EP2430136B1 - Bloc wc sphérique, son procédé de fabrication et nacelle de nettoyage de wc équipé de blocs wc sphériques - Google Patents

Bloc wc sphérique, son procédé de fabrication et nacelle de nettoyage de wc équipé de blocs wc sphériques Download PDF

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Publication number
EP2430136B1
EP2430136B1 EP10721412.4A EP10721412A EP2430136B1 EP 2430136 B1 EP2430136 B1 EP 2430136B1 EP 10721412 A EP10721412 A EP 10721412A EP 2430136 B1 EP2430136 B1 EP 2430136B1
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EP
European Patent Office
Prior art keywords
cleaning block
toilet
toilet cleaning
oil
particularly preferably
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EP10721412.4A
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German (de)
English (en)
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EP2430136A1 (fr
Inventor
Nadine Warkotsch
Brigitte Giesen
Anke Ernst
Sascha Schrecker
Christian Reichert
Ralph Butter-Jentsch
Hans-Georg MÜHLHAUSEN
Robert Stephen Cappleman
Michael Horn
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP15164184.2A priority Critical patent/EP2924099B1/fr
Priority to PL15164184T priority patent/PL2924099T3/pl
Publication of EP2430136A1 publication Critical patent/EP2430136A1/fr
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Priority to HRP20170218TT priority patent/HRP20170218T1/hr
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    • 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
    • C11D1/83—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D9/00—Sanitary or other accessories for lavatories ; Devices for cleaning or disinfecting the toilet room or the toilet bowl; Devices for eliminating smells
    • E03D9/02—Devices adding a disinfecting, deodorising, or cleaning agent to the water while flushing
    • E03D9/03—Devices adding a disinfecting, deodorising, or cleaning agent to the water while flushing consisting of a separate container with an outlet through which the agent is introduced into the flushing water, e.g. by suction ; Devices for agents in direct contact with flushing water
    • E03D9/032—Devices connected to or dispensing into the bowl
    • 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
    • C11D1/143—Sulfonic acid 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • the invention relates to a toilet cleaning block containing perfume, at least one nonionic surfactant and at least one alkylbenzenesulfonate and at least one olefinsulfonate, wherein a C 12-22 fatty alcohol alkoxylate is contained with a degree of ethoxylation of 12 to 28 and in a rolling machine or a press to a a rotationally symmetrical, in particular spherical body can be formed, a method for its production and a system of at least one such toilet cleaning block and a dispenser.
  • WC cleaning pieces also known as WC bricks
  • rim blocks edge of the pool
  • in-tank blocks or cistern blocks in-tank blocks
  • aesthetics and performance have become increasingly important. This led, for example, to the development of gel or liquid scenters, which are sometimes offered in multi-chamber containers and thus allow the combination of a detergent that is released when the toilet flushing, with a permanent Jardinbeduftung.
  • the WO 2007/148054 A1 a specific cageless toilet dispenser comprising a compacted solid block comprising titanium dioxide and at least one chemical agent adapted to be suspended inside the sanitary appliance.
  • solid toilet blocks are still relevant. So far, these have mainly been produced by extrusion and then cut to give cuboid WC rim blocks, which were then inserted into corresponding baskets.
  • Rimblocks A disadvantage of these Rimblocks is that they swell by the penetrating into the basket rinse water, rinsed unevenly and lose their shape. After a short time, therefore, an unaesthetic block remains.
  • a formulation which perfume, at least one nonionic surfactant and at least one alkylbenzenesulfonate and at least one olefinsulfonate contains, allows the production of round and therefore aesthetic toilet blocks at temperatures of 30 ° C and less.
  • These WC bricks do not swell and always have a minimal surface due to their round shape. The rinsing therefore takes place uniformly, so that the original shape is retained even after a large number of rinsing off operations.
  • the invention therefore provides a toilet cleaning block containing perfume, at least one nonionic surfactant and at least one alkylbenzenesulfonate and at least one olefinsulfonate, wherein a C 12-22 fatty alcohol alkoxylate is included with a degree of ethoxylation of 12 to 28, in a rolling machine or a press can be formed into a rotationally symmetrical body.
  • a toilet cleaning block containing perfume, at least one nonionic surfactant and at least one alkylbenzenesulfonate and at least one olefinsulfonate, wherein a C 12-22 fatty alcohol alkoxylate is included with a degree of ethoxylation of 12 to 28, in a rolling machine or a press can be formed into a rotationally symmetrical body.
  • the production of spherical WC cleaning block with high sphericity is possible.
  • the toilet cleaning block according to the invention is usually used in a dispenser, such as a so-called toilet bowl.
  • a dispenser such as a so-called toilet bowl.
  • Another object of this invention is therefore a system comprising at least one toilet cleaning block according to the invention and a dispensing device.
  • the WC cleaning block of the present invention may be prepared in a process comprising the steps of mixing the ingredients, extruding the mixture, cutting the extruded strand into portions of defined mass, and deforming into rotationally symmetric bodies.
  • the inventive system of the toilet cleaning block and the dispensing device can also be used in a method for cleaning and / or scenting and / or disinfecting Spül toilets such that the filled with the toilet block cleaning device is suspended in the toilet bowl and the Pressing the toilet flush dissolved ingredients of the toilet cleaning block get into the rinse water and there unfold their cleansing and / or fragrant and / or disinfecting effect.
  • Yet another subject of the invention is therefore a method for cleaning and / or scenting and / or disinfecting Spül toilets using a system of a toilet cleaning block according to the invention and a dispenser.
  • the International Cosmetic Ingredient Dictionary and Handbook assigns the ingredients one or more chemical classes (Chemical Classes), for example, Polymeric ether, and one or more functions (functions), for example Surfactants - Cleansing Agents to, in turn, are explained in detail and subsequently to the possibly also referred to.
  • chemical Classes for example, Polymeric ether
  • functions for example Surfactants - Cleansing Agents
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service .
  • fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 bis 18 carbon atoms, most preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms.
  • the former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them.
  • the oxo alcohols or derivatives thereof which are obtainable, for example, by ROELEN's oxo synthesis and preferably have 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, more preferably 9 to 17 carbon atoms, most preferably 11 to 15 carbon atoms, for example 9 to 11 carbon atoms , 12 to 15 or 13 to 15 carbon atoms, can be used accordingly.
  • the agent contains one or more fragrances, preferably in an amount of 0.01 to 10 wt .-%, in particular 0.05 to 8 wt .-%, particularly preferably 0.1 to 5 wt .-%.
  • a perfume component d-limonene may be contained.
  • the toilet cleaning block according to the invention contains a perfume of essential oils (also referred to as essential oils). Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil, for example, can be used as such in the context of this invention.
  • Muskateller sage oil chamomile oil, lavender oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • a fragrance In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note or body” and “base note “(end note or dry out) divided.
  • Adhesive-resistant fragrances which are advantageously usable in the perfume oils in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, Bay oil, Champacablütenöl, Edeltannenöl, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce alder oil, galbanum oil, geranium oil, Ginger Grass Oil, Guajac Wood Oil, Gurjun Balm Oil, Helichrysum Oil, Ho Oil, Ginger Oil, Iris Oil, Cajeput Oil, Calam Oil, Camomile Oil, Camphor Oil, Kanaga Oil, Cardamom Oil, Cassia Oil, Pine Needle Oil, Kopa ⁇ va Balsam Oil, Coriander Oil, Spearmint Oil, Cumin Oil, Cumin Oil, Lemongrass Oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli oil, Niaouli oil, Olibanum oil
  • fragrances of natural or synthetic origin can be used in the context of the present invention advantageously as adherent fragrances or fragrance mixtures in the perfume oils.
  • These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, borneol, bornyl acetate, ⁇ -bromostyrene, n -Decylaldehyde, n-dodecyl-aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, gerany
  • the lower-boiling fragrances include natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • the WC cleaning block according to the invention contains at least one nonionic surfactant, wherein a C 12-22 fatty alcohol alkoxylate is contained with a degree of ethoxylation of 12 to 28, and at least one alkylbenzenesulfonate and at least one olefinsulfonate.
  • other surfactants may be included.
  • the WC cleaning block according to the invention contains preferably 10 to 70 wt .-%, preferably 20 to 65 wt .-%, particularly preferably 20 to 30 wt .-% alkylbenzenesulfonate and preferably 10 to 30 wt .-%, preferably 15 to 30 wt .-%, more preferably 15 to 25 wt .-% olefinsulfonate.
  • nonionic surfactants may be included.
  • suitable nonionic surfactants in the context of the invention may be alkoxylates 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 fatty acid alkanolamides, and fatty acid polyglycol ethers.
  • nonionic surfactants which can be used according to the invention are the polyol surfactants, in particular the glycerides, such as alkyl polyglycosides and fatty acid glucamides. Particular preference is given to the alkylpolyglycosides, in particular the alkylpolyglucosides, and especially the fatty alcohol alkoxylates (fatty alcohol polyglycol ethers).
  • Preferred fatty alcohol alkoxylates are ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C 8-22 alcohols having a degree of alkoxylation up to 30, preferably ethoxylated C 12-22 fatty alcohols having a degree of ethoxylation of less as 30, preferably 12 to 28, especially 20 to 28, particularly preferably 25, for example C 16-18 fatty alcohol ethoxylates with 25 EO.
  • EO ethylene oxide
  • PO propylene oxide
  • Alkylpolyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant processes of preparative organic chemistry, wherein, depending on the nature of the preparation, a mixture of monoalkylated, oligomeric or polymeric sugars is obtained.
  • Preferred alkyl polyglycosides are the alkyl polyglucosides, the alcohol particularly preferably being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C 8 - to C 18 -alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, especially 1.1 to 3, more preferably 1.1 to 1.7, for example, C 8-10 alkyl-1.5-glucoside (DP of 1.5).
  • DP degree of oligomerization
  • fatty alcohol ethoxylates are used in amounts of up to 20% by weight, more preferably 4 to 12% by weight, particularly preferably 7 to 9% by weight.
  • further nonionic surfactants for example fatty acid monoalkanolamides and / or alkylpolyglycosides, may be present in amounts of up to 10% by weight.
  • anionic surfactants which may be used in the WC cleaning block according to the invention are aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • fatty acid cyanamides sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • sulfosuccinates sulfosuccinic esters
  • sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters sulfosuccinamates
  • fatty alcohol sulfates and / or fatty alcohol ether sulfates are products of sulfation reactions on corresponding alcohols
  • fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols.
  • the person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols.
  • a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions.
  • Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • Preferred fatty alcohol ether sulfates are the sulfates of lower ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.
  • EO ethylene oxide units
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, eg Dodecylbenzenesulfonic.
  • the agent according to the invention may also contain cationic surfactants and / or amphoteric surfactants.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO-, in which R iii is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethylbetain and C 11 -C 17 -alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X - , in which R vi to R ix are four identical or different, in particular two long and two short-chain, alkyl radicals and X- for an anion, in particular a halide ion, are, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • the toilet cleaning block according to the invention may contain further ingredients commonly used in toilet cleaning blocks, preferably selected from the group comprising acids, bases, salts, thickeners, antimicrobial agents, preservatives, complexing agents, polymers, dyes, perfumes, perfume boosters , Fillers, builders, bleaches, corrosion inhibitors, rinse off regulators, enzymes, microorganisms, biofilm removal agents, limescale inhibiting agents, soil adhesion reducing agents, processability improving agents, stickiness reducing agents, and mixtures thereof.
  • further ingredients should be included, preferably 0.01 to 60 wt .-%, in particular 0.2 to 15 wt .-%.
  • Toilet cleaning blocks according to the invention may contain one or more acids and / or salts thereof to enhance the cleaning performance against lime and urine stone.
  • the acids are preferably produced from renewable raw materials. Suitable acids are therefore in particular organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and mixtures thereof. In addition, however, it is also possible to use the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or else sulfamic acid or mixtures thereof.
  • the acids and / or their salts are particularly preferably selected from the group comprising citric acid, lactic acid, formic acid, their salts and mixtures thereof. They are preferably used in amounts of 0.01 to 10 wt .-%, particularly preferably 0.2 to 5 wt .-%.
  • the composition contains inorganic salts, preferably alkali metal or alkaline earth metal salts, in particular carbonates, sulfates, halides or phosphates, and mixtures thereof. Particular preference is given to using sodium sulfate and / or sodium carbonate.
  • Sodium sulfate may be present in an amount of up to 60 wt .-%, preferably 0.01 to 60 wt .-%, particularly preferably 20 to 60 wt .-%, in particular 35 to 55 wt .-%.
  • Sodium carbonate and further salts may be present in an amount of up to 30% by weight, preferably up to 10% by weight, more preferably up to 5% by weight.
  • alkalis it is also possible for alkalis to be present.
  • Suitable bases in agents according to the invention are preferably those from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide.
  • ammonia and / or alkanolamines having up to 9 C atoms in the molecule preferably the ethanolamines, in particular monoethanolamine.
  • the WC cleaning block therefore contains one or more antimicrobial agents, preferably in an amount of from 0.01 to 1% by weight, preferably 0, 02 to 0.8 wt .-%, in particular 0.05 to 0.5 wt .-%, particularly preferably 0.1 to 0.3 wt .-%, most preferably 0.2 wt .-%.
  • the terms disinfection, sanitation, antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention.
  • antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention
  • Derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores, active chlorine-releasing Compounds and peroxides.
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propahol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2 Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4- Chlorophenyl) -3,12-diimino-2,4,11,13-
  • Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, it is also possible to use antimicrobial-effective essential oils which at the same time ensure scenting of the cleansing agent.
  • particularly preferred antimicrobial agents are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite, sodium dichloroisocyanurate and mixtures thereof.
  • Preservatives may also be included in toilet cleaning blocks according to the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.
  • INCI chelating agents also called sequestrants, are ingredients that are capable of complexing and inactivating metal ions to prevent their detrimental effects on the stability or appearance of the agents, such as clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. The complexation of the ions of heavy metals such as iron or On the other hand, copper retards the oxidative decomposition of the finished agents. In addition, the complexing agents support the cleaning effect.
  • Suitable examples are the following according to INCI complexing agents: Aminotrimethylene Phosphonic Acid, Beta Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane diphosphonates , Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate
  • the toilet cleaning block according to the invention may further contain polymers. These can be used, for example, to reduce calcification and the tendency to re-soiling.
  • Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol.
  • the WC cleaning block according to the invention may contain one or more fragrances and / or one or more dyes ( INCI Colorants).
  • dyes both water-soluble and oil-soluble dye can be used, on the one hand, the compatibility with other ingredients, such as bleaches, is observed and on the other hand, the dye used against the toilet ceramic should not be substantive even after prolonged exposure.
  • the dyes are preferably present in an amount of 0.0001 to 0.1 wt .-%, in particular 0.0005 to 0.05 wt .-%, particularly preferably 0.001 to 0.01 wt .-%, contained.
  • water-soluble and / or water-insoluble builders can be used in the WC cleaning blocks according to the invention.
  • Water-soluble builders are preferred because they tend to be less likely to leave insoluble residues on hard surfaces.
  • Typical builders which may be present in 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 its salts, the carbonates, phosphates and silicates.
  • Water-insoluble builders include the zeolites, which may also be used, as well as mixtures of the aforementioned builders.
  • bleaching agents can be added to the cleaning agent.
  • Suitable bleaching agents include peroxides, peracids and / or perborates, particularly preferred is hydrogen peroxide.
  • Sodium hypochlorite on the other hand, is less suitable for acidic detergents due to the release of toxic chlorine gas vapors, but can be used in alkaline detergents.
  • a bleach activator may be required in addition to the bleaching agent.
  • Suitable corrosion inhibitors are, for example, the following named according to INCI : Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphates, Nitromethanes, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.
  • Suitable regulators are preferably solid long-chain fatty acids, such as stearic acid, but also salts of such fatty acids, fatty acid ethanolamides, such as coconut fatty acid monoethanolamide, or solid polyethylene oligoglycols, such as those having molecular weights between 10,000 and 50,000.
  • a sticking-in reducing agent may be added.
  • dolomite powder or titanium dioxide powder with a fine particle size distribution improves the processing behavior during spheroidization and significantly reduces abrasion or stickiness.
  • the agent may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They can be added to the composition according to the invention in any form established according to the prior art. These include solutions of the enzymes, preferably concentrated as possible, low in water and / or added with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in core-shelled form. Type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • enzyme stabilizers may be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention from damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage.
  • Suitable enzyme stabilizers are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, for example substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example Glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars.
  • benzamidine hydrochloride borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic
  • stabilizers for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the inner mass may have a higher perfume concentration than the outer, to ensure a constant fragrance impression with decreasing ball mass during the service life, or the inner mass contains a different fragrance than the outer.
  • other active ingredients can be incorporated into different layers, which are released depending on the Ab Hughesgrad at different times. Such a layered structure is also possible in the toilet cleaning block according to the invention.
  • the WC cleaning block preferably has a sphericity ⁇ between 0.8 and 1, particularly preferably between 0.85 and 1, very particularly preferably between 0.9 and 1.
  • V p denotes the volume of the body and Ap denotes its surface
  • a uniform rinsing of the toilet cleaning block is effected in such a way that the toilet cleaning block substantially maintains its spherical shape during or after the rinsing operations and a corresponding removal of the toilet cleaning block. It has been found that, in particular, a high sphericity ⁇ of the WC cleaning block at the beginning of the rinsing-water application is decisive for maintaining the spherical shape during and after the rinsing-off operations.
  • the diameter of the spherical toilet block is preferably between 1 mm and 10 cm, preferably between 5 mm and 5 cm, particularly preferably between 1 cm and 3 cm.
  • the toilet cleaning block is placed in a dispenser, which is attached with a holder on the toilet bowl edge.
  • a dispenser which is attached with a holder on the toilet bowl edge.
  • a basket with Spülwasservermaschinelement as they are already known in the art, such as in DE 102008037723 , are described and can accommodate one or more toilet cleaning blocks. These are in the FIGS. 1 to 6 explained in more detail.
  • This can be used accordingly in a method for cleaning and / or scenting and / or disinfecting flushing toilets such that the filled with the toilet cleaning block dispenser is hung in the toilet bowl and dissolved in operating the toilet flushing ingredients of the toilet cleaning block in reach the rinse water and there unfold their cleansing and / or fragrant and / or disinfecting effect.
  • FIG. 1 1 shows a dispenser 1 for a toilet cleaning block 4 with rinse water distribution element 8 arranged above the inlet opening 5 in a side view.
  • the dispensing device 1 consists of a container 3, which has an inlet opening 5 at its head end, through which rinse water can enter the container 3 via the rinsing water distribution element 8.
  • the rinse water which has entered the container 3 dissolves some of the toilet cleaning block 4 stored in the container 3, the rinse water now laden with the corresponding preparation leaving the container 3 via the outlet opening 6 and thus being dispensed into the interior of the toilet bowl.
  • the rinse water distribution element 8 is formed plate-like in the embodiment shown. In addition, however, for example, trough-like, slide-like or ramp-like formations and any combinations thereof are possible.
  • the rinse water distribution element 8 engages in the flushing water flow of the toilet bowl, wherein usually the main flow direction of the flushing water flow-as indicated by the arrow-is directed in the direction of gravity down.
  • the rinse water flow is broken by the rinse water distribution element 8, which acts similarly to a baffle plate, and distributed over the surface of the rinse water distribution element 8.
  • the surface of the rinse water distribution element 8 facing the rinse water flow can have liquid-conducting and / or distributing structures, such as, for example, transversely and / or longitudinally extending grooves, capillaries or lattices.
  • the rinse water distribution element 8 may further comprise an opening through which rinse water may flow into the inlet opening 5 of the container 3.
  • FIG. 1 can be seen, the toilet bowl shown on a holding element 2, through which the toilet bowl on the edge of a toilet bowl by a user can be releasably attached.
  • the holder 2 has a first spring element 9 and a second spring element 10, wherein when installed in the toilet state of the toilet rinser 1, the first spring element 9 has a substantially vertical spring travel and the second spring element 10 has a substantially horizontal travel, creating a improved and more flexible fixation of the toilet bowl 1 to toilets with different pool edge strengths and designs is possible.
  • FIG. 2 An alternative embodiment of a toilet bowl for the toilet cleaning block according to the invention with arranged below the inlet opening Spülwasservermaschinelement shows Fig. 2 ,
  • This dispensing device 1 has a plate-like Spülwasservermaschinelement 8, which extends in the installed state of the dispenser 1 in a Toilettenbeüken directly from below the inlet opening 5 of the container 3 in the direction of the toilet rim.
  • Fig. 3 shows a toilet bowl, in particular from the Fig. 1 and 2 known, with four side by side arranged in series containers 3a-d and a Spülwasservermaschinelement 8 in the plan.
  • the containers 3a-d can store different preparations 4a, 4b, 4c, 4d.
  • Adjacent containers 3a-d are connected to each other by a non-water-conducting connection 13.
  • Fig. 4 is a formed of transparent material dispensing device 1 for toilet cleaning block 4a-d with spherical containers 3a-d and a Spülwasservermaschinelement 8 reproduced in a perspective view.
  • the containers 3a-d are arranged in series next to one another.
  • spherical solid preparations 4a-d are stored, which may be different from each other. Due to the transparent configuration of the containers 3a-d, the user can easily visually detect the consumption status of the preparations 4a-d.
  • the plate-like Spülwasservermaschinelement 8 extending approximately at the height of the longitudinal axis is arranged below the slot-shaped inlet openings 5a-d of the container 3a-d and extends over the entire length of the toilet bowl, which also well from the front view of Fig. 4 known toilet bowl 1 can be seen as Fig. 5 shows.
  • the containers 3a-d and the distribution element 8 are integrally formed, that is, the containers 3a-d are formed from two half-shell-like elements, which are connected to a hinge-like material bridge, in particular in an injection molding process, wherein the Spülwasservermaschinelement 8 is formed on one of the half-shell-like elements , By folding the two half-shell-like elements, the containers 3a-d are then formed, wherein the elements are fixed together in the assembled state by a suitable positive and / or cohesive connection to each other.
  • the one-piece retaining element 2, by which the dispensing device 1 can be fixed on the edge of a toilet bowl, has two diamond-shaped spring elements 9,10, wherein in the toilet installed state of the toilet bowl 1, the first spring element 9 is a substantially vertical travel and the second spring element 10 has a substantially horizontal spring travel. Due to the spring travel provided an improved and more flexible fixation of the toilet bowl 1 to toilets with different pool edge thicknesses and configurations is possible.
  • Fig. 6 is a first, impinging on the spherical container flushing water flow shown in the schematic representation of an arrow A, wherein the width of the arrow A symbolizes the Spülwassermenge and the length of the arrow A, the Spülwasser Ober. If the flushing water flow hits the spherical surface of the container, the impinging flushing water flow is broken, ie a part is deflected and generates a splashing water portion, which is indicated by the arrow A1 and a part is discharged via the surface of the container, symbolized by arrow A2 is.
  • a second rinse water flow B in Fig. 6 shown which has a lower Spülwasser Ober and amount than Spülwasserstrom A, which can be seen at the lower arrow length and width.
  • the spray water content is reduced when hitting a spherical surface, and the proportion of rinse water which is discharged after impacting the spherical container surface increases.
  • the spherical containers 3a, 3b are provided for receiving spherical preparations with a diameter of 25-40mm.
  • the Spippowasservermaschinelement 8 has a depth between 2-20mm, more preferably between 5-15 mm, below depth is the horizontal extent in the suspended state of the Spülwasservermaschinelements 8 in the direction of the Spülwasserbeaufschlagten toilet rim to understand. It is also advantageous to arrange the rinse water distribution element 8 in or above the horizontal, the center-containing cutting plane of the spherical container 3a, 3b.
  • the distance between the upper edges of the Spüliganeinlassö réelleen 5a, 5b of the spherical container 3a, 3b and the Spülwasservermaschinelement 8 is according to a preferred embodiment of the invention between 2 mm and 8 mm.
  • horizontally extending slits are preferable as rinse water inlet openings 5a, 5b, the slits preferably having a height of 1-6mm, preferably 2-4mm, and a width of 5-35mm, preferably 20-25mm.
  • FIG. 7 shows a dispensing device 1 according to the invention with a bow-like holding element 2, which is provided for fastening and fixing of the dispensing device 1 at the edge of a toilet.
  • a receptacle 12 is arranged, which serves to receive the toilet cleaning block 4.
  • the receptacle 12 consists of a plate 16, from which at least one mandrel 15 extends at right angles. On the mandrel 15 a toilet cleaning block 4 is fixed by plugging, the toilet cleaning block 4 rests on the plate 16 at least partially, whereby a sufficiently good fixation of the toilet cleaning block 4 is realized in the receptacle 12. It is also conceivable that a plurality of mandrels for fixing a toilet cleaning block are formed on a plate 16.
  • FIG. 7 shown embodiment of a dispenser and a toilet cleaning block, it is thus possible to fix a dispensing device 1 with the least possible cost of materials while maintaining good aesthetic effect in a toilet bowl. Furthermore, the embodiment shown allows a simple refilling of the dispensing device 1 by a new toilet cleaning block is inserted by simply plugging into the receptacle 12 of the dispensing device 1 after rinsing the cleaning block 4.
  • the dispensing device 1 is configured such that in the installed state of the dispensing device 1, the plate 16 is substantially horizontal and the mandrel 15 is positioned substantially vertically. This prevents that the toilet cleaning block 4, in particular after a few Ab Hughesvorticiann and an associated removal of the toilet cleaning block 4, when exposed to rinse water from the receptacle 12 can slide.
  • the mandrel 15 can take any shape that is suitable to allow a plugging of a toilet cleaning block 4, without the toilet cleaning block 4 thereby mechanically disintegrated.
  • the mandrel 15 may be cylindrical, conical, pyramidal, helical or the like.
  • the mandrel 15, which is not in FIG. 7 shown having barbs that prevent removal of the toilet cleaning block 4 from the receptacle 12 after plugging.
  • Fig. 1 to 6 reproduced toilet bowl is provided in a preferred embodiment with a child-resistant closure to prevent the improper use of the spherical toilet cleaning blocks according to the invention.
  • a further process step is carried out subsequent to one of the steps b) or c), wherein the extruded strand with a lubricant is provided.
  • a permanent offset with the lubricant sponge in the form of an impeller is guided over the extruded strand that the surface is fully or partially, preferably 10 to 40%, applied with lubricant.
  • the addition of the lubricant improves the subsequent spheroidal shaping.
  • Suitable lubricants are, in particular, substances which are used, for example, as surfactants or rinse-off regulators in formulations according to the invention. Particular preference is given to using a lubricant selected from the group comprising dipropylene glycol, paraffins, nonionic surfactants, polyethylene glycols and mixtures thereof, in particular dipropylene glycol.
  • the WC cleaning block receives a spherical shape with a sphericity ⁇ between 0.8 and 1, particularly preferably between 0.85 and 1, very particularly preferably between 0.9 and 1.
  • the cleaning block according to the invention could be extruded and shaped at a maximum of 30 ° C. and moreover showed no swelling during rinsing.
  • the compositions E1 and V1 to V4 are shown in the following table. All Merigenan bin are in wt .-%. E1 V1 V2 V3 V4 C 10-13 -lin.

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Claims (15)

  1. Bloc de nettoyage de WC, contenant un parfum, au moins un tensioactif non ionique ainsi qu'au moins un sulfonate d'alkylbenzène et au moins un sulfonate d'oléfine, caractérisé en ce qu'il contient un alcoxylate d'alcool gras C12 à C22 ayant un degré d'éthoxylation de 12 à 28, et en ce que le bloc peut être formé d'un corps à symétrie de révolution dans une machine de roulage ou une presse.
  2. Bloc de nettoyage de WC selon la revendication 1, caractérisé en ce que le bloc est mis sous la forme d'un corps sphérique.
  3. Bloc de nettoyage de WC selon l'une des revendications 1 et 2, caractérisé en ce qu'il comprend 10 à 70% en poids, de préférence 20 à 65% en poids, en particulier de préférence de 20 à 30% en poids de sulfonate d'alkylbenzène.
  4. Bloc de nettoyage de WC selon l'une des revendications 1 à 3, caractérisé en ce qu'il contient 10 à 30% en poids, de préférence 15 à 30% en poids, plus préférablement 15 à 25% en poids de sulfonate d'oléfine.
  5. Bloc de nettoyage de WC selon la revendication 4, caractérisé en ce que l'alcoxylate d'alcool gras est contenu de préférence dans des quantités allant jusqu'à 20% en poids, plus préférablement de 4 à 12% en poids, en particulier 7 à 9% en poids.
  6. Bloc de nettoyage de WC selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient d'autres agents tensioactifs, de préférence choisis dans le groupe comportant les sulfates d'alcools gras, les monoalcanolamides d'acide gras, les éthers-sulfates d'alcools gras, les sulfonates d'alcanes et leurs mélanges.
  7. Bloc de nettoyage de WC selon l'une des revendications précédentes, caractérisé en ce qu'il contient un ou plusieurs autres constituants, généralement utilisés dans les blocs de nettoyage de WC, de préférence choisis dans le groupe comportant les acides, les bases, les sels, les épaississants, les agents antimicrobiens, les conservateurs, les agents complexants, les colorants, les parfums, les renforçateurs de parfum, les charges, les adjuvants, les agents de blanchiment, les inhibiteurs de corrosion, les régulateurs de lavage, les enzymes, les micro-organismes, les agents éliminant les biofilms, les agents inhibant la calcification, les agents réduisant l'adhérence de saletés et leurs mélanges.
  8. Bloc de nettoyage de WC selon l'une des revendications précédentes, caractérisé en ce que le bloc de nettoyage de WC a une forme sphérique avec une sphéricité Ψ de 0,8 à 1, de manière particulièrement préférée de 0,85 à 1, de manière particulièrement tout préférée de 0,9 à 1.
  9. Système constitué d'au moins un bloc de nettoyage de WC selon l'une des revendications précédentes et d'un distributeur.
  10. Système selon la revendication 9, caractérisé en ce que le distributeur comporte au moins un récipient (3a, 3b, 3c, 3d) destiné à recevoir au moins un bloc de nettoyage de WC (4a, 4b, 4c, 4d) selon l'une des revendications 1 à 8, le récipient (3a, 3b, 3c, 3d) pouvant être positionné au-dessous du bord des WC de telle sorte que l'eau de chasse peut s'écouler par-dessus lors de la chasse, et en ce qu'au moins un orifice d'entrée (5a, 5b, 5c, 5d) et un orifice de sortie (6a, 6b, 6c, 6d) sont formés dans la paroi du récipient (7) à destination de l'eau chassée, et en outre en ce qu'un support (2) est prévu pour fixer le distributeur (1) au bord de la cuvette et un élément de distribution d'eau de chasse (8) est disposé au niveau du distributeur et configuré de telle sorte que l'élément de distribution d'eau de chasse (8) est alimentée en eau de chasse lors de la chasse, et une distribution uniforme de l'eau de chasse est effectuée dans l'orifice d'entrée (5a, 5b, 5c, 5d) du récipient (3a, 3b, 3c, 3d).
  11. Système selon la revendication 9, caractérisé en ce que le distributeur (1) comprend un élément de retenue (2) en forme d'arceau qui peut être fixé au bord des WC et qui comporte, une fois fixé aux WC, une extrémité distale (14) qui est positionnée à l'intérieur des WC, au moins un logement (12) destiné à au moins un bloc de nettoyage de WC (4) selon l'une des revendications 1 à 9 étant prévu à l'extrémité distale (14), le logement (12) étant constitué d'au moins un mandrin (15) et d'au moins une plaque (16), au moins un bloc de nettoyage de WC (4) selon l'une des revendications 1 à 9 étant inséré sur le mandrin (15) et la plaque (16) étant disposée au-dessous du bloc de nettoyage de WC (4) par référence à la direction de la gravité et le bloc de nettoyage de WC (4) reposant sur la plaque (16), l'extrémité distale (14) de l'élément de retenue (2) et le logement (12) destiné à au moins un bloc de nettoyage de WC (4) étant configurés de telle sorte que, une fois l'élément de retenue (2) fixé aux WC, le bloc de nettoyage de WC (4) est alimenté en eau de chasse lors de la chasse.
  12. Procédé de fabrication d'un bloc de nettoyage de WC à symétrie de révolution, qui contient un parfum, un agent tensioactif non ionique, un sulfonate d'alkylbenzène et sulfonate d'oléfine, comprenant les étapes consistant à
    a) mélanger les constituants,
    b) extruder le mélange,
    c) découper la barre extrudée en portions d'une masse définie,
    d) mettre sous la forme d'un corps à symétrie de révolution.
  13. Procédé selon la revendication 12, caractérisé en ce que le bloc de nettoyage de WC a une forme de boule avec une sphéricité Ψ de 0,8 à 1, de manière particulièrement préférée de 0,85 à 1, de manière tout particulièrement préférée de 0,9 à 1.
  14. Procédé selon l'une des revendications 4 à 12 et 13, caractérisé en ce que la mise en forme d) est effectuée dans une machine de roulage de boules ou dans une presse.
  15. Procédé pour nettoyer et/ou parfumer et/ou désinfecter des WC à chasse l'aide d'un système selon l'une des revendications 9 à 11.
EP10721412.4A 2009-05-13 2010-05-07 Bloc wc sphérique, son procédé de fabrication et nacelle de nettoyage de wc équipé de blocs wc sphériques Active EP2430136B1 (fr)

Priority Applications (3)

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EP15164184.2A EP2924099B1 (fr) 2009-05-13 2010-05-07 Blocs wc sphériques, leur procédé de production et chariot de nettoyage de wc doté de blocs de wc sphériques
PL15164184T PL2924099T3 (pl) 2009-05-13 2010-05-07 Kuliste kształtki do WC, sposób ich wytwarzania i koszyczek do czyszczenia WC z kulistymi kształtkami do WC
HRP20170218TT HRP20170218T1 (hr) 2009-05-13 2017-02-10 Sferični blok za čišćenje wc-a, postupak za proizvodnju istog, i nosač koji obuhvaća sferične blokove za čišćenje wc-a

Applications Claiming Priority (2)

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DE102009003088A DE102009003088A1 (de) 2009-05-13 2009-05-13 Kugelförmige WC-Steine, Verfahren zu ihrer Herstellung und WC-Reinigungskörpchen mit kugelförmigen WC-Steinen
PCT/EP2010/056239 WO2010130645A1 (fr) 2009-05-13 2010-05-07 Bloc wc sphérique, son procédé de fabrication et nacelle de nettoyage de wc équipé de blocs wc sphériques

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EP15164184.2A Division EP2924099B1 (fr) 2009-05-13 2010-05-07 Blocs wc sphériques, leur procédé de production et chariot de nettoyage de wc doté de blocs de wc sphériques

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EP2430136B1 true EP2430136B1 (fr) 2017-01-25

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EP15164184.2A Active EP2924099B1 (fr) 2009-05-13 2010-05-07 Blocs wc sphériques, leur procédé de production et chariot de nettoyage de wc doté de blocs de wc sphériques

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US (1) US8987182B2 (fr)
EP (2) EP2430136B1 (fr)
JP (2) JP5785936B2 (fr)
KR (1) KR101736512B1 (fr)
CN (2) CN102421885A (fr)
BR (1) BRPI1012851B1 (fr)
DE (2) DE102009003088A1 (fr)
ES (2) ES2622227T3 (fr)
HR (1) HRP20170218T1 (fr)
IL (1) IL216265A (fr)
MX (2) MX359901B (fr)
PL (2) PL2430136T3 (fr)
PT (1) PT2430136T (fr)
RU (1) RU2534526C2 (fr)
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WO (1) WO2010130645A1 (fr)

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MX359901B (es) 2018-10-16
KR20120029383A (ko) 2012-03-26
KR101736512B1 (ko) 2017-05-16
JP6054469B2 (ja) 2016-12-27
CN106957745A (zh) 2017-07-18
PL2430136T3 (pl) 2017-09-29
BRPI1012851A2 (pt) 2021-06-29
MX2011011997A (es) 2011-12-08
JP2012526876A (ja) 2012-11-01
BRPI1012851B1 (pt) 2023-01-10
RU2534526C2 (ru) 2014-11-27
JP2015178629A (ja) 2015-10-08
EP2924099B1 (fr) 2019-07-03
DE202010018282U1 (de) 2015-05-15
IL216265A0 (en) 2012-01-31
HRP20170218T1 (hr) 2017-04-07
US20120047640A1 (en) 2012-03-01
EP2924099A1 (fr) 2015-09-30
ES2622227T3 (es) 2017-07-06
EP2430136A1 (fr) 2012-03-21
WO2010130645A1 (fr) 2010-11-18
ES2748208T3 (es) 2020-03-13
CN102421885A (zh) 2012-04-18
JP5785936B2 (ja) 2015-09-30
PL2924099T3 (pl) 2019-11-29
DE102009003088A1 (de) 2010-11-18
PT2430136T (pt) 2017-02-14
IL216265A (en) 2016-08-31
US8987182B2 (en) 2015-03-24
UA106613C2 (uk) 2014-09-25
RU2011150485A (ru) 2013-06-20

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