Toilet blocks with coating

Abstract

A toilet cleaning block containing perfume, characterized in that the block has a coating, the coating being a water-soluble film. Furthermore, a system comprising a dispensing device with a toilet cleaning block and packaging is described.

Description

[0001] The invention relates to a system comprising a package and at least one coated toilet cleaning block containing perfume and a dispensing device.

[0002] Toilet cleaning blocks, also known as toilet blocks, have long been used for cleaning, disinfecting, and fragrance toilets, both under the rim (so-called rim blocks) and in the cistern (in-tank blocks or cistern blocks). In recent years, aesthetics and performance have become increasingly important. This has led, for example, to the development of gel or liquid toilet bowl fresheners, some of which are offered in multi-chamber containers, thus combining a cleaning agent dispensed when the toilet is flushed with continuous room fragrance. European patents EP 2 014 758 A1, WO 2012 / 017276 A1, WO 2017 / 103875 A1, EP 1 223 113 A1, WO 2021 / 018822 A1, and DE 10 2009 003088 A1 describe toilet blocks.

[0003] However, solid toilet blocks remain relevant. These have primarily been manufactured by extrusion and then cut to size, resulting in mostly cuboid-shaped toilet rim blocks that were subsequently placed in corresponding baskets.

[0004] One disadvantage of these rim blocks is that they swell due to the rinsing water entering the basket, are rinsed unevenly, and lose their shape. After only a short time, an unsightly block remains.

[0005] Furthermore, such rim blocks are usually sold in blister packs. Blister packs are product packaging that allows the customer or buyer to see the packaged goods.

[0006] The product is presented in front of a cardboard backing, usually printed with information, and secured with a molded plastic film insert. In some display packages, the backing is also made of plastic film, or sometimes aluminum foil.

[0007] There are three main types of packaging: heat-sealed, clamp-on, and stapled. In heat-sealed packaging, the front and back of the film are fused together using heat, creating a seal. Clamp-on packaging involves bending the edges of the front film around the cardboard backing by heating the plastic. Stapled packaging uses staples to fasten the front film and cardboard backing together. The blister shape is achieved using thermoforming technology.

[0008] Blister packaging offers advantages for retailers. It can usually be slid onto standardized holders, simplifying presentation and inventory management. Another benefit is that blister packaging allows consumers to see the cleaning product through the transparent plastic front of the package.

[0009] However, from an environmental perspective, the high volume of packaging waste is a disadvantage, especially for small items like cleaning product containers, as is the poorer environmental footprint of plastic compared to cardboard. Blister packs are therefore controversial.

[0010] It was therefore desirable to formulate a shapely and aesthetically pleasing toilet block that flushes evenly throughout its lifespan and swells as little as possible. At the same time, the amount of plastic waste generated during production should be reduced as much as possible.

[0011] The invention now relates to a system encompassing: at least one toilet cleaning block containing perfume, characterized in that the toilet cleaning block has a coating, wherein the coating consists of a water-soluble film; a dispensing device comprising the at least one toilet cleaning block; and packaging for the dispensing device, comprising a back and a front, wherein the front is at least partially free of packaging, in that the front of the packaging has a recessed, packaging-free part, allowing a view of the cleaning agent body, wherein the back of the packaging is made of paper or cardboard.

[0012] Surprisingly, it has now been discovered that a toilet bowl cleaner block containing perfume and featuring a coating allows for a reduction in plastic waste. These toilet bowl cleaner blocks do not swell and, due to their predominantly round shape, always have a maximum surface area. Flushing is therefore even, so that the original shape is retained even after numerous flushes. The coating eliminates the need for blister packaging when selling the blocks, thus reducing plastic waste. In particular, a simple cardboard backing is sufficient for packaging the toilet bowl cleaner blocks. The coating prevents the diffusion of fragrances.

[0013] Optionally, the toilet cleaning block is used in a dispensing device, such as a so-called toilet basket.

[0014] The invention thus relates to a system comprising packaging, at least one toilet cleaning block, and a dispensing device, wherein the packaging has a back side, preferably made of paper or cardboard, and the front side is at least partially free of packaging. The dispensing device with the toilet block is attached to the back of the packaging. The front of the packaging has a packaging-free portion, in particular such that the cleaning block is visible through the cutout portion of the packaging, thereby essentially eliminating the need for plastic packaging. Preferably, the packaging is essentially free of plastic.Since the front is at least partially free of packaging, allowing a view of the cleaning agent block through the cutout portion, and the toilet cleaning block is in contact with its surroundings, diffusion of substances into the environment can occur. In particular, volatile perfume oils can escape. According to the invention, this is prevented by the toilet cleaning block having a coating, especially a transparent film, particularly a PVA film, since such a PVA film is essentially transparent and thus preserves the visual impression at the time of purchase. Therefore, the combination of the toilet cleaning block with a water-soluble film in the packaging described above is particularly significant according to the invention.Only through this combination can the fragrance and visual appearance of the toilet cleaning blocks be preserved while using more ecologically advantageous packaging.

[0015] The system described primarily applies to so-called "RimBlocks," i.e., toilet cleaning blocks as described above, in a dispensing device. This is because these can be easily attached to the back of the packaging using the dispensing device. However, so-called "InTank" toilet cleaning blocks, which are used inside the toilet cistern, cannot be attached using a dispensing device.

[0016] The toilet cleaning block can be manufactured in a process that includes the steps of mixing the ingredients, extruding the mixture, cutting the extruded strand into portions of a defined mass, and deforming it into rotationally symmetric bodies.

[0017] Also disclosed, but not claimed, is a method for producing a rotationally symmetric toilet cleaning block containing perfume, non-ionic surfactant, alkylbenzenesulfonate and olefinsulfonate, comprising the steps a) Mixing the ingredients, b) Extrusion of the mixture, c) Cutting the extruded strand into portions of a defined mass, d) Deformation into rotationally symmetric bodies, e) Packaging

[0018] The system according to the invention, comprising the toilet cleaning block and the dispensing device, can also be used in a method for cleaning and / or scenting and / or disinfecting flush toilets, such that the dispensing device filled with the toilet cleaning block is suspended in the toilet bowl, and when the toilet is flushed, dissolved ingredients of the toilet cleaning block enter the flush water and can exert their cleaning and / or scenting and / or disinfecting effect there. Also disclosed, but not claimed, is a method for cleaning and / or scenting and / or disinfecting flush toilets using a system comprising a toilet cleaning block and a dispensing device according to the invention.

[0019] Substances that also serve as ingredients in cosmetic products are listed below, if applicable, in accordance with the International Nomenclature Cosmetic Ingredient(INCI) nomenclature. Chemical compounds have an INCI name in English, plant-based ingredients are listed exclusively in Latin according to Linnaeus, and so-called trivial names such as "water," "honey," or "sea salt" are also given in Latin. The INCI names can be found in the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), published by The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA, which contains more than 9,000 INCI names as well as references to more than 37,000 trade names and technical designations, including their associated distributors from over 31 countries. International Cosmetic Ingredient Dictionary and Handbook assigns one or more chemical classes to the ingredients ( Chemical Classes ) , for example Polymeric Ethers, and one or more functions ( Functions ) , for example Surfactants - Cleansing Agents, to which it explains in more detail and which may also be referred to below.

[0020] The abbreviation CAS means that the following sequence of numbers is a designation of the Chemical Abstracts Service it.

[0021] 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, more preferably 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, 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 the Roelen 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. perfume

[0022] The product contains one or more fragrances, 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 toilet cleaning block contains a perfume made from 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 flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, and labdanum oil, as well as orange flower oil, neroliol, orange peel oil, and sandalwood oil.

[0023] To be perceptible, an odorant must be volatile, and in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role. Most odorants have molar masses up to about 200 Daltons, while molar masses of 300 Daltons and above are rather exceptional. Due to the varying volatility of odorants, the scent of a perfume composed of several odorants changes during evaporation, with the olfactory impressions being divided into "top note," "middle note" or "body note," and "base note" (end note or "dry out").

[0024] Adherent fragrance substances that can advantageously be used in the perfume oils within the scope of the present invention are, for example, essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lemongrass oil, musk seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, origanum oil, and palmarosa oil. Patchouli oil, Peruvian balsam oil, petitgrain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, star anise oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, and cypress oil.

[0025] However, higher-boiling or solid fragrance substances of natural or synthetic origin can also be advantageously used as adhesive fragrance substances or fragrance mixtures in the perfume oils within the scope of the present invention. These compounds include the following and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, borneol, bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, methyl heptyne ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamaldehyde alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, camphor, carvacrol, carvone, p-cresol methyl ether coumarin, p-methoxyacetophenone,Methyl n-amyl ketone, Methyl anthranilic acid methyl ester, p-Methylacetophenone, Methyl chavicol, p-Methylquinoline, Methyl β-naphthyl ketone, Methyl n-nonylacetaldehyde, Methyl n-nonyl ketone, Muscone, β-Naphthol ethyl ether, β-Naphthol methyl ether, Nerol, Nitrobenzene, n-Nonylaldehyde, Nonylacohol, n-Octylaldehyde, p-Oxy-Acetophenone, Pentadecanolide, β-Phenylethyl alcohol, Phenylacetaldehyde dimethyl acetal, Phenylacetic acid, Pulegone, Safrole, Isoamyl salicylic acid ester, Methyl salicylic acid ester, Hexyl salicylic acid ester, Cyclohexyl salicylic acid ester, Santalol, Skatole, Terpineol, Thymene, Thymol, γ-Undelactone Vanillin, veratraldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamic acid ester, benzyl cinnamic acid ester.

[0026] Among the more volatile fragrance substances that can be advantageously used in perfume oils within the scope of the present invention are, in particular, lower-boiling fragrance substances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrance substances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and propionate, menthol, menthone, methyl n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, and citronellal. surfactants

[0027] The toilet cleaning block contains at least one non-ionic surfactant, at least one alkylbenzenesulfonate, and at least one olefinsulfonate. It may also contain other surfactants.

[0028] 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. Non-ionic surfactants

[0029] 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.Preferred fatty alcohol alkoxylates are unbranched or branched, saturated or unsaturated C 8-22 alcohols with a degree of alkoxylation up to 30, alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO), preferably ethoxylated C 12-22 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 16-18 fatty alcohol ethoxylates with 25 EO.

[0030] 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 C8 to C18 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, C8-10 alkyl-1,5-glucoside (DP of 1.5).

[0031] Preferably, fatty alcohol ethoxylates are used in amounts of up to 20 wt%, particularly preferably 4 to 12 wt%, and 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%. Other anionic surfactants

[0032] Other anionic surfactants that can be used in the toilet cleaning block according to the invention 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-C8-C18 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.

[0033] 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 of low ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1,3 EO.

[0034] 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.

[0035] In addition to the surfactant types mentioned so far, the agent according to the invention can also contain cationic surfactants and / or amphoteric surfactants.

[0036] Suitable amphoteric surfactants are, for example, betaines of the formula (R iii< )(R iv< )(R v< )N +< CH 2 COO -< , in which R iii< represents an alkyl group with 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R iv< and R v< represent similar or different alkyl groups with 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethyl betaine and C 11 -C 17 -alkylamidopropyl-dimethylcarboxymethyl betaine.

[0037] Suitable cation surfactants include, among others, the quaternary ammonium compounds of the formula (R vi< )(R vii< )(R viii< )(R ix< )N +< X -< , in which R vi< to R ix< represent four identical or different, in particular two long-chain and two short-chain, alkyl groups and X -< represent an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and their mixtures. coating

[0038] A film of a water-soluble organic material, preferably polyvinyl alcohol (PVOH), is preferred as the coating. A mixture of 5-50% PVOH with a low degree of hydrolysis has proven particularly advantageous. The film is created by spraying or soaking, and the product is completely coated. A mix of different degrees of hydrolysis of PVOH ensures optimal mechanical resistance of the coating, odor barrier, and solubility. Other ingredients

[0039] In addition to the components mentioned above, the toilet cleaning block may contain further ingredients commonly used in toilet cleaning blocks, preferably selected from the group comprising acids, bases, salts, thickeners, antimicrobial agents, preservatives, complexing agents, dyes, perfume boosters, fillers, builders, bleaching agents, corrosion inhibitors, flush regulators, enzymes, microorganisms, biofilm removers, limescale inhibitors, dirt adhesion 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. Acids

[0040] Toilet cleaning blocks can contain one or more acids and / or their salts to enhance their cleaning performance against limescale and urine scale. 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, can 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% by weight, and particularly preferably 0.2 to 5% by weight.

[0041] In a preferred embodiment, the composition also contains 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 more 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 more preferably up to 5% by weight. Bases

[0042] The composition may also contain alkalis. The bases used in the composition are preferably those from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide. However, ammonia and / or alkanolamines with up to 9 carbon atoms in the molecule may also be used, preferably ethanolamines, especially monoethanolamine. Antimicrobial agents

[0043] Disinfection and sanitation represent a special form of cleaning. In a corresponding particular embodiment of the invention, the toilet cleaning block 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.%.

[0044] 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.

[0045] Suitable substances according to the invention include, for example, antimicrobial agents 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 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 and peroxides.Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)-urea, N,N'-(1,10-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. 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 hydrogen peroxide, alkali metal hypochlorite and mixtures thereof. Preservatives

[0046] Preservatives may also be present in toilet cleaning blocks. These can essentially be the same substances mentioned in connection with antimicrobial agents. Complexing agents

[0047] Complexing agents ( INCIChelating agents, 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, these complexing agents enhance the cleaning effect.

[0048] Suitable examples include the following: INCIbezeichneten 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. Fragrances and dyes

[0049] The toilet cleaning block may also contain one or more fragrances and / or one or more dyes ( INCIThe product contains colorants. Both water-soluble and oil-soluble dyes can be used, whereby compatibility with other ingredients, such as bleaching agents, must be considered, and the dye used should not have a substantial effect on the toilet bowl ceramic, even with prolonged exposure. The dyes are preferably present in an amount of 0.0001 to 0.1 wt.%, in particular 0.0005 to 0.05 wt.%, and most preferably 0.001 to 0.01 wt.%. Builder

[0050] Water-soluble and / or water-insoluble builders can be used in the toilet cleaning blocks. Water-soluble builders are preferred because they are generally less likely to leave 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 copolymeric 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. Bleach

[0051] According to the invention, bleaching agents can be added to the cleaning agent. Suitable bleaching agents include peroxides, peracids and / or perborates; a bleaching agent is particularly preferred.

[0052] Hydrogen peroxide. Sodium hypochlorite, on the other hand, is less suitable for acidic cleaning agents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents. In some cases, a bleach activator may be necessary in addition to the bleach. Corrosion inhibitors

[0053] Suitable corrosion inhibitors ( INCI Corrosion inhibitors) are, for example, the following according to INCIbenannte 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. Rinse regulators

[0054] 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. Enzymes

[0055] The composition may also contain enzymes, preferably proteases, lipases, amylases, hydrolases, and / or cellulases. These can be added to the composition 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.

[0056] 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. Sphericity

[0057] The toilet cleaning block preferably has a sphericity Ψ between 0.8 and 1, particularly preferably between 0.85 and 1, most preferably between 0.9 and 1.

[0058] The sphericity Ψ of a body K is the ratio of the surface area of ​​the body to the surface area of ​​a sphere of the same volume: Ψ = π 1 3 6 V p 2 3 A p , where V p the volume of the body and A p its surface is described

[0059] The near-ideal spherical shape of the toilet cleaning block ensures even rinsing, allowing it to essentially retain its spherical shape even during and after flushing and subsequent wear. It has been shown that a high sphericity (Ψ) of the cleaning block at the start of the flushing process is particularly crucial for maintaining its spherical shape during and after flushing.

[0060] The diameter of the spherical toilet block is preferably between 1 mm and 10 cm, preferably between 5 mm and 5 cm, and particularly preferably between 1 cm and 3 cm.

[0061] The toilet cleaning block is placed in a dispensing device, which is attached to the rim of the toilet bowl with a holder. Suitable options include baskets with a flush water distribution element, as described in prior art, for example in DE 102008037723, which can hold one or more toilet cleaning blocks. These are explained in more detail below. Alternatively, one or more open plates, on which one or more toilet cleaning blocks are fixed, can also be used. Together, the toilet cleaning block and the dispensing device form a system.This can therefore be used in a process for cleaning and / or scenting and / or disinfecting flush toilets in such a way that the dispensing device filled with the toilet cleaning block is hung in the toilet bowl and when the toilet is flushed, dissolved ingredients of the toilet cleaning block enter the flushing water and can exert their cleaning and / or scenting and / or disinfecting effect there.

[0062] The toilet cleaning block is manufactured using a process that includes the following steps: a) Mixing the ingredients, b) Extrusion of the mixture, c) Cutting the extruded strand into portions of a defined mass, d) Deformation into rotationally symmetric bodies This includes the following steps. The deformation process (d) preferably takes place in a ball rolling machine or a press. Other suitable shaping methods are casting and calendering. Steps (a) and (b) can also be combined, i.e., mixing the ingredients in an extruder.

[0063] It is particularly preferred if the toilet cleaning block has a spherical shape with a sphericity Ψ between 0.8 and 1, particularly preferably between 0.85 and 1, most preferably between 0.9 and 1. Examples of implementation

[0064] Recipes 1 to 5 were produced.

[0065] The compositions are shown in the table below and serve as comparative examples. All quantities are given in wt.%.

[0066] The comparison examples V1 to V5 are uncoated: V1 V2 V3 V4 V5 C 10-13 -lin. Alkylbenzenesulfonate-Na 26 -- 12,4 21 -- Fatty alcohol sulfate sodium -- 7,4 -- -- -- C 12 - Fatty alcohol sulfate-Na - 17,4 12,4 -- -- C 14-16 -Olefinsulfonate-Na 18 -- -- 23 20 C 16-18 fatty alcohol ethoxylate 25 EO 8 17 17 -- 17 Cellulose -- 3 -- -- -- Trisodium citrate dihydrate 1 2 2 0,3 2 Sodium sulfate ad 100 ad 100 ad 100 ad 100 ad 100 Sodium carbonate -- 0,95 0,95 -- 0,95 C12-18 fatty acid monoethanolamide -- 8 15 -- 15 Sodium silicate -- -- -- 3 -- perfume 4,5 4 4,5 4,5 4,5 dye + + + + +

[0067] The compositions E1 to E5 according to the invention are shown in the following table and represent the examples according to the invention. All quantities are given in wt.%. In the case of the examples according to the invention, the cleaning agent molds were coated with a PVOH film. E1 E2 E3 E4 E5 C 10-13 -lin. Alkylbenzenesulfonate-Na 26 -- 12,4 21 -- Fatty alcohol sulfate sodium -- 7,4 -- -- -- C 12 - Fatty alcohol sulfate-Na - 17,4 12,4 -- -- C 14-16 -Olefinsulfonate-Na 18 -- -- 23 20 C 16-18 fatty alcohol ethoxylate 25 EO 8 17 17 -- 17 Cellulose -- 3 -- -- -- Trisodium citrate dihydrate 1 2 2 0,3 2 Sodium sulfate ad 100 ad 100 ad 100 ad 100 ad 100 Sodium carbonate -- 0,95 0,95 -- 0,95 C12-18 fatty acid monoethanolamide -- 8 15 -- 15 Sodium silicate -- -- -- 3 -- perfume 4,5 4 4,5 4,5 4,5 dye + + + + +

[0068] A system consisting of packaging, toilet cleaning blocks according to the preceding comparative examples and examples, and a dispensing device was provided, wherein the packaging has a back made of paper or cardboard and the front is partially free of packaging. This allowed for a clear view of the toilet cleaning blocks. After two weeks, comparative examples V1 to V5 had essentially lost their fragrance. In contrast, the fragrance was still substantially retained in the coated examples E1 to E5 according to the invention.

[0069] Since the front is at least partially free of packaging, allowing a view of the cleaning agent block through the cutout portion, and the toilet cleaning block is in contact with its surroundings, diffusion of substances into the environment can occur. In particular, volatile perfume oils can escape. According to the invention, this is prevented by the toilet cleaning block having a coating, especially a transparent film, particularly a PVA film, since such a PVA film is essentially transparent and thus preserves the visual impression at the time of purchase. Therefore, the combination of the toilet cleaning block with a water-soluble film in the packaging described above is particularly significant according to the invention.Only through this combination can the fragrance and visual appearance of the toilet cleaning blocks be preserved while using more ecologically advantageous packaging.

[0070] The coated cleaning agent molds are therefore particularly suitable for packaging with a cardboard back and a front that is essentially free of plastic packaging.

Claims

1. System comprising: at least one toilet cleaning block containing perfume, characterized in that the toilet cleaning block has a coating, wherein the coating consists of a water-soluble film;a dispensing device comprising the at least one toilet cleaning block; andpackaging for the dispensing device, comprising a back side and a front side wherein the front side is at least partially free of packaging, in that the front side of the packaging has a recessed, packaging-free part, whereby the cleaning agent molded body is visible, wherein the back side of the packaging comprises paper or cardboard.

2. System according to claim 1, characterized in that the coating consists of a water-soluble film comprising PVOH.

3. System according to one of claims 1 or 2, characterized in that it contains 10 to 70 wt.%, preferably 20 to 65 wt.%, particularly preferably 20 to 30 wt.% alkylbenzenesulfonate and 10 to 30 wt.%, preferably 15 to 30 wt.%, more preferably 15 to 25% by weight olefin sulfonate.

4. System according to one of claims 1 to 3, characterized in that the toilet cleaning block comprises a nonionic surfactant, preferably a fatty alcohol alkoxylate.

5. System according to claim 4, characterized in that the fatty alcohol alkoxylate is preferably contained in amounts of up to 20% by weight, particularly preferably 4 to 12% by weight, especially 7 to 9% by weight.

6. System according to one of the preceding claims, characterized in that it contains further surfactants, preferably selected from the group comprising fatty alcohol sulfates, fatty acid monoalkanolamides, fatty alcohol ether sulfates, alkanesulfonates, and mixtures thereof.

7. System according to one of the preceding claims, characterized in that it contains one or more further ingredients selected from the group comprising acids, bases, salts, thickeners, antimicrobial agents, preservatives, complexing agents, dyes, fillers, builders, bleaching agents, corrosion inhibitors, rinse regulators, enzymes, microorganisms, biofilm removal agents, limescale inhibition agents, dirt adhesion reduction agents, and mixtures thereof.

8. System according to one of the preceding claims, characterized in that the toilet cleaning block has a spherical shape with a sphericity Ψ between 0.8 and 1, in particular preferably between 0.85 and 1, and most preferably between 0.9 and 1.

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