EP2924099B1 - Blocs wc sphériques, leur procédé de production et chariot de nettoyage de wc doté de blocs de wc sphériques - Google Patents

Blocs wc sphériques, leur procédé de production et chariot de nettoyage de wc doté de blocs de wc sphériques Download PDF

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Publication number
EP2924099B1
EP2924099B1 EP15164184.2A EP15164184A EP2924099B1 EP 2924099 B1 EP2924099 B1 EP 2924099B1 EP 15164184 A EP15164184 A EP 15164184A EP 2924099 B1 EP2924099 B1 EP 2924099B1
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EP
European Patent Office
Prior art keywords
toilet
cleaning block
toilet cleaning
oil
acid
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EP15164184.2A
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German (de)
English (en)
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EP2924099A1 (fr
Inventor
Nadine Warkotsch
Brigitte Giesen
Anke KLEMMSTEIN
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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    • 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 and can be formed in a rolling machine or a press to a rotationally symmetric, in particular spherical body, further a process for its preparation 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 has led, for example, to the development of gel-type or liquid scenters, some of which are offered in multi-compartment containers, thus allowing the combination of a cleaning agent which is dispensed upon actuation of the toilet flush with a permanent room fragrance.
  • 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.
  • EP 2 031 047 A1 relates to a solid or powder mixture for releasing CO 2 on contact with liquid water, comprising in each case 10 to 45% by weight of a carbonate salt and a disulfite salt.
  • WC bricks have been described in the prior art and have two different compositions.
  • WO 2007/099313 describes cleaning blocks having two portions, the portions having different densities.
  • EP 0 791 047 81 B1 describes a cleaning agent piece, which consists of at least two differently composed masses, wherein one of the masses of the other masses or at least partially enclosed and the enclosed mass and at least one of the other compositions contain at least one same active ingredient.
  • 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.
  • the invention therefore relates to a toilet cleaning block containing perfume, at least one nonionic surfactant and at least one alkylene sulfonate and at least one Olefinsulfonat that can be formed in a rolling machine or a press to a rotationally symmetrical body, and wherein a fatty alcohol alkoxylate is included, and further the WC cleaning block consists of masses of different composition and one or more of the masses is completely or partially enclosed by the other mass, the WC cleaning block containing 10 to 30% by weight of olefinsulfonate and containing 20 to 65% by weight of alkylbenzenesulfonate.
  • 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, balm oil, mint oil, cinnamon 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. Most fragrances have molecular weights of up to about 200 daltons, while molar masses 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 -Decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl
  • 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 comprises at least one nonionic surfactant 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 in 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. Also useful are ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers.
  • Another important class of 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, with the alcohol particularly preferably branching out to a long-chain fatty alcohol or a mixture of long-chain fatty alcohols or unbranched C 8 - to C 18 -alkyl chains and the degree of oligomerization (DP) of the sugars is between 1 and 10, preferably 1 to 6, in particular 1.1 to 3, more preferably 1.1 to 1.7, for example C 8-10- alkyl-1,5-glucoside (DP of 1.5).
  • 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.
  • 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 - are an anion, in particular a halide ion, 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 usually 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, tack 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.
  • 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.
  • 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 .-%.
  • disinfection, sanitation, antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention. While disinfection in the narrower sense of the medical practice means the killing of - in theory all - infectious germs, sanitation is to be understood as the greatest possible elimination of all - including the saprophytic - normally harmless to humans saprophytic - germs. Here, the extent of disinfection or sanitation depends on the antimicrobial effect of the applied agent, which decreases with decreasing content of antimicrobial agent or increasing dilution of the agent for use.
  • 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-propanol, 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'-methylene-bis (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
  • 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. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays 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 dyes 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 glycols, 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.
  • 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
  • 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 one to during the Duration of use to ensure a constant fragrance impression with decreasing ball mass, 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 A p 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 accordingly be used in a method for cleaning and / or scenting and / or disinfecting flush toilets in such a way, that the filled with the toilet cleaning block dispenser is hung in the toilet bowl and enter the flushing water dissolved ingredients of the toilet cleaning block when pressing the toilet flush and unfold their cleansing and / or fragrant and / or disinfecting effect there.
  • 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 toilet bowl 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, i. 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 integrally 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 rinsing water distribution member 8 has a depth of between 2-20mm, especially preferably between 5-15 mm, wherein the depth is the horizontal extent in the suspended state of the rinse water distribution element 8 in the direction of the Spülwasserbeaufschlagten toilet rim is to be understood. 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 in Is positioned substantially vertically. This prevents that the toilet cleaning block 4, in particular after a few Ab Hughesvor réellen 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 following one of the steps b) or c), in which the extruded strand is provided with a lubricant.
  • 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.
  • compositions E1 and V1 to V4 are shown in the following table. All quantities 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 du parfum, au moins un agent tensioactif non ionique ainsi qu'au moins un sulfonate d'alkylbenzène et au moins un sulfonate d'oléfine, caractérisé en ce que le bloc peut être façonné dans une machine à rouler ou une presse pour former un corps à symétrie de rotation, et en ce qu'un alcoxylate d'alcool gras y est contenu, le bloc de nettoyage de WC étant constitué de masses de composition différente, et l'une de ces masses étant entièrement ou partiellement entourée par l'autre/les autres masse(s), le bloc de nettoyage de WC contenant 10 à 30 % en poids de sulfonate d'oléfine et 20 à 65 % en poids de sulfonate d'alkylbenzène.
  2. Bloc de nettoyage de WC selon la revendication 1, caractérisé en ce que le bloc est façonné pour former un corps sphérique.
  3. Bloc de nettoyage de WC selon l'une des revendications 1 et 2, caractérisé en ce qu'il contient 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 15 à 30 % en poids, de préférence 15 à 25 % en poids de sulfonate d'oléfine.
  5. Bloc de nettoyage de WC selon l'une des revendications 1 à 4, caractérisé en ce que l'agent tensioactif non ionique est de préférence un alcoxylate d'alcool gras.
  6. Bloc de nettoyage de WC selon la revendication 5, caractérisé en ce que l'alcoxylate d'alcool gras est de préférence présent en des quantités allant jusqu'à 20 % en poids, en particulier de 4 à 12 % en poids, de manière particulièrement préférée de 7 à 9 % en poids.
  7. Bloc de nettoyage de WC selon l'une des revendications précédentes, caractérisé en ce qu'il contient d'autres agents tensioactifs, de préférence choisis dans le groupe comprenant les sulfates d'alcools gras, les monoalcanolamides d'acides gras, les sulfates d'éther d'alcool gras, les alcanesulfonates et leurs mélanges.
  8. Bloc de nettoyage de WC selon l'une des revendications précédentes, caractérisé en ce qu'il contient un ou plusieurs autres ingrédients couramment utilisés dans les blocs de nettoyage de WC, de préférence choisis dans le groupe comprenant les acides, les bases, les sels, les épaississants, les agents antimicrobiens, les conservateurs, les agents de chélation, les colorants, les parfums, les booster de parfums, les charges, les adjuvants, les agents de blanchiment, les inhibiteurs de corrosion, les régulateurs d'entraînement, les enzymes, les micro-organismes, les agents pour l'élimination de biofilm, agents permettant d'inhiber la calcification, les agents permettant de diminuer l'adhérence de la saleté, ainsi que leurs mélanges.
  9. 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 comprise entre 0,8 et 1, de manière particulièrement préférée entre 0,85 et 1, de manière tout particulièrement préférée entre 0,9 et 1.
  10. Système comprenant au moins un bloc de nettoyage de WC selon l'une des revendications précédentes, et un dispositif de distribution.
  11. Système selon la revendication 10, caractérisé en ce que le dispositif de distribution comprend au moins un récipient (3a, 3b, 3c, 3d) pour recevoir au moins un bloc de nettoyage de WC (4a, 4b, 4c, 4d) selon l'une des revendications 1 à 9, dans lequel le récipient (3a, 3b, 3c, 3d) peut être positionné sous le rebord de la cuvette de telle sorte que de l'eau de chasse peut s'écouler en excès lorsque la chasse est tirée et qu'au moins une ouverture d'entrée (5a, 5b, 5c, 5d) et une ouverture de sortie (6a, 6b, 6c, 6d) sont formées dans la paroi du récipient (7) pour le passage de l'eau de chasse, dans lequel, en outre un support (2) est prévu pour la fixation du dispositif de distribution (1) au bord de la cuvette, et dans lequel un élément de distribution d'eau de chasse (8) est disposé et configuré sur le dispositif de distribution (1) de telle sorte que l'élément de distribution d'eau de chasse (8) est sollicité par l'eau de chasse pendant la chasse d'eau et que la distribution de l'eau de chasse dans l'ouverture d'entrée (5a, 5b, 5c, 5d) du récipient (3a, 3b, 3c, 3d) est effectuée de manière uniforme.
  12. Système selon la revendication 10, caractérisé en ce que le dispositif de distribution (1) comprend un élément de retenue (2) en forme d'arceau, lequel peut être fixé sur le rebord de la cuvette et, à l'état fixé sur le rebord de la cuvette, comprend une extrémité distale (14) positionnée à l'intérieur de la cuvette, au moins un logement (12) pour 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 formé par au moins une broche (15) et au moins un plateau (16), au moins un bloc de nettoyage de WC (4) selon l'une des revendications 1 à 9 étant fixé sur la broche (15), et le plateau (16) étant disposé sous le bloc de nettoyage de WC (4) dans la direction de la force de gravité, le bloc de nettoyage de WC (4) étant posé sur le plateau (16), l'extrémité distale (14) de l'élément de retenue (2) et le logement (12) pour au moins un bloc de nettoyage de WC (4) étant configurés de telle sorte que le bloc de nettoyage de WC (4) est sollicité par l'eau de chasse lors de l'actionnement de la chasse d'eau lorsque l'élément de retenue (2) est fixé au bord de la cuvette.
  13. Procédé de fabrication d'un bloc de nettoyage de WC à symétrie de rotation selon l'une des revendications 1 à 9, lequel contient du parfum, un tensioactif non ionique, du sulfonate d'alkylbenzène et du sulfonate d'oléfine, comprenant les étapes de
    a) de mélange des ingrédients,
    b) d'extrusion du mélange,
    c) de découpe du boudin extrudé en portions d'une masse définie,
    d) de déformation en corps à symétrie de rotation.
  14. Procédé selon la revendication 13, caractérisé en ce que la déformation d) a lieu dans une machine à rouler à billes ou dans une presse.
  15. Procédé permettant de nettoyer et/ou de parfumer et/ou de désinfecter des toilettes à chasse d'eau à l'aide d'un système selon l'une des revendications 10 à 12.
EP15164184.2A 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 Active EP2924099B1 (fr)

Priority Applications (1)

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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

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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
EP10721412.4A EP2430136B1 (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
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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EP10721412.4A Division-Into EP2430136B1 (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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EP10721412.4A Active EP2430136B1 (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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JP (2) JP5785936B2 (fr)
KR (1) KR101736512B1 (fr)
CN (2) CN106957745B (fr)
BR (1) BRPI1012851B1 (fr)
DE (2) DE102009003088A1 (fr)
ES (2) ES2748208T3 (fr)
HR (1) HRP20170218T1 (fr)
IL (1) IL216265A (fr)
MX (2) MX359901B (fr)
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IL216265A (en) 2016-08-31
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PT2430136T (pt) 2017-02-14
JP2015178629A (ja) 2015-10-08
RU2011150485A (ru) 2013-06-20
RU2534526C2 (ru) 2014-11-27
PL2924099T3 (pl) 2019-11-29
CN102421885A (zh) 2012-04-18
MX359901B (es) 2018-10-16
JP6054469B2 (ja) 2016-12-27
MX2011011997A (es) 2011-12-08
HRP20170218T1 (hr) 2017-04-07
JP2012526876A (ja) 2012-11-01
DE102009003088A1 (de) 2010-11-18
BRPI1012851B1 (pt) 2023-01-10
DE202010018282U1 (de) 2015-05-15
KR20120029383A (ko) 2012-03-26
US20120047640A1 (en) 2012-03-01
KR101736512B1 (ko) 2017-05-16
WO2010130645A1 (fr) 2010-11-18
US8987182B2 (en) 2015-03-24
EP2430136A1 (fr) 2012-03-21
EP2924099A1 (fr) 2015-09-30
BRPI1012851A2 (pt) 2021-06-29
CN106957745B (zh) 2020-04-28
IL216265A0 (en) 2012-01-31
ES2622227T3 (es) 2017-07-06
UA106613C2 (uk) 2014-09-25
ES2748208T3 (es) 2020-03-13
EP2430136B1 (fr) 2017-01-25

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