EP3004474B1 - Device for dispensing an active-substance preparation into a toilet bowl - Google Patents

Description

The invention relates to a multi-chamber device for dispensing active substance preparations into a toilet bowl with a receptacle for the active substance preparation, which is typically arranged under the edge of the toilet bowl and overflows during flushing.

For the automatic cleaning of toilet bowls, it is known to apply active substance preparations in lumpy or substantially solid form ("toilet blocks") in a cage-like receptacle on the inner edge of the toilet bowl. With each flushing process, part of the active ingredient preparation of a toilet block dissolves in the flushing water and is distributed together with the flushing water in the toilet bowl. Such a device is, for example, out of EP2310582 (A1 ) known. In addition, a smaller part of the dissolved active ingredient preparation remains in the residual water in the toilet bowl and also ensures cleaning there. However, the amount of active ingredient preparation that remains in the toilet bowl after flushing is quite small.

The same problem also exists for devices (toilet baskets) for dispensing liquid active substance preparations. Such a device is, for example, out of EP1334239 B1 known.

A major disadvantage of all these toilet baskets is accordingly that the metering of all possibly different active substance preparations present in the receptacle proceeds essentially simultaneously and during the rinsing process. As a result, active ingredient preparations which should have their effect after the start or at least partially after the end of the rinsing process cannot function optimally.

Out US 6,662,380 a device is known which overcomes this disadvantage by the delayed delivery of a dissolved active substance. This device has a complicated structure due to the combination of a liquid and a solid active ingredient.

The object of the invention is therefore to provide a simply constructed device for dispensing active substance preparations into a toilet bowl, the active substance preparations being dispensed into a toilet bowl at the optimal time.

This object is achieved by a device with the features of claim 1. Preferred embodiments are described by the dependent claims.

The device according to the invention for dispensing active substance preparations into a toilet bowl comprises a receptacle to be arranged in the toilet bowl, the receptacle can be attached to the toilet bowl. The receptacle comprises a first chamber and at least a second chamber. The first chamber releases a first active substance preparation into the toilet bowl when flushing water flows over it and the second or further chamber releases a second or further active substance preparation into the toilet bowl when flushing water flows over it. The chambers are designed in such a way that at least the first active substance preparation and the second or further active substance preparation are released into the toilet bowl both at different times from one another and at least one of the active substance preparations with a delay in relation to the flushing process. If more than two chambers are present, the further chambers can again contain the first, second or another active substance preparation which are released into the toilet bowl at different times or preferably at the same time as the corresponding preparations from the first or second chamber. However, they can also contain one or more further active substance preparations, which in turn can be released into the toilet bowl either simultaneously with one of the other preparations or at different times.

For the purposes of this invention, an "active substance preparation" is understood to mean a solid preparation which is dissolved by rinsing water when it is in contact with it and is subsequently used as a solution containing the active substance, ie. H. Mixture of flushing water and active ingredient can be released into the toilet bowl. Such a solution containing the active ingredient can also be created, for example, by the flushing water in the receptacle flowing over a solid toilet cleaning block and then being released into the toilet bowl.

The time offset enables the targeted delivery of the same or different active substance preparations into the toilet bowl at different times. A normal flushing process within a normal toilet bowl has two characteristic points in time, namely the start of flushing and the end of flushing. These times define the time windows: before the rinsing process, during the rinsing process, and after the rinsing process. The first and the second active substance preparations are different. Since different active substance preparations can have different functions, it often makes sense for different active substance preparations to be delivered at different times during the rinsing process in order to optimally fulfill these functions. Delivery optimized in this way saves preparation of active ingredients and achieves the best performance.

The device according to the invention, which does not have an additional, for example electrical, mechanism for the independent release of active substance, can be used at the earliest when the Dispense the active ingredient preparation from the first chamber into the flushing water and thus into the toilet bowl. The rinsing water overflows the first chamber, among other things, and enters the first chamber via an inlet, overflows the first active substance preparation, and flows as an active substance-containing solution enriched with the first active substance preparation via an outlet out towards the toilet bowl. In the same way, the second preparation of active substance reaches the toilet bowl from the second chamber, but the delivery is delayed.

1. i) die Abgabe der mindestens zwei unterschiedlichen Wirkstoffzubereitungen in Bezug auf den Spülvorgang zu mindestens zwei verschiedenen Zeitpunkten einsetzt und/oder
2. ii) die Abgabe der mindestens zwei unterschiedlichen Wirkstoffzubereitungen in Bezug auf den Spülvorgang zu mindestens zwei verschiedenen Zeitpunkten endet.

The first and the second chambers are designed in such a way that, with the same overflow, the first active substance preparation and the second active substance preparation are dispensed into the toilet bowl at different times. In terms of the invention, the delivery of active substance preparation into the toilet bowl at different times means that:

1. i) the delivery of the at least two different active substance preparations in relation to the rinsing process starts at at least two different times and / or
2. ii) the delivery of the at least two different active substance preparations with respect to the rinsing process ends at at least two different times.

For example, the delivery of the second active substance preparation can begin at least 1 s, preferably at least 2 s after the start of the delivery of the first active substance preparation, and / or it takes, for example, at least 1 s, preferably at least 2 s longer than the delivery of the first active substance preparation.

There are different types of toilets, with different flushing ratios and flushing times. The device according to the invention is designed for toilet bowls with a flushing process in which the flushing water overflows at least one point on the inner wall of the toilet bowl. The device according to the invention is therefore suitable, inter alia, for toilet bowls according to standard EN 997 (2003 + A1: 2006) Class 1.

The term "same overflow" in the sense of the invention also presupposes a simultaneous start of overflow. The device preferably comprises a rinsing water distribution element, for example a distribution plate as in EP2310582 is known, which is arranged and configured so that the rinse water distribution element is subjected to rinse water during rinsing and causes a uniform release of the rinse water in all chambers.

The time delay is achieved by a time delay device designed as a siphon. The time delay device is arranged in series within the flushing water flow, which can flow through one of the chambers, in order to influence the flow.

The siphon defines a trigger threshold level and an abort threshold level for rinsing water with active ingredient-containing solution in the receiving container, via which the rinsing water with active ingredient-containing solution can begin or stop flowing through the siphon. The preferred variants for the time delay device are explained in detail below.

According to the invention, at least the second chamber comprises the time delay device designed as a siphon.

In a further embodiment of the invention, the second chamber comprises a time delay device designed as a siphon, and the first chamber a further time delay device which has a different time delay than the time delay device of the second chamber.

In another embodiment of the invention, the second chamber comprises a time delay device, while the first chamber has no time delay device. The first preparation of active ingredient from the first chamber is thus dispensed into the toilet bowl immediately after the start of the overflow of the receptacle from the first chamber. In this case, the time interval between the start of the overflow of the receiving container and the discharge from the first chamber is significantly shorter than 1 s, preferably shorter than 0.2 s. Basically, a chamber in the sense of the invention does not have a time delay device when a defined amount of flushing water can flow out of a chamber essentially as quickly or faster than it flows into the relevant chamber.

According to the invention, the outlet opening (s) of the second chamber have a smaller overall cross-section in relation to the first outlet opening (s) of the first chamber. For example, given the same number of outlet openings in the individual chambers, the individual outlet openings of the first chamber have a larger individual diameter than the outlet openings of the second chamber. Although the first and the second chamber simultaneously absorb rinsing water with the same overflow, the rinsing water with solution containing the active substance flows out of the second chamber more slowly due to the smaller overall cross section of the outlet openings, and thus causes the release of active substance preparation from the second chamber takes a long time. With this variant, a time delay can be brought about in the delivery of the active substance in relation to the actual rinsing process in a very favorable manner.

In a further advantageous embodiment of the invention, the second chamber with a time delay device has fewer outlet openings than the other chambers without a time delay device. If necessary, there is only a single outlet opening in the second chamber. As a result of this smaller number, only a smaller flushing water volume can flow away at the same time, so that a time delay compared to the first chamber with more outlet openings is brought about.

According to the invention, the time delay device is a siphon. It was found that chambers with smaller volumes fill up with rinsing water very quickly during the rinsing process, and leave little adjustment possibility for setting the time delay for the start of the spout. On the other hand, it was found that a siphon can be designed very flexibly, so that the drain can be delayed a few seconds compared to the start of flushing even in smaller chambers. A siphon is also preferred for chambers with a water collection volume of less than or equal to 50 cm ³ , even more preferably less than or equal to 30 cm ³ . In a preferred variant with a siphon, the siphon comprises a pipe and a cover, the cover being attached to the pipe.

By dispensing active substance preparations at different times, targeted dispensing of active substance preparations, in particular different active substance preparations, is possible in the different periods of the rinsing process. This ensures a particularly effective and targeted delivery of individual active ingredients at the best possible time without using a complicated control unit.

In one embodiment of the invention, the first and the second active substance preparation contain ingredients which are incompatible with one another. When present in a preparation at the same time, these could, for example, enter into undesired chemical reactions with one another or lead to a phase separation. However, they can also be different dyes, the mixing of which in a single phase would lead to a changed, undesired color impression. Examples of ingredients that may be incompatible with one another are bleaches and dyes or fragrances, or proteases and other enzymes. Other examples are well known to those skilled in the art. Due to the staggered delivery, both active substance preparations can at least partially develop their effects independently of one another.

In another embodiment of the invention, the first active substance preparation and the second active substance preparation are compatible with one another, but should have their effect at different times, so that they are kept in different chambers of the device. In a preferred further development, the first and the second active substance preparation contain different active substances of the same active substance class, but which are chemically different. For example, different surfactants or different enzymes can be used. Furthermore, the first and the second active substance preparation can contain the same active substances in different concentrations.

In one embodiment of the invention, the second active substance preparation comprises at least one active substance which is supposed to have its effect mainly after a rinsing process. An example of such an active ingredient is a water-soluble dye which colors the rinse water, a blue color being preferred. This dye is not rinsed away even after the rinsing process has ended, but remains in sufficient concentration in the toilet sump, ie in the rest of the rinse water remaining in the toilet bowl, to give it a, preferably blue, color. Further examples of active ingredients which also or mainly have an effect after the rinsing process has ended are fragrances, ingredients which dissolve lime and urine, rinse aid or substances to increase the gloss, Surface treatment agents such as soil repellent agents or agents to combat bad smells, disinfectants or bleaches, foam boosters.

In another embodiment of the invention, one of the active substance preparations comprises an active substance which is supposed to have its effect mainly during a rinsing process. For example, a surfactant for foaming. The rinsing process is used to form foam by mixing surfactant-enriched rinsing water and air. This surfactant should essentially be released into the rinsing water during the rinsing process in order to avoid excessive release of the surfactant active ingredient.

Another example is an active ingredient preparation that is supposed to clean the toilet bowl by chemical-mechanical cleaning. This must be given off during the rinsing process, preferably starting at the beginning of the rinsing process. The flow of the enriched rinse water takes care of the mechanical part of the toilet cleaning.

Perfume

At least one of the active substance preparations preferably contains one or more fragrances. These are in the solid, gel-like or liquid active substance preparation, ie in the toilet block or toilet cleaner, preferably in an amount of 0.01 to 10% by weight, in particular 0.05 to 8% by weight, particularly preferably 0 , 1 to 5 wt .-% contain. D-limonene can be included as a perfume component. In a particularly preferred embodiment, the active substance preparation contains sticky odoriferous substances, in particular essential oils (also referred to as essential oils). For example, pine, citrus, jasmine, patchouly, rose or ylang-ylang oil can be used as such for the purposes of this invention. Also suitable are muscatel sage oil, chamomile oil, lavender oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. However, further adhesive fragrances, such as the higher-boiling or solid fragrances of natural or synthetic origin, or also more volatile fragrances, in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures, are within the scope of the present invention Perfume oil can be used advantageously. It can furthermore be preferred that the agents used in the different chambers contain different fragrances, so that the scent impression changes after the rinsing process is complete. Furthermore, it may also be preferred that the agents used in the different chambers contain the same fragrances, but which are different in their Differentiate concentration so that the scent is perceived in a different intensity after the rinsing process.

Surfactants

At least one of the active substance preparations contains at least one surfactant. This is selected from the group of anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants and mixtures thereof. At least one anionic surfactant is preferably contained.

In the context of the present invention, unless otherwise stated, fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms, most preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The former are preferred for ecological reasons, in particular because of their vegetable basis than based on renewable raw materials, but without restricting the teaching according to the invention to them. In particular, the oxo alcohols or their derivatives obtainable, for example, according to ROELEN's oxo synthesis are also preferably having 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, particularly preferably 9 to 17 carbon atoms, extremely preferably 11 to 15 carbon atoms, for example 9 to 11 , 12 to 15 or 13 to 15 carbon atoms, can be used accordingly.

Solid toilet blocks preferably containing at least one alkylbenzenesulfonate and at least one olefin sulfonate. In addition, further surfactants can be contained, in particular from the group of anionic and / or nonionic surfactants.

In the case of the alkylbenzenesulfonates, preference is given in particular to those having about 12 carbon atoms in the alkyl part, for example linear sodium C10-13-alkylbenzenesulfonate. Preferred olefin sulfonates have a carbon chain length of 14 to 16. The toilet cleaning block preferably contains 10 to 70% by weight, preferably 20 to 65% by weight, particularly preferably 20 to 30% by weight of alkylbenzenesulfonate and preferably 10 to 30% by weight, preferably 15 to 30% by weight. -%, particularly preferably 15 to 25 wt .-% olefin sulfonate.

Aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic can be used as further anionic surfactants in the toilet block Sulfonates such as alkane sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and -di-C ₈ -C ₁₈ alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid carboxylic acid arcosinates, ether carboxylic acid arcosinates (ether carboxylic acid arcosinates), and ether carboxylic acid arcosinates (ether carboxylic acid arcosinates), are also usable within the scope of the present invention as well as α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

Preferred within the scope of the present invention are the fatty alcohol sulfates and / or fatty alcohol ether sulfates, in particular the fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, while fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the sense of the present invention preferably with longer-chain alcohols. As a rule, 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. A further embodiment of the alkoxylation consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Preferred fatty alcohol ether sulfates are the sulfates of low ethoxylated fatty alcohols with 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 can 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 acidity, e.g. Dodecylbenzenesulfonic acid.

Nonionic surfactants

Nonionic surfactants in the context of the invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides and fatty acid polyglycol ethers can also be used. Another important class of nonionic surfactants that can be used according to the invention are the polyol surfactants and here in particular the glycotene surfactants, such as alkyl polyglycosides and fatty acid glucamides.

The alkyl polyglycosides, in particular the alkyl polyglucosides, and especially the fatty alcohol alkoxylates (fatty alcohol polyglycol ethers) are particularly preferred.

Preferred fatty alcohol _{alkoxylates are} unbranched or branched, saturated or unsaturated C _{8-22 alcohols alkoxylated} with ethylene oxide (EO) and / or propylene oxide (PO) with a degree of alkoxylation of up to 30, preferably ethoxylated C _12-22 fatty alcohols with a degree of ethoxylation of less as 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example C _16-18 fatty alcohol ethoxylates with 25 EO.

Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant methods of preparative organic chemistry, which, depending on the type of production, results in a mixture of monoalkylated, oligomeric or polymeric sugars. Preferred alkyl polyglycosides are the alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C ₈ to C ₁₈ alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, is in particular 1.1 to 3, most preferably 1.1 to 1.7, for example C _8-10- alkyl-1,5-glucoside (DP of 1.5).

Fatty alcohol ethoxylates are preferably used in amounts of up to 20% by weight, particularly preferably 4 to 12% by weight, particularly preferably 7 to 9% by weight. In addition, further nonionic surfactants, such as fatty acid monoalkanolamides and / or alkyl polyglycosides, can be present in amounts of up to 10% by weight.

In addition to the previously mentioned types of surfactants, the active substance preparation according to the invention can also contain cationic surfactants and / or amphoteric or zwitterionic 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 with 8 to 25, preferably 10 to 21, carbon atoms and R, which is optionally interrupted by heteroatoms or heteroatom groups ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyldimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -alkylamidopropyldimethylcarboxymethylbetaine.

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 for four identical or different types, in particular two long and two short-chain, alkyl radicals and X ^{- represent} an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Quaternary ammonium compounds with an antimicrobial effect are preferred.

In addition to the previously mentioned components, other ingredients that are usually used in toilet cleaning agents can be included, preferably selected from the group comprising acids, bases, salts, thickeners, antimicrobial agents, preservatives, complexing agents, polymers, dyes, agents for reducing bad odors, perfume boosters , Fillers, builders, bleaches, corrosion inhibitors, rinse regulators, enzymes, microorganisms, active substances for biofilm removal, active substances for inhibiting limescale deposits, active substances for reducing dirt adhesion, active substances for improving processability, active substances for reducing stickiness and mixtures thereof. In total, no more than 60% by weight of further ingredients should be present, preferably 0.01 to 60% by weight, in particular 0.2 to 15% by weight.

Acids

To enhance the cleaning performance against lime and urine scale, at least one of the active substance preparations can contain one or more acids and / or their salts. The acids are preferably produced from renewable raw materials. Suitable acids are therefore in particular organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and mixtures thereof. In addition, however, the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or amidosulfonic acid or mixtures thereof can also be used. 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% by weight, particularly preferably 0.2 to 5% by weight. This active ingredient is particularly suitable for the agent to be used in the chamber with the time delay device, since the lime and urine-dissolving action of the acids should, if possible, continue even after the rinsing process has been completed.

In addition, agents which can be used according to the invention contain, in a preferred embodiment, inorganic salts, preferably alkali metal or alkaline earth metal salts, in particular carbonates, sulfates, halides or phosphates and mixtures thereof. Sodium sulfate and / or sodium carbonate are particularly preferably used. Sodium sulfate can be present in an amount of up to 60% by weight, preferably 0.01 to 60% by weight, particularly preferably 20 to 60% by weight, in particular 35 to 55% by weight. Sodium carbonate and other salts can be contained in an amount of up to 30% by weight, preferably up to 10% by weight, particularly preferably up to 5% by weight.

Bases

Alkali can also be present in agents which can be used according to the invention. Bases from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide, are preferably used. In addition, however, ammonia and / or alkanolamines with up to 9 carbon atoms in the molecule can also be used, preferably the ethanolamines, in particular monoethanolamine.

Antimicrobial agents

Disinfection and sanitation represent a special form of cleaning. In a corresponding particular embodiment of the invention, the agent which can be used according to the invention therefore contains one or more antimicrobial active ingredients, preferably in an amount of 0.01 to 5% by weight, preferably 0 02 to 4% by weight, in particular 0.1 to 3.5% by weight, particularly preferably 0.5 to 3% by weight.

The terms disinfection, sanitation, antimicrobial activity and antimicrobial agent have the usual meaning in the context of the teaching according to the invention. While disinfection in the narrower sense of medical practice means the killing of - theoretically - all infection germs, sanitation is understood to mean the greatest possible elimination of all - including the saprophytic germs that are normally harmless to humans. The extent of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial agent content or increasing dilution of the agent for use.

Suitable according to the invention are, for example, antimicrobial active substances from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and the like 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 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, glycerin, 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 '- (1st , 10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11,13 -tetraazatetradecanediimidamide, antimicrobial quaternary surface-active compounds, guanidines and sodium dichloroisocyanurate (DCI, 1,3-dichloro-5H-1,3,5-triazine-2,4,6-trione sodium salt). Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, antimicrobial essential oils can also be used, which at the same time ensure that the cleaning agent is fragranced. However, particularly preferred antimicrobial agents are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular sodium percarbonate, phthalimidoperoxyhexanoic acid or hydrogen peroxide, alkali metal hypochlorite, trichloroisocyanuric acid, sodium dichloroisocyanurate and mixtures thereof. Sodium dichloroisocyanurate is very particularly preferred.

Preservatives

Preservatives can also be contained in active substance preparations according to the invention. Essentially, the substances mentioned for the antimicrobial active substances can be used as such.

Complexing agent

Complexing agents ( INCI chelating agents), also called sequestering agents, are ingredients which can complex and inactivate metal ions in order to prevent their adverse effects on the stability or the appearance of the agents, for example cloudiness. On the one hand, it is important to complex the calcium and magnesium ions of water hardness, which are incompatible with numerous ingredients. The complexation of the ions of heavy metals such as iron or copper on the other hand delays the oxidative decomposition of the finished agent. The complexing agents also support the cleaning effect.

For example, the following complexing agents designated according to INCI are suitable: 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 Dista, Dipotassium EDTA Dis Diphosphonates, disodium EDTA, disodium pyrophosphates, EDTA, etidronic acid, galactaric acid, gluconic acid, glucuronic acid, HEDTA, hydroxypropyl cyclodextrin, methyl cyclodextrin, pentapotassium triphosphate, pentasodium aminotrimethylene phosphate, pentasodium ethylenediamine, tetras , Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxide, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium Gluconate, Sodium Gluconate -1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA-Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine e, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

Polymers

At least one of the active substance preparations according to the invention can furthermore contain polymers. These can be used, for example, to reduce limescale formation and the tendency to re-soiling (so-called soil repellent polymers).

Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol.

Dyes

The agent which can be used according to the invention can contain one or more dyes ( INCI colorants) as further ingredients. Both water-soluble and oil-soluble dyes can be used as dyes, whereby on the one hand the compatibility with other ingredients, for example bleaching agents, must be taken into account and on the other hand the dye used should not have a substantive effect on the toilet ware even after prolonged exposure. It is preferred if the second active substance preparation comprises a water-soluble dye which colors the rinse water, a blue color being preferred. The rinsing water colored with this dye remains in the toilet sump in sufficient concentration due to the after-running after the actual rinsing process has ended, that is to say in the remaining rinsing water remaining in the toilet bowl to give this, preferably blue, color. The dyes are preferably present in an amount of 0.0001 to 0.1% by weight, in particular 0.0005 to 0.05% by weight, particularly preferably 0.001 to 0.01% by weight.

In addition, active substances for preventing or reducing bad odors, so-called malodor repellents, can be used. These are usually substances that adsorb, complex, oxidize or form inclusion compounds with the volatile substances that produce the bad smell, so that they are odorically inactivated (so-called deodorants), or fragrances that have their own odor mask the unpleasant bad smell and neutralize it in this way (so-called odor improver).

Builder

Water-soluble and / or water-insoluble builders can optionally be used in the agents which can be used according to the invention. Water-soluble builders are preferred because they tend to be less likely to leave insoluble residues on hard surfaces. Common builders which may be present in the context of the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the citric acid and their salts, the carbonates, phosphates and silicates. Water-insoluble builders include the zeolites, which can also be used, as well as mixtures of the abovementioned builder substances.

Bleach

According to the invention, bleaching agents can be added to at least one of the active substance preparations. Suitable bleaching agents include peroxo compounds, in particular peroxides, peracids, percarbonates and / or perborates, particularly preferred are sodium percarbonate, phthalimidoperoxyhexanoic acid or hydrogen peroxide. In contrast, alkali metal hypochlorites such as sodium hypochlorite are less suitable for acidic cleaning agents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents. Trichloroisocyanuric acid and in particular sodium dichloroisocyanurate are also suitable. In addition to the bleach, a bleach activator may also be required.

Corrosion inhibitors

Suitable corrosion inhibitors ( INCI Corrosion Inhibitors) are, for example, the following substances named according to INCI : Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinonium, Hexoxyethylammate, Hexoxyethylammate, Hexoxyethyl Diethylammonium, Hexoxyethylammate, Hexoxyethyl Diethylammonium, Hexoxyethylammate, Hexoxyethyl Diethylammonium, Hexoxyethyl Diethylammonium, Hexoxyethyl Diethylammonium Potassium, Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.

Rinse regulators

The substances referred to as rinse regulators primarily serve to control the consumption of the agents during use in such a way that the intended service life is observed. 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 with molecular weights between 10,000 and 50,000, are preferably suitable as regulators.

Active substances to reduce stickiness

To improve the processability in the manufacture of solid toilet cleaning blocks which can be used according to the invention, in particular those in spherical form, an active ingredient can be added to reduce the stickiness. The addition of dolomite powder or titanium dioxide powder with a fine particle size distribution improves the processing behavior during ball molding and significantly reduces abrasion and stickiness. The results with such active ingredients are better than with other customary measures, for example coating the balls with a lubricant, powdering or coating the form rollers with Teflon.

Enzymes

The agent can also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They can be added to the agent which can be used according to the invention in any form established according to the prior art. This includes solutions of the enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extruding the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

Enzyme stabilizers can furthermore be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage. Suitable enzyme stabilizers, depending on the enzyme used, are particularly suitable: 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 the acids mentioned; 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. Further suitable stabilizers are known from the prior art. Combinations of stabilizers are preferably used, 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.

Multi-layer toilet cleaning blocks

From the prior art, for example EP 791047B1 , it is known to produce essentially solid toilet cleaning blocks from masses of different compositions, one or the masses being completely or partially enclosed by the other mass or masses. For example, the inner mass may have a higher perfume concentration than the outer one, in order to ensure a constant fragrance impression with decreasing ball mass during the period of use, or the inner mass contains a different fragrance than the outer one. Besides other active ingredients can also be incorporated into different layers, which are released at different times depending on the degree of rinsing. Such a layered structure is also possible with the toilet cleaning block that can be used according to the invention.

In one embodiment of the invention, the second active substance preparation comprises a surface treatment agent, preferably a soil repellent active substance.

In a further embodiment of the invention, the second active substance preparation comprises a lime and urine stone-releasing ingredient, preferably one or more acids or salts. This means that they can continue to work even after the rinsing process is complete.

In a further embodiment of the invention, the second active substance preparation comprises a bleaching agent. This is particularly preferred if an active ingredient which is incompatible with bleach is present in the first active ingredient preparation, for example an enzyme, a special fragrance, a color, or other organic or polymeric active ingredients.

In a preferred embodiment of the invention, the second active substance preparation comprises a water-soluble dye for coloring the rinsing water. This is preferably a blue dye which, after the actual flushing process has ended, remains in sufficient concentration in the toilet sump, that is to say in the rest of the flushing water remaining in the toilet bowl, and gives it a blue color. In this case, it is further preferred if other active ingredients incompatible with the dye, such as bleaching agents or other water-soluble dyes, are not present in this active ingredient preparation, but rather are contained in the agent held in the first (or any further chamber that may be present).

In further refinements of the invention, the second active substance preparation comprises fragrances, rinse aids, substances for increasing the gloss, active substances for combating bad odors or foam boosters.

According to the invention, the first and second active substance preparations are present as solids in the receptacle, as any, geometrically shaped toilet blocks (also referred to as toilet stones). The preferred shape of the toilet blocks is rotationally symmetrical, in particular spherical, among other things in order to set a particularly favorable ratio of volume to surface for the toilet block. This is particularly advantageous in a chamber with a time delay device. For example, if the second chamber is one Has time delay device, in particular a siphon, the chamber remains filled with rinse water at a certain level longer. A spherical toilet block therefore has little contact with the flushing water in the lower area and is therefore not unnecessarily dissolved.

In one embodiment of the invention, the receptacle comprises at least one wall that separates the first and the second and possibly further chamber. This ensures that the possibly incompatible active substance preparations located in the at least one first chamber and the at least one second chamber do not come into contact, as a result of which, for example, undesired reactions between the individual active substance preparations or color transfers between the chambers can be avoided.

In a special embodiment of the invention, the second chamber is carried out centrally within the receptacle. For example, the second chamber is enclosed on one side by the first chamber and on the other side by another chamber. Of course, additional chambers can also be formed as required.

It is particularly preferred that the first chamber and the second chamber, which form the receptacle, are coupled to one another, are further preferably formed in one piece.

The holder is held by the holder on the toilet bowl, so that in the position of use with the chambers it lies below the holder. The bracket is preferably designed as a bow-shaped hanging bracket, for example.

In addition, the receptacle is preferably made of plastic, such as PET or PP. It is also preferred that the receptacle has a transparent design in order to also ensure an insight into the chambers filled with active substance preparation. In a further development of the invention, the receptacle is transparent or translucent and has a color, preferably blue.

The first, second and, if present, further chambers are preferably not further subdivided. This is particularly preferred if the chambers are each designed to adapt to the geometry of a toilet block. A very compact design is thus achieved.

• Fig. 1A eine Perspektivansicht auf die Vorrichtung, wobei die Vorrichtung offen und ohne Wirkstoffzubereitungen dargestellt ist;
• Fig. 1B einen Schnitt durch eine erfindungsgemäße Vorrichtung entlang der Schnittebene A-A; aus Figur 1;
• Fig. 2 eine erfindungsgemäße Vorrichtung mit Wirkstoffzubereitungen, wobei die Zeitverzögerungsvorrichtung ein Siphon ist.
• Fig. 3 eine weitere erfindungsgemäße Vorrichtung mit Wirkstoffzubereitungen, wobei die Zeitverzögerungsvorrichtung ein Siphon ist.

The invention is explained in more detail below using the drawings as an example. These examples do not exhaustively describe all possible devices conforming to the invention, which the person skilled in the art can carry out with the aid of the description. It is essential that the chambers are designed in such a way that the first active substance preparation and the second active substance preparation are dispensed into the toilet bowl at different times. The figures show in:

• Fig. 1A a perspective view of the device, the device being shown open and without active substance preparations;
• Figure 1B a section through a device according to the invention along the section plane AA; out Figure 1 ;
• Fig. 2 a device according to the invention with active substance preparations, the time delay device being a siphon.
• Fig. 3 a further device according to the invention with active substance preparations, the time delay device being a siphon.

Fig. 1A is a perspective view of a device 1 not according to the invention because of the missing siphon, the device 1 being shown open and without active substance preparations. Fig.1B shows a section of the same device 1, with toilet blocks comprising the active substance preparations 5 and 6, these do not necessarily have to be rectangular and are preferably spherical. The device 1 is conveniently hung by a hanger 12 on the toilet bowl. However, other known fastening variants are also possible. The device 1 comprises a receptacle with a first chamber 3 and a second chamber 4. The first chamber 3 comprises inlet 7 and outlet openings 9. The outlet openings 9 are designed in such a way that overflowing rinsing water which flows in through the inlet has essentially no time delay can flow out through the outlet openings 9 into the toilet bowl. The second chamber 4 comprises at least one inlet opening 8 and a time delay device 11 with an outlet opening 10. The time delay device 11 is a tube 11 which projects into the second chamber 4. When rinsing water runs into the second chamber 4, it runs to the inner end of the pipe before it can run through the pipe 11. Residual water remaining in the second chamber after the rinsing process evaporates slowly.

The device 1 is indeed within the 1A-B drawn angular, other shapes for the receptacle 2 are also possible. Additional chambers can also be provided as required. The wall 13 is preferably present, it is further preferred that the receptacle 2 has a lid and the wall 13 extends from the bottom to the lid and thus separates the first chamber 3 from the second chamber 4.

Fig. 2 is a perspective view of a device 1 according to the invention. The device 1 is conveniently hung by a hanger 12 on the toilet bowl. Other known fastening variants are alternatively possible. The device 1 comprises a receptacle 2 with a first chamber 3 and a second chamber 4. The first and second chambers are preferably rotationally symmetrical, in particular spherical, and comprise toilet blocks which contain the active substance preparations 5 and 6. These toilet blocks are also preferably rotationally symmetrical, in particular spherical. The first chamber 3 comprises inlet 7 and outlet openings 9. The outlet openings 9 are designed in such a way that overflowing rinsing water which flows in through the inlet openings 7 can flow out through the outlet openings 9 into the toilet bowl substantially without a time delay. The second chamber 4 comprises at least one inlet opening 8 and a time delay device 11 with an outlet opening 10. The time delay device 11 is designed here as a siphon 11 which projects into the second chamber 4. When rinsing water flows into the second chamber, it runs to the trigger level. Then the rinse water begins to flow through the siphon until the breaking threshold level is reached. It is particularly preferred that the siphon is designed such that the second chamber 4 runs essentially empty. Additional chambers can also be provided as required. A wall is preferably present which separates the first chamber 3 from the second chamber 4.

Fig. 3 is a perspective view of a device 1 according to the invention. This device is preferably formed from a transparent plastic, except for the siphon 11 and outlet 10, only the external contour is shown for ease of illustration. The device 1 is preferably attached to the toilet bowl in the manner already described above (attachment not shown). The device 1 comprises a receptacle 2 with a first chamber 3, a second chamber 4, and a further chamber 14. The first, second and further chambers 3, 4, 14 are preferably rotationally symmetrical, in particular spherical, and comprise correspondingly designed toilet blocks , which contain the active substance preparations (not shown in the figure). These toilet blocks are also preferably rotationally symmetrical, in particular spherical. The first chamber 3 comprises inlet 7 and outlet openings 9. The outlet openings 9 are designed such that overflowing rinsing water which flows in through the inlet openings 7 can flow out through the outlet openings 9 into the toilet bowl substantially without any time delay. The second chamber 4 comprises at least one inlet opening 8 and a time delay device 11 with an outlet opening 10. The time delay device 11 is designed here as a siphon 11 which projects into the second chamber 4. When rinsing water flows into the second chamber 4, it runs to the trigger level. Then the rinse water begins to flow through the siphon 11 until the breaking threshold level is reached. It is particularly preferred that the siphon 11 is designed such that the second chamber 4 runs essentially empty. Additional chambers can also be provided as required. Walls 13 are preferably provided which separate the chambers 3, 4, 14 from one another.

Design example:

Solid, water-soluble WC active ingredient preparations (so-called WC cleaning blocks or WC stones) were formulated in accordance with the general formulations shown in the table below. E1 and E2 each comprise two different compositions, one of which is intended to release their active ingredient with a time delay. The quantities are in% by weight of the active ingredient, based on the particular toilet block. E1 E2 blue yellow blue White Lin. Alkyl benzene sulfonate 10-30 10-30 10-30 10-30 α-olefin sulfonate 10-25 10-25 10-25 10-25 Fatty alcohol ethoxylate 5-15 5-15 5-15 1-15 Trisodium citrate dihydrate 0.1-3 0.1-3 0.1-3 0.1-3 Perfume 0.1-8 0.1-8 0.1-8 0.1-8 Water sol. Dye blue 0.5-8 - 0.5-8 - Dye yellow - 0.001-1 - - Titanium dioxide - - - 0.1-1 Sodium dichloroisocyanurate - - - 0.1-5 Sodium lauryl sulfate - - - 1-8 Paraffin oil 0-2 0-2 0-2 0-2 Dipropylene glycol 0-2 0-2 0-2 0-2 water 0-2 0-2 0-2 0-2 Sodium sulfate 20-60 20-60 20-60 20-60

In a device after Fig. 2 the block marked "blue" from E1 or E2 was placed in the second chamber and the block marked "yellow" or "white" was placed in the first chamber. The "blue" block contained a water-soluble blue dye. In E1 the yellow block contained foam-forming surfactants, in E2 the white block also included the bleaching agent sodium isocyanurate. The devices in accordance with E1 and E2 were each hung in a toilet bowl according to standard EN 997 (2003 + A1: 2006) Class 1 with a flush volume of 8-10L. When flushing, it was observed that foam began to form in the toilet bowl at the start of the flushing process and that blue-colored flushing water with active ingredient-containing solution began to flow out of the second chamber 1 s after the start of flushing. At the end of the flushing, the dispensing of flushing water with active ingredient-containing solution from the first chamber also ceased, while the dispensing of flushing water with active ingredient-containing solution from the second chamber continued for about 4-6 seconds, turning the residual water in the toilet bowl blue.

Claims (9)

1. A device (1) for dispensing active ingredient preparations (5, 6) into a toilet bowl, comprising a receptacle (2) to be arranged in the toilet bowl, the receptacle (2) being attachable to the toilet bowl, the receptacle (2) comprising at least a first chamber (3) having at least one outlet opening and a second chamber (4) having at least one outlet opening, the first chamber comprising a first active ingredient preparation and the second chamber comprising a second active ingredient preparation, the first chamber (3) dispensing the first active ingredient preparation (5) as an active ingredient-containing solution into the toilet bowl when flushing water flows over and dissolves the active ingredient preparation, and the second chamber (4) dispensing the second active ingredient preparation (6) as an active ingredient-containing solution into the toilet bowl when flushing water flows over and dissolves the active ingredient preparation, at least the second chamber (4) comprising a time delay device (11) in order to dispense the second active ingredient preparation (6) into the toilet bowl at a time delay in comparison to the flushing process, and the chambers (3, 4) being designed such that the first active ingredient preparation (5) and the second active ingredient preparation (6) are each dispensed as an active ingredient-containing solution into the toilet bowl at a time offset from one another when they are equally flowed over, by the at least one outlet opening of the chamber (4) having the time delay device (11) having a smaller overall cross-section compared to the outlet opening(s) of the other chamber (3) without the time delay device (11), characterized in that the first and the second active ingredient preparation (5, 6) are each present as a solid in the receptacle (2), and in that the time delay device (11) is a siphon.
2. The device according to claim 1, characterized in that the receptacle (2) comprises a wall (13) which separates the first chamber (3) from the second chamber (4).
3. The device according to one of the preceding claims, characterized in that the second chamber (4) is arranged centrally in the receptacle (2).
4. The device according to one of the preceding claims, characterized in that the first chamber (3), the second chamber (4) and, if present, further chambers (14) are coupled to one another.
5. The device according to one of the preceding claims, characterized in that the second active ingredient preparation (6) comprises an active ingredient which mainly and/or additionally manifests its effect after a flushing process and is metered.
6. The device according to one of the preceding claims, characterized in that the second active ingredient preparation (6) comprises an active ingredient which mainly manifests its effect during a flushing process.
7. The device according to one of the preceding claims, characterized in that the second active ingredient preparation (5) comprises a surface treatment agent, preferably a soil-repellent active ingredient.
8. The device according to one of the preceding claims, characterized in that the second active ingredient preparation (6) comprises a bleaching agent or an antimicrobial active ingredient.
9. The device according to one of the preceding claims, characterized in that the second active ingredient preparation (6) comprises a water-soluble dye.

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