006-09-01 2008-03-05 The Procter and Gamble Company Composition pâteuse pour articles sanitaires
EP1894578A1 (fr) * 2006-09-01 2008-03-05 The Procter and Gamble Company Procédé d'application d'une composition pâteuse pour articles sanitaires
EP1894990A1 (fr) * 2006-09-01 2008-03-05 The Procter and Gamble Company Dose d'unité de la composition pâteuse pour des articles sanitaires
US7414016B1 (en) * 2007-11-01 2008-08-19 The Clorox Company Acidic cleaning compositions
US8143206B2 (en) * 2008-02-21 2012-03-27 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion 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
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
US9410111B2 (en) 2008-02-21 2016-08-09 S.C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
DE102009001841A1 (de) * 2009-03-25 2010-09-30 Henkel Ag & Co. Kgaa System aus Reinigungsmittel und Abgabevorrichtung
JP5579593B2 (ja) * 2010-12-22 2014-08-27 ニュートリー株式会社 ゼリー状洗浄組成物
EP2662435B1 (fr) 2012-05-11 2016-12-28 Eurvest Composition hygiénique
JP2016526057A (ja) * 2013-04-25 2016-09-01 ユニリーバー・ナームローゼ・ベンノートシヤープ 分配性および懸濁性の改良された洗浄組成物
WO2014180579A1 (fr) 2013-05-10 2014-11-13 Eurvest Sa Nouvelle composition sanitaire
DE102013226098A1 (de) 2013-12-16 2015-06-18 Henkel Kgaa Silylenolether von Riechstoffketonen oder -aldehyden
DE102013226216A1 (de) 2013-12-17 2015-06-18 Henkel Ag & Co. Kgaa Michael-Systeme für die Duftstoff-Stabilisierung
DE102013226602A1 (de) 2013-12-19 2015-06-25 Henkel Ag & Co. Kgaa Verwendung von CNGA2-Agonisten zur Verstärkung der olfaktorischen Wirkung eines Riechstoffs
EP2963103A1 (fr) 2014-07-04 2016-01-06 Henkel AG & Co. KGaA Nanocapsules sensibles au pH
DE102017123282A1 (de) 2017-10-06 2019-04-11 Henkel Ag & Co. Kgaa Hydrolyselabile Silylenolether von Riechstoffketonen oder -aldehyden
DE102017124612A1 (de) 2017-10-20 2019-04-25 Henkel Ag & Co. Kgaa Hydrolyselabile Dienolsilylether von Riechstoffketonen oder -aldehyden
DE102017124611A1 (de) 2017-10-20 2019-04-25 Henkel Ag & Co. Kgaa Thermolabile Duftspeicherstoffe von Riechstoffketonen
DE102017127776A1 (de) 2017-11-24 2019-05-29 Henkel Ag & Co. Kgaa Hydrolyselabile Heterocyclen von Riechstoffketonen oder -aldehyden
DE102018210801A1 (de) * 2018-06-29 2020-01-02 Henkel Ag & Co. Kgaa Selbsthaftende schäumende Sanitärmittel
PL3722401T3 (pl) 2019-04-10 2024-05-13 Henkel Ag & Co. Kgaa Żelowy środek sanitarny dla unikania biofilmu
EP4098734B1 (fr) 2021-06-02 2025-03-19 Henkel AG & Co. KGaA Système de toilettes à composition gel multiphasée
DE102022121761A1 (de) 2022-08-29 2024-02-29 Henkel Ag & Co. Kgaa Wasserverlust-stabile gelzusammensetzung
DE102022121759A1 (de) 2022-08-29 2024-02-29 Henkel Ag & Co. Kgaa Temperaturstabile gelzusammensetzungen
DE102023202758A1 (de) * 2023-03-27 2024-10-02 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines gelförmigen Reinigungsmittels
DE102023202757A1 (de) 2023-03-27 2024-10-02 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines gelförmigen Reinigungsmittels
DE102023211954A1 (de) 2023-11-29 2025-06-05 Henkel Ag & Co. Kgaa Applikator mit separatorschicht für selbsthaftende sanitäre mittel

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4668422A (en) * 1985-05-31 1987-05-26 A. E. Staley Manufacturing Company Liquid hand-soap or bubble bath composition
CA1321115C (fr) * 1987-12-30 1993-08-10 Robert Corring Composes de gel detergent
US5047167A (en) * 1987-12-30 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Clear viscoelastic detergent gel compositions containing alkyl polyglycosides
CA2014220C (fr) * 1989-04-11 1995-11-07 Peter Leonard Dawson Liquide de nettoyage
FI931367L (fi) * 1990-09-28 1993-04-26 Procter & Gamble Tvaettmedelskompositioner, som innehaoller polyhydroxifettsyraamider ochen skumfoerstaerkare
GB9103090D0 (en) * 1991-02-14 1991-04-03 Unilever Plc Hair care compositions
GB2288186A (en) * 1994-02-17 1995-10-11 Kelco Int Ltd Toilet cleansing gel block

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9846712A1 *

Also Published As

Publication number Publication date
ATE269389T1 (de) 2004-07-15
EP0975721B1 (fr) 2004-06-16
ES2224390T3 (es) 2005-03-01
DE19715872C2 (de) 1999-04-29
JP2001518969A (ja) 2001-10-16
WO1998046712A1 (fr) 1998-10-22
DE59811584D1 (de) 2004-07-22
DE19715872A1 (de) 1998-10-22
DK0975721T3 (da) 2004-10-25
CA2287449A1 (fr) 1998-10-22
BR9811461A (pt) 2000-09-12

Similar Documents

Publication Publication Date Title
EP0975721B1 (fr) Produit gelifie de nettoyage de toilettes a chasse d'eau
EP0268967B1 (fr) Bloc de nettoyage pour le bac à eau de toilettes
EP1325103B1 (fr) Agent sanitaire et desodorisant adhesif
US6336977B1 (en) Gelled cleaning agent for flush toilets
EP0355551B1 (fr) Agent de lavage et de nettoyage sous forme de pâte et son procédé de préparation
DE2407947A1 (de) Reinigungsblock
DE19853110A1 (de) Gelförmiges Reinigungsmittel für Spültoiletten
EP0864637A1 (fr) Bloc nettoyant à base de gel pour une hygiène des toilettes avec de l'air parfumé en permanence
DE4332849A1 (de) Pastenförmiges Waschmittel
EP1029911A1 (fr) Gel pour le nettoyage des toilettes
DE69311854T2 (de) Flüssiges Reinigungsmittel auf der Basis von starkschäumenden, nichtionischen, oberflächenaktiven Mitteln
EP0844303B1 (fr) Article solide pour les WC
DE19910788A1 (de) Gelförmiges Reinigungsmittel für Spültoiletten
WO2000071665A1 (fr) Nettoyant aqueux acide a plusieurs phases
EP1036157B1 (fr) Detergent a vaisselle a profil de viscosite specifique
EP0523681B1 (fr) Composition détergente pour le lavage automatique de la vaisselle et méthode pour sa production
EP2655585A1 (fr) Compositions contenant un sulfonate de paraffine secondaire et un alcoxylat d'alcool
DE10020090A1 (de) Vorrichtung zur Abgabe einer Wirkstoffzubereitung ein ein Toilettenbecken
DE4026809A1 (de) Fluessiges waschmittel mit erhoehter viskositaet
EP0721493B1 (fr) Detergent pateux pour textiles
DD241747A1 (de) Mittel zur reinigung und desinfektion von toilettenspuelkaesten und -becken
DE19752454B4 (de) Geschirrspülmittel mit spezifischem Viskositätsprofil
DE4239679A1 (de) Viskose wäßrige Tensidzubereitungen
DD216953A1 (de) Mittel zur reinigung und desinfektion von toilettenspuelkaesten und -becken
EP1382664A1 (fr) Composition liquide neutre de nettoyage

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19991007

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE DK ES FI FR GB IT NL SE

17Q First examination report despatched

Effective date: 20021125

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE DK ES FI FR GB IT NL SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 59811584

Country of ref document: DE

Date of ref document: 20040722

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20040906

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2224390

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20050317

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20140311

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20140409

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20140326

Year of fee payment: 17

Ref country code: NL

Payment date: 20140410

Year of fee payment: 17

Ref country code: FI

Payment date: 20140410

Year of fee payment: 17

Ref country code: FR

Payment date: 20140409

Year of fee payment: 17

Ref country code: SE

Payment date: 20140411

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20140414

Year of fee payment: 17

Ref country code: DK

Payment date: 20140410

Year of fee payment: 17

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20150430

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 269389

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150411

Ref country code: SE

Ref legal event code: EUG

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20150411

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20150501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150411

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150411

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20151231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150430

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150412

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150430

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20160527

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150412

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20160427

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150430

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20170419

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59811584

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170411