Delayed release of an active ingredient preparation comprising bacterial spores

Abstract

The invention relates to a device (1) for releasing water-soluble active ingredient preparations (5, 6) into a toilet bowl, comprising a receptacle (2) to be arranged in the toilet bowl, wherein the receptacle (2) can be secured to the toilet bowl, wherein the receptacle (2) comprises at least one first chamber (3) and a second chamber (4), wherein the first chamber (3) releases a first active ingredient preparation (5) into the toilet bowl when flushing water flows over it, and the second chamber (4) releases a second active ingredient preparation (6) into the toilet bowl when flushing water flows over it, and wherein the chambers (3, 4) are designed such that the first active ingredient preparation (5) and the second active ingredient preparation (6) are released into the toilet bowl at different times from one another, characterised in that either the first active ingredient preparation (5) and / or the second active ingredient preparation (6) contains bacterial spores.

Description

[0001] Delayed release of an active ingredient preparation containing bacterial spores

[0002] The invention relates to a multi-chamber device for dispensing active ingredient preparations into a toilet bowl, with a receiving container for the active ingredient preparation containing bacterial spores, typically arranged below the rim of the toilet bowl and overflowing during flushing.

[0003] Bacterial spores are a special, resilient form of bacteria that allows them to survive under extreme environmental conditions. They are produced by certain types of bacteria, such as Clostridium. These spores are resistant to heat, desiccation, radiation, and many chemical disinfectants. Toilet blocks that are placed under the rim of the toilet bowl are a popular alternative to those placed inside the cistern.

[0004] These products, often called toilet bowl fresheners or toilet baskets, offer several advantages: Because they are placed directly in the toilet bowl, they release cleaning agents with each flush, targeting the inner walls of the bowl. This helps to effectively reduce limescale and dirt. Most of these products are integrated into a plastic basket or holder that is simply hung under the rim of the toilet bowl. This makes them quick and easy to use. However, the unpleasant odors that develop in the toilet bowl are often only partially masked by the use of fragrances.

[0005] Therefore, there remains a need to provide improved solutions for toilet blocks. The task was thus to find a composition that is improved compared to conventional toilet blocks known from the state of the art.

[0006] This problem is solved by a device having the features of claim 1. An active ingredient preparation comprising bacterial spores is used. Preferred embodiments are described by the dependent claims.

[0007] The use of spores in cleaning agents is well-known and generally refers to the use of probiotic cleaners containing beneficial bacterial spores. These cleaning agents utilize the natural abilities of certain microorganisms to break down organic soils and eliminate unpleasant odors. For example, WO 2017 / 157772A1 describes various applications for a variety of bacterial spores in cleaning agents. 2024P00102WC

[0008] However, when used in conventional baskets, e.g. with a single chamber but also in multi-chamber systems, it was surprisingly found that the effectiveness of the spores was reduced.

[0009] Without being tied to any specific theory, the process of sporulation could be responsible. This often occurs when bacteria are exposed to unfavorable conditions, such as nutrient deficiency or extreme temperatures. In this form, the bacteria can remain dormant for extended periods.

[0010] Such conditions could also exist in solid toilet blocks. As soon as conditions are favorable again, the spores can germinate and develop into active, vegetative cells.

[0011] The device according to the invention aims to achieve precisely this. It comprises a receiving container to be positioned in the toilet bowl, which can be attached to the toilet bowl. The receiving container comprises a first chamber and at least one second chamber. Upon the flow of flushing water, the first chamber releases a first active ingredient preparation into the toilet bowl, and the second or further chamber releases a second or further active ingredient preparation into the toilet bowl upon the flow of flushing water. The chambers are designed such that at least the first active ingredient preparation and the second or further active ingredient preparation are released into the toilet bowl both at different times and with a delay relative to the flushing process. At least one of the compositions comprises bacterial spores. The staggered release allows the spores to be sufficiently activated.

[0012] If more than two chambers are present, the additional chambers can contain the first, second, or a further active ingredient preparation, which are dispensed into the toilet bowl at different times, or preferably at the same time, as the corresponding preparations from the first or second chamber. They can also contain one or more further active ingredient preparations, which in turn can be dispensed into the toilet bowl either simultaneously with one of the other preparations or at a later time.

[0013] For the purposes of this invention, an "active ingredient preparation" is understood to be a liquid, gel-like, or solid preparation that, upon contact with flushing water, is dissolved by it and can then be dispensed into the toilet bowl as an active ingredient-containing solution, i.e., a mixture of flushing water and active ingredient. Such an active ingredient-containing solution can, for example, also be produced by the flow of water over a solid or gel-like toilet cleaning block through the 2024P00102WQ

[0014] The flushing water is generated in the collection container and then released into the toilet bowl.

[0015] The time offset allows for the targeted release of identical or different active ingredient preparations into the toilet bowl at different times. A typical flush in a standard toilet bowl has two characteristic points in time: the beginning and the end of the flush. These points define the time windows: before, during, and after the flush. The first and second active ingredient preparations are preferably different. Since different active ingredient preparations can have different functions, it is often advantageous to release them at different times during the flush to optimally fulfill these functions. Such optimized release saves active ingredient preparation and achieves the best performance.

[0016] The device according to the invention, which does not have an additional mechanism, for example an electric one, for independent drug delivery, can release the drug preparation from the first chamber into the flushing water and thus into the toilet bowl at the earliest at the start of the flushing process. The flushing water flows over the first chamber, among other things, and enters the first chamber through an inlet, flows over the first drug preparation, and then flows out of the first chamber as a drug-containing solution enriched with the first drug preparation through an outlet towards the toilet bowl. Similarly, the second drug preparation enters the toilet bowl from the second chamber, but the release occurs at a later time.

[0017] The first and second chambers are designed such that, with the same flow rate, the first and second active ingredient preparations are dispensed into the toilet bowl at staggered times. For the purposes of the invention, staggered dispensing of the active ingredient preparations into the toilet bowl means that: i) the dispensing of the at least two different active ingredient preparations begins at at least two different times in relation to the flushing process, and / or ii) the dispensing of the at least two different active ingredient preparations ends at at least two different times in relation to the flushing process.

[0018] For example, the release of the second active ingredient preparation can begin at least 1 second, preferably at least 2 seconds, after the release of the first active ingredient preparation has begun, and / or it can last, for example, at least 1 second, preferably at least 2 seconds, longer than the release of the first active ingredient preparation. There are various types of toilets with different flushing characteristics and flushing times. The device according to the invention is designed for toilet bowls with a flushing process in which the flushing water washes over at least one point on the inner wall of the toilet bowl. Therefore, the device according to the invention is suitable, among other things, for toilet bowls according to standard EN 997 (2003+A1 :2006) Class 1.

[0019] The term "uniform overflow" in the context of the invention primarily requires a simultaneous start of the overflow. Preferably, the device comprises a rinsing water distribution element, e.g., a distribution plate as known from EP2310582, which is arranged and configured such that the rinsing water distribution element is supplied with rinsing water during rinsing and ensures a uniform distribution of the rinsing water into all chambers.

[0020] The time delay is preferably achieved by a time delay device. The time delay device is arranged in series within the rinsing water flow that can flow through one of the chambers in order to influence the flow.

[0021] In a preferred embodiment of the invention, the time delay device is arranged such that it influences the current flow out of the chamber. Examples of the time delay device within a chamber are:

[0022] (i) fewer outlet holes and / or smaller diameter compared to the other chambers without a time delay device, so that the outflow from the chamber starts significantly later and / or proceeds more slowly;

[0023] (ii) a lower outlet opening located above a lower floor of the chamber, so that the chamber must first fill up to the level of this lower outlet opening before emptying;

[0024] (iii) a pipe extending into the chamber as an outlet, so that the chamber must first fill up to the height of the inner pipe end before it empties;

[0025] (iv) a siphon through which a trigger threshold level and a stop threshold level for rinsing water containing the drug solution in the receiving container are defined, above which the flow of rinsing water containing the drug solution through the siphon can begin or cease. The preferred variants for the time-delay device are explained in detail below.

[0026] In one embodiment of the invention, at least one of the first and second chambers, preferably the second chamber, comprises a time delay device. 2024P00102WÖ

[0027] In a further embodiment of the invention, the second chamber comprises a time delay device, and the first chamber comprises a further time delay device which has a different time delay than the time delay device of the second chamber.

[0028] In another embodiment of the invention, the second chamber comprises a time-delay device, while the first chamber does not have a time-delay device. The first active ingredient preparation from the first chamber is thus dispensed into the toilet bowl immediately after the start of the overflow from the first chamber into the receiving container. In this case, the time interval between the start of the overflow from the receiving container and the dispensing from the first chamber is significantly shorter than 1 s, preferably shorter than 0.2 s.

[0029] In principle, a chamber within the meaning of the invention does not have a time delay device if a defined quantity of rinsing water can flow out of a chamber at the same speed or faster than it flows into the chamber in question.

[0030] In a preferred embodiment of the invention, the outlet opening(s) of the second chamber have a smaller overall cross-sectional area compared to the first outlet opening(s) of the first chamber. For example, with the same number of outlet openings in the individual chambers, the individual outlet openings of the first chamber have a larger diameter than the outlet openings of the second chamber. Although the first and second chambers receive rinsing water simultaneously with the same flow rate, the rinsing water containing the active ingredient solution flows out of the second chamber more slowly due to the smaller overall cross-sectional area of ​​the outlet openings, thus resulting in the release of the active ingredient preparation from the second chamber occurring over a longer period. This variant allows for a very advantageous time delay in the release of the active ingredient relative to the actual rinsing process.

[0031] In a further advantageous embodiment of the invention, the second chamber with the time-delay device has fewer outlet openings than the other chambers without a time-delay device, down to a single opening, compared to the number of outlet openings in the first chamber. Optionally, only a single outlet opening is present in the second chamber. Due to this smaller number, only a smaller volume of rinse water can flow out in the same amount of time, thus creating a time delay compared to the first chamber with more outlet openings.

[0032] In another embodiment of the invention, the time delay device is designed as a tube, which is preferably arranged at the bottom of the second chamber and further preferably projects into the second chamber.

[0033] In a particularly preferred embodiment of the invention, the time-delay device is a siphon. It has been found that chambers with smaller volumes fill up with rinse water quite quickly during the rinsing process, offering little room for adjusting the time delay of the start of the drain. On the other hand, it has been found that a siphon can be designed very flexibly so that even in smaller chambers the drain can be delayed by a few seconds compared to the start of the rinsing process. A siphon is therefore a preferred time-delay device. A siphon is also preferred for chambers with a water collection volume of 50 cm³ or less. 3 , even more preferably less than or equal to 30 cm 3 .

[0034] By staggering the release of active ingredient preparations, targeted delivery of specific active ingredient preparations, particularly different preparations, is possible during the various phases of the rinsing process. This ensures a particularly effective and targeted delivery of individual active ingredients at the optimal time without the need for a complex control unit.

[0035] In one embodiment of the invention, the first and second active ingredient preparations contain mutually incompatible ingredients. If these ingredients are present simultaneously in a single preparation, they could, for example, undergo undesirable chemical reactions or lead to phase separation. This is particularly true if incompatibility with the spores occurs. Examples of ingredients incompatible with spores (or spore activation) include bleaching agents and highly reactive dyes. Depending on the type, enzymes may also be included. Furthermore, acids and bases may sometimes be included. Due to the staggered release, both active ingredient preparations can exert their effects at least partially independently of one another.

[0036] In another embodiment of the invention, the first and second active ingredient preparations are compatible with each other but are intended to exert their effect at different times, so they are stored in different chambers of the device. In a preferred further development, the first and second active ingredient preparations contain different active ingredients of the same class, which are, however, chemically different. For example, different surfactants or different enzymes can be used.

[0037] In one embodiment of the invention, the second active ingredient preparation comprises, in addition to the spores, at least one further active ingredient which is intended to exert its effect primarily after a rinsing process. An example of such an active ingredient, according to the invention, is bacterial spores, but also, for example, a water-soluble dye that colors the rinsing water, with a blue color being preferred.

[0038] Due to a significant amount of water continuing to run even after the flushing process has ended, the spores are not washed away, but remain in sufficient concentration in the toilet sump, i.e., in the residual flush water that remains in the toilet bowl, and are distributed on the surface of the toilet.

[0039] In another embodiment of the invention, one of the active ingredient preparations comprises an active ingredient that is intended to exert its effect primarily during a rinsing process. For example, a surfactant for foam formation. The rinsing process is used to form foam by mixing rinse water enriched with surfactant and air. This surfactant is intended to be released into the rinse water essentially during the rinsing process in order to avoid excessive release of the surfactant active ingredient.

[0040] Another example is an active ingredient preparation designed to clean the toilet bowl through a chemical-mechanical cleaning process. This preparation must be dispensed during the flushing process, preferably starting at the very beginning. The flow of the enriched flush water then performs the mechanical part of the toilet cleaning.

[0041] spores

[0042] Spores of robust environmental strains from the genus Bacillus are particularly suitable for use in solid toilet cleaning cubes, as they tolerate the pH levels, surfactants, and fluctuating humidity conditions of such formulations well. Species such as Bacillus subtilis, Bacillus amyloliquefaciens, and Bacillus licheniformis form resilient endospores with thick protective layers, ensuring long-term survival within the compressed solid. These spores withstand the mechanical stresses of the manufacturing process, elevated storage temperatures, and contact with oxidizing additives, yet reliably activate upon contact with water. The vegetative cells that develop after germination produce a broad spectrum of enzymes that break down organic residues such as proteins, carbohydrates, lipids, and persistent biofilm components.

[0043] In addition to classic Bacillus spores, spores from Paenibacillus and Geobacillus strains can also be used, particularly when increased thermal stability or specific enzymatic activity profiles are required. These spores possess defined germination triggers that allow controlled activation only after partial dissolution of the cube. Suitable strains can be selected or modified to prevent the formation of unpleasant odors, rapidly colonize ceramic surfaces, and remain compatible with typical toilet bowl cleaner ingredients such as anionic surfactants and fragrance systems. The combination of high spore resistance and targeted enzyme production results in a long-lasting biological cleaning effect that significantly surpasses the performance of purely chemical products.

[0044] Preferably, at least one of the active ingredient preparations contains one or more fragrances. These are present in the solid, gel-like, or liquid active ingredient preparation, i.e., in the toilet block or toilet cleaner, preferably in an amount of 0.01 to 10 wt.%, particularly 0.05 to 8 wt.%, and most preferably 0.1 to 5 wt.%. d-Limonene may be included as a perfume component. In a particularly preferred embodiment, the active ingredient preparation contains adhesive fragrance substances, in particular essential oils. For example, pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil can be used as such in accordance with this invention. Also suitable are clary 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, other adhesive fragrance substances, such as higher-boiling or solid fragrance substances of natural or synthetic origin, or more volatile fragrance substances, in particular lower-boiling fragrance substances of natural or synthetic origin, which can be used alone or in mixtures, can also be advantageously used in perfume oil within the scope of the present invention. It may further be preferred that the agents used in the different chambers contain different fragrance substances, so that the fragrance impression changes after the rinsing process is complete. It may also be preferred that the agents used in the different chambers contain the same fragrance substances, but differ in their concentration, so that the fragrance is perceived with a different intensity after the rinsing process is complete.

[0045] surfactants

[0046] At least one of the active ingredient preparations contains at least one surfactant. This surfactant is selected from the group of anionic surfactants, non-ionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants, and mixtures thereof. Preferably, at least one anionic surfactant is included.

[0047] Within the scope of the present invention, fatty acids or fatty alcohols or their derivatives—unless otherwise specified—are representative of branched or unbranched carboxylic acids or alcohols or their derivatives, preferably with 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, especially 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, particularly because of their plant-based origin as they are derived from renewable raw materials, without, however, limiting the teaching of the invention to them. In particular, oxo alcohols obtainable, for example, by RoELEN's oxo synthesis are also considered.whose derivatives preferably have 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, especially 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, can be used accordingly.

[0048] Solid toilet blocks preferably containing at least one alkylbenzenesulfonate and at least one olefinsulfonate. They may also contain other surfactants, in particular from the group of anionic and / or nonionic surfactants.

[0049] Of the alkylbenzenesulfonates, those with approximately 12 carbon atoms in the alkyl moiety are particularly preferred, such as 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 wt.%, preferably 20 to 65 wt.%, particularly preferably 20 to 30 wt.% alkylbenzenesulfonate and preferably 10 to 30 wt.%, preferably 15 to 30 wt.%, particularly preferably 15 to 25 wt.% olefin sulfonate.

[0050] Other anionic surfactants that can be used in the toilet cleaning block include aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, and aliphatic sulfonates such as alkanesulfonates, ethersulfonates, n-alkyl ethersulfonates, estersulfonates, and lignosulfonates. Also usable within the scope of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-Ca-Cia alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates, as well as α-sulfofatisfied acid salts, acylglutamates, monoglyceride disulfates, and alkyl ethers of glycerin disulfate.

[0051] Preferred within the scope of the present invention are fatty alcohol sulfates and / or fatty alcohol ether sulfates, in particular 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. Those skilled in the art generally understand alkoxylated alcohols to be the reaction products of alkylene oxides, preferably ethylene oxide, with alcohols, and, within the meaning of the present invention, preferably with longer-chain alcohols. Typically, from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, a complex mixture of addition products with varying degrees of ethoxylation is formed. Another embodiment of the alkoxylation involves the use of mixtures of alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.Preferred fatty alcohol ether sulfates are the sulfates 2024P00102WC of low ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1,3 EO.

[0052] 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, as well as in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, and in the case of sulfonates also in the form of their corresponding acid, e.g. dodecylbenzenesulfonic acid.

[0053] Non-ionic surfactants

[0054] Nonionic surfactants within the scope of the invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, and fatty acid polyglycol esters. Ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers are also suitable. Another important class of nonionic surfactants that can be used according to the invention are the polyol surfactants, and in particular the glycotidical surfactants, such as alkyl polyglycosides and fatty acid glucamides. Alkyl polyglycosides, especially alkyl polyglucosides, and especially fatty alcohol alkoxylates (fatty alcohol polyglycol ethers) are particularly preferred.

[0055] Preferred fatty alcohol alkoxylates are unbranched or branched, saturated or unsaturated Cs-22 alcohols with a degree of alkoxylation up to 30, alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO), preferably ethoxylated Ci2-22 fatty alcohols with a degree of ethoxylation of less than 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example C -is fatty alcohol ethoxylates with 25 EO.

[0056] Alkyl polyglycosides are surfactants that can be obtained by reacting sugars and alcohols according to the relevant processes of preparative organic chemistry, resulting, depending on the method of preparation, in a mixture of monoalkylated, oligomeric, or polymeric sugars. Preferred alkyl polyglycosides are the alkyl polyglucosides, wherein the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched Cs to Cis alkyl chains, and the degree of oligomerization (DP) of the sugars is between 1 and 10, preferably 1 to 6, particularly 1.1 to 3, and most preferably 1.1 to 1.7, for example, Cs-w-alkyl-1,5-glucoside (DP of 1.5).

[0057] Preferably, fatty alcohol ethoxylates are used in amounts of up to 20 wt.%, particularly preferably 4 to 12 wt.%, particularly preferably 7 to 9 wt.%. In addition, other nonionic surfactants, such as fatty acid monoalkanolamides and / or alkyl polyglycosides, may be present in amounts of up to 10 wt.%. 2024P00102WG

[0058] In addition to the surfactant types mentioned so far, the active ingredient preparation according to the invention can also contain cationic surfactants and / or amphoteric or zwitterionic surfactants.

[0059] Suitable amphoteric surfactants include, for example, betaines of the formula (R''')(R' V )(R V )N + CH2COO _ , in which R'" optionally interrupted by heteroatoms or heteroatom groups, an alkyl group with 8 to 25, preferably 10 to 21 carbon atoms and R' v as well as R vsimilar or different alkyl groups with 1 to 3 carbon atoms, in particular Cw-Cis-alkyl-dimethylcarboxymethylbetaine and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetaine.

[0060] Suitable cationic surfactants include, among others, the quaternary ammonium compounds of the formula (R V ')(R V '')(R V "')(R' X )N + X , in the R vi to R' x The alkyl groups can be four identical or different, in particular two long-chain and two short-chain, and X- can represent an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof. Quaternary ammonium compounds with antimicrobial activity are preferred.

[0061] In addition to the components mentioned above, the product may contain other ingredients commonly used in toilet cleaning agents, preferably selected from the group comprising acids, bases, salts, thickeners, antimicrobial agents, preservatives, complexing agents, polymers, dyes, odor reducers, perfume boosters, fillers, builders, bleaching agents, corrosion inhibitors, flush regulators, enzymes, microorganisms, biofilm removers, limescale inhibitors, dirt adhesion reducers, workability improvers, stickiness reducers, and mixtures thereof. The total amount of other ingredients should not exceed 60% by weight, preferably 0.01 to 60% by weight, and in particular 0.2 to 15% by weight.

[0062] Acids

[0063] To enhance cleaning performance against limescale and urine scale, at least one of the active ingredient preparations may contain one or more acids and / or their salts. Preferably, the acids are produced from renewable raw materials. Suitable acids include, 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, as well as mixtures thereof. In addition, the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, or even sulfamic acid or mixtures thereof, may also be used. Particularly preferred are the acids and / or their salts selected from the group comprising citric acid, lactic acid, formic acid, their salts, and mixtures thereof. They are preferably used in amounts of 0.01 to 10 wt.%, and particularly preferably 0.2 to 5 wt.%.This active ingredient is particularly suitable for use in the chamber with the time-delay device, 2024P00102WC, as the limescale and urinary scale dissolving effect of the acids should continue, if possible, even after the flushing process has been completed.

[0064] In addition, compositions usable according to the invention, in a preferred embodiment, contain inorganic salts, preferably alkali or alkaline earth metal salts, in particular carbonates, sulfates, halides or phosphates, as well as mixtures thereof. Sodium sulfate and / or sodium carbonate are particularly preferred. Sodium sulfate may 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, and particularly preferably 35 to 55% by weight. Sodium carbonate and other salts may be present in an amount of up to 30% by weight, preferably up to 10% by weight, and particularly preferably up to 5% by weight.

[0065] Bases

[0066] The compositions usable according to the invention may also contain alkalis. Preferably, bases from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide, are used. However, ammonia and / or alkanolamines with up to 9 carbon atoms in the molecule can also be used, preferably ethanolamines, in particular monoethanolamine.

[0067] Antimicrobial agents

[0068] Disinfection and sanitation represent special forms of cleaning. In a corresponding particular embodiment of the invention, the agent usable according to the invention therefore contains one or more antimicrobial agents, preferably in an amount of 0.01 to 1 wt.%, preferably 0.02 to 0.8 wt.%, in particular 0.05 to 0.5 wt.%, especially preferably 0.1 to 0.3 wt.%, most preferably 0.2 wt.%.

[0069] Within the context of the invention, the terms disinfection, sanitation, antimicrobial effect, and antimicrobial agent have their customary meanings. While disinfection, in the narrower sense of medical practice, means the killing of—theoretically all—infectious agents, sanitation refers to the elimination of all germs—including saprophytic germs, which are normally harmless to humans—to the greatest extent possible. The degree of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing concentration of antimicrobial agent or increasing dilution of the agent.

[0070] Suitable for use according to the invention are, for example, antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, 2024P00102WÖ

[0071] Phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surfactants, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butylcarbamate, iodine, iodophores, active chlorine-releasing compounds and peroxides.Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2'-methylenebis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)-urea, N,N'-(1,10-decandiyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine)-dihydrochloride, N,N'-bis-(4-chlorophenyl)-3,12-diimino-2,4,11 13-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines, and sodium dichloroisocyanurate (DCI, 1,3-dichloro-5H-1,3,5-triazine-2,4,6-trione sodium salt). Preferred antimicrobial quaternary surfactants contain an ammonium, sulfonium, phosphonium, iodonium, or arsonium group.Furthermore, antimicrobial essential oils can also be used, which simultaneously provide fragrance to the cleaning agent. Particularly preferred antimicrobial agents are selected from the group comprising salicylic acid, quaternary surfactants, especially benzalkonium chloride, peroxo compounds, especially sodium percarbonate, phthalimidoperoxyhexanoic acid or hydrogen peroxide, alkali metal hypochlorite, trichloroisocyanuric acid, sodium dichloroisocyanurate, and mixtures thereof. Sodium dichloroisocyanurate is particularly preferred.

[0072] Preservatives

[0073] Preservatives may also be included in the active ingredient preparations according to the invention. Essentially, the substances mentioned in connection with the antimicrobial active ingredients can be used as such.

[0074] Complexing agents

[0075] Chelating agents (JNCI), also known as sequestering agents, are ingredients that can complex and inactivate metal ions to prevent their adverse effects on the stability or appearance of the product, such as turbidity. On the one hand, it is important to complex the calcium and magnesium ions associated with water hardness, which are incompatible with numerous other ingredients. On the other hand, the complexation of ions from heavy metals such as iron or copper delays the oxidative degradation of the finished product. Furthermore, the chelating agents enhance the cleaning effect. 2024P00102WC

[0076] Geeignet sind beispielsweise die folgenden gemäß INCI bezeichneten Komplexbildner: 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 Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid, 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 EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA-Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

[0077] Polymers

[0078] At least one of the active ingredient preparations according to the invention may further contain polymers. These can, for example, serve to reduce limescale formation and the tendency to re-soil (so-called soil repellent polymers).

[0079] Preferred polymers are acrylic polymers, such as those commercially available from the company Rhodia under the trade name Mirapol.

[0080] Dyes

[0081] The composition according to the invention may contain one or more colorants (INCI colorants) as further ingredients. Both water-soluble and oil-soluble colorants can be used, whereby, on the one hand, compatibility with other ingredients, for example, bleaching agents, must be considered, and on the other hand, the colorant used should not have a substantial effect on the toilet bowl ceramic, even with prolonged exposure. It is preferred if the second active ingredient preparation comprises a water-soluble colorant that colors the flushing water, with a blue color being preferred. The flushing water colored with this colorant remains in sufficient concentration in the toilet bowl sump, i.e., in the residual flushing water remaining in the toilet bowl after the actual flushing process, to impart a color, preferably blue. The colorants are preferably present in an amount of 0.0001 to 0.1 wt.-%, in particular 0.0005 to 0.05 wt%, especially preferably 0.001 to 0.01 wt%. The dye is then preferably present in the same active ingredient composition as the bacterial spores.

[0082] Builder

[0083] The agents used according to the invention may optionally contain water-soluble and / or water-insoluble builders. Water-soluble builders are preferred because they generally tend to leave less insoluble residues on hard surfaces. Common builders that may be present within the scope of the invention include low-molecular-weight polycarboxylic acids and their salts, homopolymeric and copolymer polycarboxylic acids and their salts, citric acid and its salts, carbonates, phosphates, and silicates. Water-insoluble builders include zeolites, which can also be used, as well as mixtures of the aforementioned builder substances.

[0084] Bleach

[0085] According to the invention, bleaching agents can be added to at least one of the active ingredient preparations. Suitable bleaching agents include peroxo compounds, in particular peroxides, peracids, percarbonates, and / or perborates; sodium percarbonate, phthalimidoperoxyhexanoic acid, or hydrogen peroxide are particularly preferred. Alkali metal hypochlorites such as sodium hypochlorite, on the other hand, 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 some cases, a bleach activator may also be required in addition to the bleaching agent.

[0086] Corrosion inhibitors

[0087] Geeignete Korrosionsinhibitoren (JNCI Corrosion Inhibitors) sind beispielsweise folgende gemäß INCI benannte Substanzen: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, 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 Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine. Abspülregulatoren

[0088] The substances known as rinsing regulators primarily serve to control the consumption of the cleaning agent during use, ensuring that the intended service life is maintained. Suitable regulators include 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 with molecular weights between 10,000 and 50,000.

[0089] Active ingredients to reduce stickiness

[0090] To improve the processability during the manufacture of solid toilet cleaning blocks according to the invention, particularly those in spherical form, an active ingredient to reduce stickiness can be added. For example, the addition of dolomite powder or titanium dioxide powder with a fine particle size distribution improves the processing behavior during sphere forming and significantly reduces abrasion and stickiness. The results with such active ingredients are better than with other conventional measures, such as coating the spheres with a lubricant, dusting them with powder, or coating the forming rollers with Teflon.

[0091] Enzymes

[0092] The agent may also contain enzymes, preferably proteases, lipases, amylases, hydrolases, and / or cellulases. These can be added to the agent usable according to the invention in any form established in the prior art. This includes solutions of the enzymes, advantageously as concentrated as possible, with low water content, and / or containing stabilizers. Alternatively, the enzymes can be encapsulated, for example, by spray drying or extrusion of the enzyme solution together with a polymer, preferably a natural one, or in the form of capsules, for example, capsules in which the enzymes are enclosed as if in a solidified gel, or capsules 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, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can also be applied in superimposed layers.Such capsules are produced using known methods, for example by shake or roll granulation or in fluid-bed processes. Advantageously, such granules are low in dust, for example through the application of polymeric film formers, and are stable for storage due to the coating.

[0093] Furthermore, enzyme stabilizers may be present in enzyme-containing agents to protect an enzyme contained in an agent according to the invention from damage such as inactivation, denaturation or degradation, for example by physical influences, oxidation or proteolytic cleavage.Depending on the specific enzyme used, the following are particularly suitable as enzyme stabilizers: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, such as substituted phenylboronic acids or their salts or esters; peptide aldehydes (oligopeptides with a reduced C-terminus), amino alcohols such as mono-, di-, triethanolamine and ethanol-propanolamine and their mixtures, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of the aforementioned acids; end-capped fatty acid amido alkoxylates; lower aliphatic alcohols and especially polyols, for example, glycerol, ethylene glycol, propylene glycol or sorbitol; as well as reducing agents and antioxidants such as sodium sulfite and reducing sugars. Further suitable stabilizers are known from the prior art.Preferably, combinations of stabilizers are 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.

[0094] Multi-layer toilet cleaning blocks

[0095] From the prior art, for example EP 791047B1, it is known to produce essentially solid toilet cleaning blocks from differently composed masses, wherein one of the masses is wholly or partially enclosed by the other mass(s). For example, the inner mass can have a higher perfume concentration than the outer mass to ensure a consistent fragrance impression during use as the mass of the sphere decreases, or the inner mass can contain a different fragrance than the outer mass. In addition, other active ingredients can be incorporated into different layers, which are released at different times depending on the degree of flushing. Such a layered structure is also possible in the toilet cleaning block usable according to the invention.

[0096] In a preferred embodiment of the invention, the first and second active ingredient preparations are present as solids in the receiving container, as arbitrarily geometrically shaped toilet blocks (also referred to as toilet blocks). The preferred shape of the toilet blocks is rotationally symmetrical, in particular spherical, among other things to achieve a particularly favorable volume-to-surface-area ratio for the toilet block. This is particularly advantageous in a chamber with a time-delay device. For example, if the second chamber has a time-delay device, in particular a siphon, the chamber remains filled with flushing water at a certain level for a longer period. Consequently, a spherical toilet block has minimal contact with the flushing water in the chamber in its lower region and is therefore not unnecessarily dissolved. 2024P00102WG

[0097] In one embodiment of the invention, the receiving container comprises at least one wall that separates the first chamber from the second and any further chambers. This ensures that the potentially incompatible active ingredient preparations located in the at least one first chamber and the at least one second chamber do not come into contact, thereby preventing, for example, undesirable reactions between the individual active ingredient preparations or color transfer between the chambers.

[0098] In a particular embodiment of the invention, the second chamber is located centrally within the receiving container. For example, the second chamber is enclosed on one side by the first chamber and on the other side by another chamber. Naturally, the addition of further chambers is also possible as required.

[0099] It is particularly preferred that the first chamber and the second chamber, which form the receiving container, are coupled to each other, and further preferably are formed in one piece.

[0100] The collection container is held by the holder on the toilet bowl, so that in its operating position it lies with the chambers below the holder. The holder is preferably designed as a hanging bracket, for example, in the shape of a bracket.

[0101] Furthermore, the receiving container is preferably made of plastic, such as PET or PP. It is also preferred that the receiving container has a transparent design to allow a view into the chambers filled with the active ingredient preparation.

[0102] The invention is explained in more detail below with reference to the drawings. These examples do not exhaustively describe all possible devices conforming to the invention that a person skilled in the art can implement with the help of the description. It is essential that the chambers are designed such that the first active ingredient preparation and the second active ingredient preparation are dispensed into the toilet bowl at different times. The figures show:

[0103] Fig. 1A shows a perspective view of the device, where the device is shown open and without active ingredient preparations;

[0104] Fig. 1B shows a section through a device according to the invention along the sectioning plane AA; from Figure 1;

[0105] Fig. 2 shows a device according to the invention with active ingredient preparations, wherein the time-delay device is a tube. 2024P00102WC

[0106] Fig. 1A is a perspective view of a device 1 according to the invention, wherein the device 1 is shown open and without active ingredient preparations. Fig. 1B shows a section of the same device 1, with WC blocks comprising the active ingredient preparations 5 and 6; these need not necessarily be rectangular and are preferably spherical. The device 1 is expediently suspended from the toilet bowl by a hanger 12. However, other known fastening methods are also possible. The device 1 comprises a receiving container with a first chamber 3 and a second chamber 4. The first chamber 3 comprises inlet openings 7 and outlet openings 9. The outlet openings 9 are designed such that overflowing flushing water flowing in through the inlet can flow out into the toilet bowl through the outlet openings 9 essentially without 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 a tube 11 that projects into the second chamber 4. When rinsing water flows into the second chamber 4, it fills up to the inner end of the tube before it can drain out through the tube 11. Any residual water remaining in the second chamber after the rinsing process evaporates slowly.

[0107] Although the device 1 is shown as rectangular in Fig. 1 AB, other shapes for the receiving container 2 are also possible. Additional chambers can also be provided as needed. The wall 13 is preferably present; further preferably, the receiving container 2 has a lid and the wall 13 extends from the bottom to the lid, thus separating the first chamber 3 from the second chamber 4.

[0108] Fig. 2 is a perspective view of a device 1 according to the invention. The device 1 is expediently suspended from the toilet bowl by a hanger 12. Other known fastening methods are alternatively possible. The device 1 comprises a receiving container 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 containing the active ingredient preparations 5 and 6. These toilet blocks are also preferably rotationally symmetrical, in particular spherical. The first chamber 3 comprises inlet openings 7 and outlet openings 9. The outlet openings 9 are designed such that overflowing flushing water flowing in through the inlet openings 7 can flow out through the outlet openings 9 into the toilet bowl essentially without 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 that projects into the second chamber 4. When rinsing water flows into the second chamber, it fills up to the trigger threshold level. The rinsing water then begins to flow out through the siphon until the termination threshold level is reached. It is particularly preferred that the siphon is designed such that the second chamber 4 empties substantially. Further chambers may also be provided as required. A wall is preferably provided that separates the first chamber 3 from the second chamber 4. The use of a siphon is particularly advantageous because spores can be present in this aqueous environment for an extended period and can be sufficiently activated.

[0109] 2024P00102WC

[0110] Example implementation:

[0111] Solid, water-soluble toilet cleaning agent preparations (so-called toilet cleaning blocks or toilet blocks) were formulated according to the framework formulations shown in the table below.

[0112] E1 and E2 each comprise two different compositions, one of which is designed to release its active ingredient with a time delay. The quantities are given in wt% of the active ingredient, based on the respective toilet bowl cleaner block.

[0113]

[0114] Water-soluble blue dye was used to illustrate the effect and distribution of spores.

[0115] To simulate the effect of the time offset, a dye (to simulate the spore effect) was used in the middle chamber. In a device according to Fig. 2, the block marked "blue" consisting of E1 or E2 was placed in the second chamber, and the one marked "yellow" or E2 in the middle chamber.

[0116] The block marked "white" was placed in the first chamber. The "blue" block contained a water-soluble blue dye. In E1, the yellow block contained foaming surfactants, while in E2, the white block also contained the bleaching agent sodium isocyanurate. The devices according to E1 and E2 were each suspended in a toilet bowl conforming to standard EN 997 (2003+A1 :2006) Class 1 with a flushing volume of 8-1 OL. During flushing, it was observed that foam formed in the toilet bowl at the beginning of the flushing process, and that 1 second after the start of the flush, blue-colored flush water containing the active ingredient solution began to flow from the second chamber. At the end of the flush, the release of flush water containing the active ingredient solution from the first chamber also ceased, while the release of flush water containing the active ingredient solution from the second chamber continued for approximately 4-6 seconds, thus coloring the remaining water in the toilet bowl blue.Overall, it was shown that the spores spread across the toilet surface and thus remained on the moist surface for a sufficiently long time to activate.

Claims

Patent claims 1. Device (1) for dispensing active ingredient preparations (5, 6) into a toilet bowl, comprising a receiving container (2) to be arranged in the toilet bowl, wherein the receiving container (2) is attachable to the toilet bowl, wherein the receiving container (2) comprises at least a first chamber (3) and a second chamber (4), wherein the first chamber (3) dispenses a first active ingredient preparation (5) into the toilet bowl when flush water flows over it, and the second chamber (4) dispenses a second active ingredient preparation (6) into the toilet bowl when flush water flows over it, characterized in that the chambers (3, 4) are designed such that the first active ingredient preparation (5) and the second active ingredient preparation (6) are dispensed into the toilet bowl at different times when flush water flows over them simultaneously, characterized in that either the first active ingredient preparation (5) and / or the second active ingredient preparation (6) contains bacterial spores.

2. Device according to claim 1, characterized in that it has means to release at least one active ingredient preparation into the toilet bowl with a time delay compared to the flushing process, and that the second active ingredient preparation contains bacterial spores and the second active ingredient preparation (6) is released into the toilet bowl after the first active ingredient preparation (5) with the same overflow.

3. Device according to one of the preceding claims, characterized in that the receiving container (2) comprises a wall (13) that separates the first chamber (3) from the second chamber (4).

4. Device according to one of the preceding claims, characterized in that the second chamber (4) is located centrally in the receiving container (2).

5. Device according to one of the preceding claims, characterized in that the first chamber (3), the second chamber (4) and, if present, further chambers are coupled to each other.

6. Device according to one of the preceding claims, characterized in that at least one chamber (4) comprises a time delay device (11), preferably the second chamber (4).

7. Device according to claim 6, characterized in that the chamber (4) with time delay device (11) has at least one outlet opening which is opposite the(s) 23 2024P00102WG The outlet opening(s) of the other chambers (3) without time delay device (11) has a smaller overall cross-section and is characterized in that chamber (4) with time delay device (11) has at least one outlet opening which is present in smaller numbers compared to the outlet openings of the other chambers (3) without time delay device (11).

8. Device according to claim 6 or 7, characterized in that the time delay device (11) is a tube which is preferably arranged at the bottom of the relevant chamber (4) and further preferably projects into this chamber (4).

9. Device according to claims 6 to 8, characterized in that the time delay device (11) is a siphon.

10. Device according to one of the preceding claims, characterized in that the first and second active ingredient preparations (5, 6) are present as solids in the receiving container (2).

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