EP2638137B1 - Blocs wc sphériques à base d'agents tensioactifs anioniques - Google Patents

Blocs wc sphériques à base d'agents tensioactifs anioniques Download PDF

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Publication number
EP2638137B1
EP2638137B1 EP11787809.0A EP11787809A EP2638137B1 EP 2638137 B1 EP2638137 B1 EP 2638137B1 EP 11787809 A EP11787809 A EP 11787809A EP 2638137 B1 EP2638137 B1 EP 2638137B1
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EP
European Patent Office
Prior art keywords
cleaning block
toilet cleaning
oil
block according
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP11787809.0A
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German (de)
English (en)
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EP2638137A1 (fr
Inventor
Marc-Steffen Schiedel
Brigitte Giesen
Anke Ernst
Christian Reichert
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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Priority to PL11787809T priority Critical patent/PL2638137T3/pl
Publication of EP2638137A1 publication Critical patent/EP2638137A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0056—Lavatory cleansing blocks
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • E03D9/005—Devices adding disinfecting or deodorising agents to the bowl
    • 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
    • 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 alkylbenzenesulfonate and at least one olefinsulfonate and perfume , characterized in that the block contains one or more antimicrobial agents and not more than 2.5 wt .-% of nonionic surfactants and in a rolling machine or is formed of a press to a rotationally symmetrical, especially spherical body, and a system of at least one such a toilet cleaning block, and a delivery device. Furthermore, a method for its production is disclosed.
  • 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.
  • 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.
  • Chlorine carriers are suitable as disinfectants for solid WC bricks, but they are not stable in every formulation. So is in the off DE 102009003088 known composition containing a perfume, at least one nonionic surfactant and at least one alkylbenzenesulfonate and at least one olefinsulfonate, with additional use of a chlorine-containing disinfectant such as Dichloriscyanurat already short After production, a markedly reduced chlorine content is recorded, and after a relatively short period of use the chlorine content is only detectable in traces.
  • a chlorine-containing disinfectant such as Dichloriscyanurat
  • a formulation which contains perfume, at least one alkylbenzenesulfonate and at least one olefinsulfonate and does not contain more than 2.5% by weight of nonionic surfactants permits the stable incorporation of chlorine-containing antimicrobial agents.
  • 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 alkylbenzenesulfonate and at least one olefinsulfonate, characterized in that the block contains one or more antimicrobial agents and not more than 2.5 wt .-% of nonionic surfactants and in a roll machine or a press is 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.
  • oxo alcohols or their derivatives having preferably 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, 12 to 15 or 13 to 15 carbon atoms, respectively used.
  • 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. 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
  • Fragrance mixtures are used 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 formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde,
  • 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 toilet cleaning block according to the invention contains at least one alkylbenzenesulfonate and at least one olefinsulfonate.
  • other surfactants in particular anionic 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.
  • 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 WC cleaning block according to the invention contains at least one fatty alcohol sulfate in an amount of up to 20 wt .-%, preferably 4 to 12 wt .-%, particularly preferably 7 to 10 wt .-%.
  • 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.
  • nonionic surfactant in the context of this invention are 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 suitable are block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers.
  • nonionic surfactants which can be used according to the invention are the amine oxides and the sugar surfactants, in particular the alkyl polyglucosides.
  • the WC cleaning block according to the invention contains not more than 2.5% by weight of nonionic surfactants, advantageously those in particulate form. This is particularly important in the formulation of toilet cleaning blocks with chlorine-containing disinfectants, as these two components can react with each other.
  • the WC cleaning block according to the invention is free of nonionic surfactants.
  • 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. Preference is given to quaternary ammonium compounds having an antimicrobial effect. In a particularly preferred embodiment, however, the WC cleaning block according to the invention is free of cationic surfactants.
  • a special form of cleaning provide disinfection and sanitation.
  • Let D contains toilet cleaning block of the present invention, one or more antimicrobial active ingredients, preferably in an amount of up to 40 wt .-%, preferably 0.01 to 25 parts by weight %, in particular 0.1 to 5 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 strict sense of the medical practice means the killing of - in theory all - infectious germs, under sanitation the greatest possible elimination of all - including the for the People usually harmless saprophytic - to understand 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 agents Compounds and peroxides.
  • Preferred antimicrobial agents are preferably selected from the group comprising 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 '.
  • Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group.
  • antimicrobially effective essential oils can be used, which at the same time provide for a scenting of the cleaning agent.
  • particularly preferred antimicrobial active ingredients are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular sodium percarbonate or phthalimidoperoxyhexanoic acid, alkali metal hypochlorite, trichloroisocyanuric acid, sodium dichloroisocyanurate and mixtures thereof.
  • the WC cleaning block according to the invention very particularly preferably contains sodium dichloroisocyanurate.
  • the WC cleaning block according to the invention may comprise further ingredients usually used in toilet cleaning blocks, preferably selected from the group comprising acids, bases, salts, thickeners, preservatives, complexing agents, polymers, dyes, fragrances, perfume boosters, fillers, Builders, bleaching agents, corrosion inhibitors, Ab Hughesregulatoren, enzymes, microorganisms, agents for biofilm removal, active ingredients for the inhibition of calcification, active ingredients for Reduction of soil adhesion, processability enhancing 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 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 amidosulfonic acid.
  • the acids and / or their salts are particularly preferably selected from the group comprising citric acid, lactic acid, sulfamic 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 .-%. In a very particularly preferred embodiment, however, the WC cleaning block according to the invention is free of acids.
  • 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.
  • 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, more preferably sodium percarbonate or phthalimidoperoxyhexanoic acid.
  • chlorine-containing bleaching agents such as trichloroisocyanuric acid or sodium dichloroisocyanurate, are less suitable for acid-formulated cleaning agents due to the release of toxic chlorine gas vapors, but they can be used in alkaline cleaning agents. Under certain circumstances, a bleach activator may be required in addition to the bleaching agent.
  • Suitable corrosion inhibitors are, for example, the following named according to INCI substances: cyclohexylamine, diammonium phosphates, dilithium oxalates, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphate, Nitromethane, 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.
  • active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes
  • Such capsules are known per se Methods, for example, by shaking or rolling granulation or applied 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 ParFum concentration than the outer, in order 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 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.
  • 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 formability of the mass and thus the possibility for optimal rounding can be adjusted by the addition of a small amount of liquid.
  • water, dipropylene glycol or paraffin in an amount of 0.1 to 1 wt .-% can be used as liquids.
  • 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.
  • one or more open plates on which one or more WC cleaning blocks are fixed, are used.
  • inventive toilet cleaning block and dispensing device form a system. 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.
  • Appropriate systems are in DE 102009003088 described.
  • 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.
  • a sponge for strand lubrication for example, simple dripping or spraying on, also dip wheels, plunge baths for belts or strands, etc. It can also be combined with different methods, such as diving a wheel through a lubricant bath and then rolling on the strand with the dripping.
  • the extruded strand and the rollers can be provided with the lubricant.
  • 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.
  • Three WC cleaning blocks according to the invention with formulations E1 to E4 and one comparative formulation V1 were prepared.
  • the compositions are shown in the table below, all amounts in wt .-% of the active ingredient.
  • E1 E2 E3 E4 V1 C 10-13 -lin.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Detergent Compositions (AREA)

Claims (12)

  1. Bloc de nettoyage de toilettes contenant un parfum, au moins un sulfonate de benzène d'alkyle et au moins un sulfonate d'oléfine, caractérisé en ce que le bloc contient un ou plusieurs agents antimicrobiens, ainsi que pas plus de 2,5% en poids de tensio-actifs non ioniques et est mise en forme dans une machine à rouler ou une presse pour obtenir un corps sphérique.
  2. Bloc de nettoyage de toilettes selon à la revendication 1, caractérisé en ce qu'il contient de 10 à 70% en poids, de préférence de 20 à 65% en poids, de manière particulièrement préférée de 20 à 30% en poids, de sulfonate de benzène d'alkyle.
  3. Bloc de nettoyage de toilettes selon l'une des revendications 1 et 2, caractérisé en ce qu'il contient de 10 à 30%, de préférence de 15 à 30% en poids, de manière particulièrement préférée de 15 à 25% en poids, de sulfonate d'oléfine.
  4. Bloc de nettoyage de toilettes selon l'une des revendications 1 à 3, caractérisé en ce qu'il contient au moins un autre tensio-actif anionique.
  5. Bloc de nettoyage de toilettes selon la revendication 4, caractérisé en ce que l'au moins un tensio-actif anionique est de préférence un sulfate d'alcool gras et de préférence dans des quantités allant jusqu'à 20% en poids, de manière particulièrement préférée de 4 à 12% en poids, en particulier de 7 à 10% en poids.
  6. Bloc de nettoyage de toilettes selon l'une des revendications précédentes, caractérisé en ce qu'il est exempt de tensioactifs non ioniques.
  7. Bloc de nettoyage de toilettes selon l'une des revendications précédentes, caractérisé en ce qu'il contient d'autres tensioactifs, de préférence choisi dans le groupe comportant des sulfates d'éthers d'alcools gras, des sulfonates d'alcane, et leurs mélanges.
  8. Bloc de nettoyage de toilettes selon l'une des revendications précédentes, caractérisé en ce que le ou les agents antimicrobiens sont de préférence choisis dans le groupe comprenant l'acide salicylique, les tensioactifs quaternaires, en particulier le chlorure de benzalkonium, des composés peroxyde, en particulier le percarbonate de sodium ou l'acide phthalimidoperoxyhexanoïque, un hypochlorite de métal alcalin, le dichloroisocyanurate de sodium et leurs mélanges, le dichloroisocyanurate de sodium étant tout particulièrement préféré.
  9. Bloc de nettoyage de toilettes selon l'une des revendications précédentes, caractérisé en ce qu'il contient un ou plusieurs autres ingrédients habituellement utilisés dans les blocs de nettoyage de toilettes, de préférence choisis dans le groupe constitué par des acides, des bases, des sels, des épaississants, des conservateurs, des complexants, des colorants, des parfums , les renforçateurs de parfum, des charges, des adjuvants, des agents de blanchiment, des inhibiteurs de corrosion, des régulateurs de lavage, des enzymes, des micro-organismes, des agents d'élimination de biofilm, des agents d'inhibition de calcification, des agents de réduction d'adhérence de saleté et leurs mélanges.
  10. Bloc de nettoyage de toilettes selon l'une des revendications précédentes, caractérisé en ce que le bloc de nettoyage de toilettes a une forme sphérique avec une sphéricité ψ comprise entre 0,8 et 1, de manière particulièrement préférée entre 0,85 et 1, de préférence entre 0,9 et 1.
  11. Système constitué d'au moins un bloc de nettoyage de toilettes selon l'une des revendications précédentes et d'un dispositif de distribution.
  12. Procédé pour nettoyer et/ou parfumer et/ou désinfecter des toilettes à chasse d'eau à l'aide d'un système selon la revendication 11.
EP11787809.0A 2010-11-12 2011-11-11 Blocs wc sphériques à base d'agents tensioactifs anioniques Active EP2638137B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL11787809T PL2638137T3 (pl) 2010-11-12 2011-11-11 Kuliste kostki do WC na bazie anionowych środków powierzchniowo czynnych

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010043848A DE102010043848A1 (de) 2010-11-12 2010-11-12 Kugelförmige WC-Steine auf Aniontensidbasis
PCT/EP2011/069965 WO2012062914A1 (fr) 2010-11-12 2011-11-11 Blocs wc sphériques à base d'agents tensioactifs anioniques

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EP2638137A1 EP2638137A1 (fr) 2013-09-18
EP2638137B1 true EP2638137B1 (fr) 2017-08-23

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JP (1) JP5934715B2 (fr)
KR (1) KR20130119446A (fr)
CN (1) CN103210072B (fr)
AU (1) AU2011327998B2 (fr)
BR (1) BR112013011456A2 (fr)
CA (1) CA2817413C (fr)
CR (1) CR20130215A (fr)
DE (1) DE102010043848A1 (fr)
GE (1) GEP20176613B (fr)
GT (1) GT201300120A (fr)
HK (1) HK1187362A1 (fr)
HU (1) HUE035591T2 (fr)
IL (1) IL226254A0 (fr)
MX (1) MX2013005308A (fr)
MY (1) MY161254A (fr)
NZ (1) NZ611639A (fr)
PL (1) PL2638137T3 (fr)
RU (1) RU2013126792A (fr)
SG (1) SG190192A1 (fr)
WO (1) WO2012062914A1 (fr)
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD841120S1 (en) 2017-01-31 2019-02-19 S. C. Johnson & Son, Inc. Toilet rim-block
USD850578S1 (en) 2017-01-31 2019-06-04 S. C. Johnson & Son, Inc. Toilet rimblock
USD912761S1 (en) 2019-06-07 2021-03-09 S. C. Johnson & Son, Inc. Toilet rim-block
USD914131S1 (en) 2019-06-07 2021-03-23 S. C. Johnson & Son, Inc. Toilet rim-block holder
USD923139S1 (en) 2019-06-07 2021-06-22 S. C. Johnson & Son, Inc. Set of toilet rim-blocks
US11312922B2 (en) 2019-04-12 2022-04-26 Ecolab Usa Inc. Antimicrobial multi-purpose cleaner comprising a sulfonic acid-containing surfactant and methods of making and using the same
EP4011406A1 (fr) 2020-12-09 2022-06-15 Henkel AG & Co. KGaA Processus de moulage continu des blocs pour toilettes sphériques

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012106742A1 (de) 2012-07-25 2014-01-30 Geting Solutions Gmbh Stückförmiges Mittel zur Applikation auf einem Sanitärgegenstand
US20140075663A1 (en) * 2012-09-14 2014-03-20 Impact Products, Llc Urinal screen
RU2017111624A (ru) 2014-09-08 2018-10-10 Эс.Си.ДЖОНСОН ЭНД САН, ИНК. Ободковые блоки для унитаза и чистящие изделия, а также способы выполнения таких блоков и изделий
CA2978555A1 (fr) 2015-03-05 2016-09-09 Crossford International, Llc Systemes et procedes de nettoyage de tube a l'aide de comprimes
USD752198S1 (en) 2015-03-18 2016-03-22 S.C. Johnson & Son, Inc. Toilet rim block holder
USD752733S1 (en) 2015-03-18 2016-03-29 S.C. Johnson & Son, Inc. Toilet rim block holder
DE102015215135A1 (de) * 2015-08-07 2017-02-09 Henkel Ag & Co. Kgaa WC-Stein und WC-Körbchen
USD791911S1 (en) * 2015-09-15 2017-07-11 Tomil S.R.O. Toilet rim blocks
EP3168284A1 (fr) * 2015-11-13 2017-05-17 Unilever N.V. Bloc de nettoyage de toilette mis en forme
USD784491S1 (en) 2016-05-17 2017-04-18 S. C. Johnson & Son, Inc. Toilet rim block
USD789485S1 (en) 2016-05-17 2017-06-13 S. C. Johnson & Son, Inc. Toilet rim block holder
US10669705B2 (en) 2016-07-05 2020-06-02 Willert Home Products, Inc. Toilet bowl treatment apparatus and method of making same
US10493177B2 (en) 2017-01-12 2019-12-03 Impact Products, Llc Solid state fragrancing
WO2018145165A1 (fr) * 2017-02-10 2018-08-16 Zhongshan Newtour Housechem Co. Ltd Bloc de nettoyage de toilettes
CN107503417A (zh) * 2017-08-17 2017-12-22 福州大学厦门工艺美术学院 一种模块化移动式坐便器
CN109701369B (zh) * 2018-12-29 2021-04-16 陈红 一种利用柑橘皮渣制备的便池除臭丸
DE102019211571A1 (de) * 2019-08-01 2021-02-04 Henkel Ag & Co. Kgaa Mehrphasiger Reinigungsmittelformkörper
DE102019211566A1 (de) * 2019-08-01 2021-02-04 Henkel Ag & Co. Kgaa Reinigungsmittelformkörper
CN114585715A (zh) * 2019-11-19 2022-06-03 西姆莱斯有限公司 家庭护理产品或制剂
US11499124B2 (en) 2020-03-13 2022-11-15 YFY Consumer Products, Co. Solid granules used for cleaning agents
US11767495B2 (en) 2020-03-13 2023-09-26 YFY Consumer Products, Co. Systems and methods for manufacturing solid granules
KR102240245B1 (ko) * 2021-01-07 2021-04-13 김종덕 소변 냄새 방지 기능을 강화한 반려동물용 수세식 배변판
WO2023180053A1 (fr) 2022-03-22 2023-09-28 Unilever Ip Holdings B.V. Composition solide de nettoyage de surfaces dures

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE756790A (fr) * 1969-10-01 1971-03-29 Henkel & Cie Gmbh Detergent faconne a base de surfactifs synthetiques
JPS6369146U (fr) * 1986-10-24 1988-05-10
GB9013539D0 (en) * 1990-06-18 1990-08-08 Unilever Plc Lavatory cleansing block
DE4439677A1 (de) 1994-11-07 1996-05-09 Henkel Kgaa Reinigungsmittelstück für Spültoiletten
US6184192B1 (en) * 1997-04-24 2001-02-06 S. C. Johnson & Son, Inc. Chlorinated in-tank toilet cleansing block
GB2333778B (en) * 1998-01-29 2000-02-09 Reckitt & Colman France A lavatory block
MXPA04004515A (es) * 2001-11-13 2004-09-10 Reckitt Benckiser Inc Mejoras referentes a articulos para limpieza de inodoro.
CN1234624C (zh) * 2002-06-04 2006-01-04 陈平 一种芳香除臭滤洁块及其制造方法
DE102004020400A1 (de) * 2004-04-23 2005-11-17 Henkel Kgaa Parfümierte Feststoffe
DE102008037723A1 (de) 2008-08-14 2010-02-25 Henkel Ag & Co. Kgaa WC-Körbchen mit Spülwasserverteilelement
DE102009003088A1 (de) 2009-05-13 2010-11-18 Henkel Ag & Co. Kgaa Kugelförmige WC-Steine, Verfahren zu ihrer Herstellung und WC-Reinigungskörpchen mit kugelförmigen WC-Steinen
FR2957085B1 (fr) * 2010-03-05 2012-06-01 Eurvest Bloc detergent pour toilettes, dispositif de nettoyage de toilettes comportant un bloc detergent et procede de fabrication d'un bloc detergent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD841120S1 (en) 2017-01-31 2019-02-19 S. C. Johnson & Son, Inc. Toilet rim-block
USD850578S1 (en) 2017-01-31 2019-06-04 S. C. Johnson & Son, Inc. Toilet rimblock
US11312922B2 (en) 2019-04-12 2022-04-26 Ecolab Usa Inc. Antimicrobial multi-purpose cleaner comprising a sulfonic acid-containing surfactant and methods of making and using the same
USD912761S1 (en) 2019-06-07 2021-03-09 S. C. Johnson & Son, Inc. Toilet rim-block
USD914131S1 (en) 2019-06-07 2021-03-23 S. C. Johnson & Son, Inc. Toilet rim-block holder
USD923139S1 (en) 2019-06-07 2021-06-22 S. C. Johnson & Son, Inc. Set of toilet rim-blocks
EP4011406A1 (fr) 2020-12-09 2022-06-15 Henkel AG & Co. KGaA Processus de moulage continu des blocs pour toilettes sphériques
WO2022122869A1 (fr) 2020-12-09 2022-06-16 Henkel Ag & Co. Kgaa Procédé continu de mise en forme de blocs de toilettes sphériques

Also Published As

Publication number Publication date
NZ611639A (en) 2015-05-29
SG190192A1 (en) 2013-06-28
CA2817413A1 (fr) 2012-05-18
KR20130119446A (ko) 2013-10-31
GT201300120A (es) 2015-07-06
IL226254A0 (en) 2013-07-31
RU2013126792A (ru) 2014-12-20
MX2013005308A (es) 2013-06-03
ZA201304285B (en) 2014-03-26
BR112013011456A2 (pt) 2016-08-09
AU2011327998B2 (en) 2014-11-27
EP2638137A1 (fr) 2013-09-18
CN103210072A (zh) 2013-07-17
JP5934715B2 (ja) 2016-06-15
DE102010043848A1 (de) 2012-05-16
PL2638137T3 (pl) 2018-01-31
CN103210072B (zh) 2015-11-25
CR20130215A (es) 2013-06-28
HUE035591T2 (en) 2018-05-28
HK1187362A1 (zh) 2014-04-04
GEP20176613B (en) 2017-02-10
JP2014501801A (ja) 2014-01-23
AU2011327998A1 (en) 2013-07-04
WO2012062914A1 (fr) 2012-05-18
US20130239313A1 (en) 2013-09-19
CA2817413C (fr) 2018-09-25
MY161254A (en) 2017-04-14

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