Toilet block with improved shine

Description

[0001] The invention relates to a toilet cleaning block, a system comprising such a toilet cleaning block and its use.

[0002] In particular, spherical toilet blocks are enjoying increasing popularity. It has been found that using a surfactant system in sufficiently large quantities, especially over 50 percent by weight of the total composition, leaves an aesthetically pleasing shine on the surface of the toilet bowl.

[0003] However, from an economic and ecological perspective, it is desirable to reduce the total amount of surfactant in the composition. However, reducing the amount of the surfactant system results in a less appealing visual gloss impression on the toilet surface.

[0004] Toilet blocks comprising polymers are known from DE 43 14 659 A1.

[0005] It was therefore an object of the present invention to provide a way to leave an attractive optical shine on the surface of the toilet.

[0006] This is achieved by using a system comprising a dispenser and at least two toilet blocks arranged in a row next to each other for improving shine in a toilet bowl, wherein the toilet block comprises a surfactant system and comprises a polymer, and wherein the surfactant system is present in an amount of less than 50% by weight in the total composition, and wherein the polymer is an acrylate-based polymer.

[0007] The use of an economical and ecological toilet block is provided, which leaves an attractive visual shine on the surface of the toilet.

[0008] According to the invention, the polymer is an acrylate-based polymer.

[0009] Because the polymer is an acrylate-based polymer, it reliably leaves a shine on the surface of the toilet bowl.

[0010] According to a preferred embodiment, a toilet block is described for use according to the invention, wherein the toilet block essentially has a spherical geometry. Uniform wetting of the surface of the toilet bowl is particularly possible if the toilet block has good flushing properties. The spherical geometry allows the toilet block to be flushed evenly, with the polymer being applied to the surface of the toilet bowl.

[0011] According to a preferred embodiment, a toilet block is described in the use according to the invention, wherein the surfactant system is present in an amount of less than 40% by weight in the total composition.

[0012] According to a preferred embodiment, a toilet block is described in the use according to the invention, wherein the composition comprises at least one anionic surfactant, wherein the total amount of anionic surfactant is preferably less than 40% by weight.

[0013] According to a further preferred embodiment, a toilet block is described in the use according to the invention, wherein the composition comprises at least one alkylbenzenesulfonate as anionic surfactant, wherein the total amount of anionic surfactant is less than 40% by weight and the amount of alkylbenzenesulfonate is preferably less than 25% by weight.

[0014] According to a further preferred embodiment, a toilet block is described in the use according to the invention, wherein the composition comprises at least one olefin sulfonate as anionic surfactant, wherein the total amount of anionic surfactant is less than 40% by weight and the amount of olefin sulfonate is preferably less than 15% by weight.

[0015] According to a further preferred embodiment, a toilet block is described in the use according to the invention, wherein the composition comprises at least one olefin sulfonate and at least one alkylbenzenesulfonate as anionic surfactant, wherein the total amount of anionic surfactant is less than 40 wt.% and the amount of alkylbenzenesulfonate is preferably less than 25 wt.% and the amount of olefin sulfonate is preferably less than 15 wt.%.

[0016] According to a preferred embodiment, a toilet block is described in the use according to the invention, wherein the composition comprises a non-ionic surfactant in an amount of less than 8% by weight.

[0017] According to a further preferred embodiment, a toilet block is described in the use according to the invention, wherein the composition comprises at least one olefin sulfonate and at least one alkylbenzenesulfonate as anionic surfactant, wherein the total amount of anionic surfactant is less than 40 wt.% and the amount of alkylbenzenesulfonate is preferably less than 25 wt.% and the amount of olefin sulfonate is preferably less than 15 wt.% and wherein the composition comprises a non-ionic surfactant in an amount of less than 8 wt.%.

[0018] According to a preferred embodiment, a system is described in the described use for improving shine, comprising a dispensing device and at least three and more preferably at least four of the toilet blocks, and these more preferably at least three and more preferably at least four toilet blocks are arranged next to one another in a row.

[0019] Uniform and, in particular, complete wetting of the toilet bowl surface is particularly possible when the flushing water is applied to as large a portion of the toilet bowl surface as possible. This is made possible by arranging at least two, more preferably at least three, and even more preferably at least four toilet blocks in a row next to one another. Arranging several toilet blocks in a row is particularly preferred, as this creates a broad "water front" with dissolved toilet block composition, which can wet as large a portion of the toilet bowl surface as possible. It is particularly preferred if the toilet blocks also have a spherical geometry, as this also exhibits particularly good flushing behavior.

[0020] The toilet cleaning block according to the invention can be produced in a process comprising the steps of mixing the ingredients, extruding the mixture, cutting the extruded strand into portions of a defined mass and deforming into rotationally symmetrical bodies.

[0021] For the production of a rotationally symmetrical toilet cleaning block containing perfume, non-ionic surfactant, alkylbenzenesulfonate and olefinsulfonate, a process is suitable comprising the steps a) Mixing of the ingredients, b) Extrusion of the mixture, c) Cutting of the extruded strand into portions of a defined mass, d) Deformation into rotationally symmetrical bodies.

[0022] The system 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 in such a way 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.

[0023] Substances that also serve as ingredients in cosmetic products are referred to below, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds bear an INCI name in English; plant ingredients are listed exclusively in Latin according to Linnaeus. 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. This INCI name contains more than 9,000 INCI names as well as references to more than 37,000 trade names and technical names, including the associated distributors, from over 31 countries.The International Cosmetic Ingredient Dictionary and Handbook assigns the ingredients one or more chemical classes, for example, polymeric ethers, and one or more functions, for example, surfactants - cleansing agents, which it explains in more detail and to which reference may also be made below.

[0024] The CAS designation means that the following sequence of numbers is a designation of the Chemical Abstracts Service.

[0025] In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless stated otherwise - represent branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms, extremely preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The former are particularly preferred for ecological reasons because of their plant-based nature as they are based on renewable raw materials, without, however, limiting the teaching of the invention to them. In particular, the oxo alcohols or oxo alcohols obtainable, for example, by the Roelen oxo synthesis are also suitable.their derivatives having preferably 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, particularly preferably 9 to 17 carbon atoms, extremely preferably 11 to 15 carbon atoms, for example 9 to 11, 12 to 15 or 13 to 15 carbon atoms, can be used accordingly. perfume

[0026] The agent contains one or more fragrances, preferably in an amount of 0.01 to 10 wt.%, in particular 0.05 to 8 wt.%, particularly preferably 0.1 to 5 wt.%. d-Limonene can be included as a perfume component. In a particularly preferred embodiment, the toilet cleaning block according to the invention contains a perfume made from essential oils. Examples of suitable fragrances within the meaning of this invention include pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil. 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.

[0027] To be perceptible, a fragrance must be volatile, whereby, in addition to the nature of the functional groups and the structure of the chemical compound, the molecular mass also plays an important role. Most fragrances have molecular masses of up to about 200 Daltons, while molecular masses of 300 Daltons and above are rather rare. Due to the varying volatility of fragrances, the scent of a perfume composed of several fragrances changes during evaporation. The olfactory impressions are divided into "top note," "middle note" (body), and "base note" (end note) (dry out).

[0028] Adhesive fragrances that can be advantageously 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 blossom oil, basil oil, bay oil, champaca blossom oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, gingergrass 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, copaïva 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, palmarosa oil, Patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice 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.

[0029] However, the higher-boiling or solid fragrances of natural or synthetic origin can also be used advantageously as adherent fragrances or fragrance mixtures in the perfume oils within the scope of the present invention. These compounds include the following compounds and mixtures thereof: Ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester, 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, heptynecarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamal alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmone, 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, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyl acetal, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester, santalol, skatole, terpineol, thymene, thymol, γ-Undelactone, Vanilin, Veratrumaldehyde, Cinnamaldehyde, Cinnamyl alcohol, Cinnamic acid, Cinnamic acid ethyl ester, Cinnamic acid benzyl ester.

[0030] The more volatile fragrances that can be advantageously used in perfume oils within the scope of the present invention include, in particular, lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, and citronellal. Surfactants

[0031] The toilet cleaning block according to the invention contains at least one nonionic surfactant, at least one alkylbenzenesulfonate, and at least one olefinsulfonate. Other surfactants may also be present.

[0032] Among the alkylbenzenesulfonates, those with approximately 12 carbon atoms in the alkyl moiety are particularly preferred, such as linear sodium C10-13 alkylbenzenesulfonate. Preferred olefinsulfonates have a carbon chain length of 14 to 16. The toilet cleaning block according to the invention preferably contains 10 to 70 wt.%, preferably 20 to 65 wt.%, particularly preferably 20 to 30 wt.% of alkylbenzenesulfonate and preferably 10 to 30 wt.%, preferably 15 to 30 wt.%, particularly preferably 15 to 25 wt.% of olefinsulfonate. Non-ionic surfactants

[0033] 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 and hydroxy mixed ethers, and fatty acid polyglycol esters. Ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers can also be used. Another important class of nonionic surfactants that can be used according to the invention are polyol surfactants, particularly glycosurfactants 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.

[0034] Preferred fatty alcohol alkoxylates are unbranched or branched, saturated or unsaturated C8-22 alcohols alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO) and having a degree of alkoxylation of up to 30, preferably ethoxylated C12-22 fatty alcohols having a degree of ethoxylation of less than 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example C16-18 fatty alcohol ethoxylates with 25 EO.

[0035] Alkyl polyglycosides are surfactants that can be obtained by the reaction of sugars and alcohols using the relevant methods of preparative organic chemistry, resulting in a mixture of monoalkylated, oligomeric, or polymeric sugars, depending on the type of preparation. Preferred alkyl polyglycosides are alkyl polyglucosides, with the alcohol particularly preferably being 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 sugar being between 1 and 10, preferably 1 to 6, in particular 1.1 to 3, and most preferably 1.1 to 1.7, for example C8-10 alkyl 1,5-glucoside (DP of 1.5).

[0036] Fatty alcohol ethoxylates are preferably 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.%. Other anionic surfactants

[0037] Other anionic surfactants that may be present 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, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lignin sulfonates. 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-sulfofatty acid salts, acylglutamates, monoglyceride disulfates, and alkyl ethers of glycerol disulfate.

[0038] 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, whereas fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. In this context, the skilled person generally understands alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably with longer-chain alcohols within the meaning of the present invention. Depending on the reaction conditions, n moles of ethylene oxide and one mole of alcohol generally form a complex mixture of addition products with varying degrees of ethoxylation. A further embodiment of the alkoxylation involves the use of mixtures of alkylene oxides, preferably a 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.

[0039] 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.

[0040] In addition to the surfactant types mentioned above, the agent according to the invention may also contain cationic surfactants and / or amphoteric surfactants.

[0041] Suitable amphoteric surfactants are, for example, betaines of the formula (R <iii> )(R <iv> )(R <v>)N<+>CH2COO<->, in which R <iii>an alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R <iv>and R <v>identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C10-C18 alkyldimethylcarboxymethylbetaine and C11-C17 alkylamidopropyldimethylcarboxymethylbetaine.

[0042] Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R <vi> )(R <vii> )(R <viii> )(R <ix>)N<+>X<->, in which R <vi>to R <ix>represent four identical or different, in particular two long-chain and two short-chain, alkyl radicals and X<-> represents an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof. Other ingredients

[0043] In addition to the components mentioned above, the toilet cleaning block according to the invention can contain other ingredients commonly used in toilet cleaning blocks, preferably selected from the group comprising acids, bases, salts, thickeners, antimicrobial agents, preservatives, complexing agents, polymers, dyes, fragrances, perfume boosters, fillers, builders, bleaching agents, corrosion inhibitors, flush regulators, enzymes, microorganisms, biofilm removal agents, limescale inhibition agents, dirt adhesion reduction agents, processability improvement agents, stickiness reduction agents, and mixtures thereof. The total amount of other ingredients should not exceed 60% by weight, preferably 0.01 to 60% by weight, in particular 0.2 to 15% by weight. Acids

[0044] Toilet cleaning blocks according to the invention can contain one or more acids and / or their salts to enhance their cleaning performance against limescale and urine scale. The acids are preferably produced from renewable raw materials. Particularly suitable acids are therefore 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 amidosulfonic acid or mixtures thereof, can also be used. The acids and / or their salts are particularly preferably selected from the group comprising citric acid, lactic acid, formic acid, their salts, and mixtures thereof. They are preferably used in amounts of 0.01 to 10 wt.%, particularly preferably 0.2 to 5 wt.%.

[0045] In addition, in a preferred embodiment, the agent contains inorganic salts, preferably alkali or alkaline earth metal salts, in particular carbonates, sulfates, halides or phosphates, and mixtures thereof. Particular preference is given to using sodium sulfate and / or sodium carbonate. Sodium sulfate can be present in an amount of up to 60 wt.%, preferably 0.01 to 60 wt.%, particularly preferably 20 to 60 wt.%, in particular 35 to 55 wt.%. Sodium carbonate and other salts can be present in an amount of up to 30 wt.%, preferably up to 10 wt.%, particularly preferably up to 5 wt.%. Bases

[0046] Alkalis may also be present in agents according to the invention. Bases preferably used in agents according to the invention are those from the group of alkali and alkaline earth metal hydroxides and carbonates, especially 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

[0047] Disinfection and sanitation represent a special form of cleaning. In a corresponding special embodiment of the invention, the toilet cleaning block therefore contains one or more antimicrobial active ingredients, preferably in an amount of 0.01 to 1% by weight, preferably 0.02 to 0.8% by weight, in particular 0.05 to 0.5% by weight, particularly preferably 0.1 to 0.3% by weight, extremely preferably 0.2% by weight.

[0048] The terms disinfection, sanitation, antimicrobial effect, and antimicrobial agent have the usual technical meaning within the context of the teaching of the invention. While disinfection in the narrower sense of medical practice means the killing of – theoretically all – infectious germs, sanitation is understood to mean the elimination of all germs as far as possible – including saprophytic germs that are normally harmless to humans. The extent of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial agent content or increasing dilution of the agent used.

[0049] Suitable according to the invention are, for example, antimicrobial active ingredients from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides,

[0050] 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 surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butyl carbamate, iodine, iodophores, active chlorine-releasing compounds and peroxides.Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine) dihydrochloride, N,N'-Bis-(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary 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, antimicrobially active essential oils can also be used, which also provide a fragrance for the cleaning agent. However, particularly preferred antimicrobial active ingredients are selected from the group comprising salicylic acid, quaternary surfactants, especially benzalkonium chloride, peroxo compounds, especially hydrogen peroxide, alkali metal hypochlorite, sodium dichloroisocyanurate, and mixtures thereof. Preservatives

[0051] Preservatives can also be included in toilet cleaning blocks according to the invention. Essentially, the substances mentioned under antimicrobial active ingredients can be used as such. Complexing agents

[0052] Chelating agents (INCIChelating agents), also called sequestering agents, are ingredients capable of complexing and inactivating metal ions to prevent their adverse effects on the stability or appearance of the product, such as cloudiness. On the one hand, it is important to complex the calcium and magnesium ions that cause water hardness, which are incompatible with many ingredients. On the other hand, complexing the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished product. Furthermore, the complexing agents support the cleaning effect.

[0053] Geeignet sind beispielsweise die folgenden gemäßINClbezeichneten 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., Polymers

[0054] The WC cleaning block according to the invention can furthermore contain polymers. These can serve, for example, to reduce scale formation and the tendency to recontamination.

[0055] Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol. Fragrances and dyes

[0056] The toilet cleaning block according to the invention can contain one or more fragrances and / or one or more dyes (INCI colorants) as additional ingredients. Both water-soluble and oil-soluble dyes can be used as dyes, whereby compatibility with other ingredients, such as bleaching agents, must be taken into account, and the dye used should not have a substantive effect on the toilet ceramic, even after prolonged contact. The dyes are preferably present in an amount of 0.0001 to 0.1 wt.%, in particular 0.0005 to 0.05 wt.%, particularly preferably 0.001 to 0.01 wt.%. Builder

[0057] Water-soluble and / or water-insoluble builders can be used in the toilet cleaning blocks according to the invention. Water-soluble builders are preferred, as they generally have less tendency to leave insoluble residues on hard surfaces. Common builders that can be present in the context of the invention are 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

[0058] According to the invention, bleaching agents can be added to the cleaning agent. Suitable bleaching agents include peroxides, peracids, and / or perborates; hydrogen peroxide is particularly preferred. 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 circumstances, a bleach activator may also be required in addition to the bleaching agent. Corrosion inhibitors

[0059] Geeignete Korrosionsinhibitoren (INCICorrosion Inhibitors) sind beispielsweise folgende gemäßINClbenannte 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

[0060] The substances known as rinse regulators primarily serve to control the consumption of the detergent during use so that the intended service life is maintained. Suitable regulators are preferably solid long-chain fatty acids, such as stearic acid, but also salts of such fatty acids, fatty acid ethanolamides, such as coconut fatty acid monoethanolamide, or solid polyethylene glycols, such as those with molecular weights between 10,000 and 50,000. Active ingredients to reduce stickiness

[0061] To improve processability during the production of the toilet cleaning block according to the invention, an active ingredient can be added to reduce stickiness. For example, the addition of dolomite powder or titanium dioxide powder with a fine particle size distribution improves processing behavior during ball forming and significantly reduces abrasion and stickiness.

[0062] The results with such agents are better than with other common measures, such as coating the balls with a lubricant, powdering them or coating the forming rollers with Teflon. Enzymes

[0063] The agent may also contain enzymes, preferably proteases, lipases, amylases, hydrolases, and / or cellulases. They can be added to the agent according to the invention in any form established according to the prior art. These include solutions of the enzymes, advantageously as concentrated as possible, low in water, and / or containing stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray-drying or extrusion of the enzyme solution together with a, preferably natural, polymer, or in the form of capsules, for example those in which the enzymes are enclosed as if in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers.Such capsules are applied using conventional methods, for example, by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example, through the application of polymeric film formers, are low in dust and, due to the coating, are storage-stable.

[0064] Furthermore, enzyme stabilizers may be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention from damage such as inactivation, denaturation or degradation, for example due to physical influences, oxidation or proteolytic cleavage.Particularly suitable enzyme stabilizers, depending on the enzyme used, are: 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-, triethanol- and -propanolamine and mixtures thereof; aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of the acids mentioned; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; as well as reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other 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. Multi-layer toilet cleaning blocks

[0065] From the prior art, for example EP 791047B1, it is known to produce toilet cleaning blocks from masses of different compositions, wherein one of the masses is completely or partially enclosed by the other mass(es). For example, the inner mass can have a higher perfume concentration than the outer one in order to ensure a consistent fragrance impression over the period of use as the ball mass decreases, or the inner mass contains a different fragrance than the outer one. In addition, other active ingredients can be incorporated into different layers, which are released at different times depending on the degree of rinsing. Such a layered structure is also possible with the toilet cleaning block according to the invention.

[0066] The almost ideal spherical shape of the toilet cleaning block ensures even flushing, meaning the toilet cleaning block essentially retains its spherical shape even during and after the flushing process and the corresponding wear of the toilet cleaning block. It has been shown that a high sphericity Ψ of the toilet cleaning block at the beginning of the flushing water exposure is particularly crucial for maintaining the spherical shape during and after the flushing process.

[0067] The diameter of the spherical toilet block is preferably between 1 mm and 10 cm, preferably between 5 mm and 5 cm, particularly preferably between 1 cm and 3 cm.

[0068] The toilet cleaning block is inserted into a dispensing device, which is attached to the rim of the toilet bowl with a holder. Suitable for this purpose are, on the one hand, baskets with a flush water distribution element, as already described in the prior art, for example in DE 102008037723, which can accommodate one or more toilet cleaning blocks. Together, the toilet cleaning block according to the invention and the dispensing device form a system. This can accordingly be used in a method 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 suspended in the toilet bowl, and when the toilet is flushed, dissolved ingredients of the toilet cleaning block enter the flush water, where they can exert their cleaning and / or scenting and / or disinfecting effect.

[0069] In a preferred embodiment, the toilet basket according to the invention is provided with a child-resistant closure to prevent improper use of the spherical toilet cleaning blocks according to the invention.

[0070] The toilet cleaning block according to the invention is manufactured in a process 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. The deformation takes place d) preferably in a ball rolling machine or a press. Other suitable shaping processes are casting and calendering. Steps a) and b) can also be combined, i.e., mixing the ingredients in an extruder. The process steps may take place at different temperatures, so heating or cooling steps can be interspersed between the steps. These are at the discretion of the person skilled in the art.

[0071] In a preferred embodiment, a further process step is performed following one of steps b) or c), in which the extruded strand is provided with a lubricant. For this purpose, a sponge in the form of an impeller, permanently impregnated with the lubricant, is guided over the extruded strand in such a way that the surface is fully or partially coated with lubricant, preferably to a level of 10 to 40%. The addition of the lubricant improves the subsequent spheroidization.

[0072] Suitable lubricants are, in particular, substances used, for example, as surfactants or rinse regulators in formulations according to the invention. Particular preference is given to using a lubricant selected from the group comprising dipropylene glycol, paraffins, nonionic surfactants, polyethylene glycols, and mixtures thereof, in particular dipropylene glycol.

[0073] 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

[0074] A toilet cleaning block according to the invention was produced using formulation E1. In addition, other non-inventive formulations C1 and C2 were produced. For all compositions, experiments were conducted to extrude the mixtures, cut pieces of a defined mass from the extruded strand, and then form them into balls using a rolling machine.

[0075] The compositions E1, C1, and C2 can be found in the table below. All quantities are given in wt.%. Komponente C1 C2 E1 Alkyl Benzene Sulfonic Acid, Na-salt 26,00 22,10 22,10 Olefinsulfonat-Na C14-16 18,00 11,40 11,40 Fatty alcohol ethoxylate C16-18 25EO 8,00 6,00 6,00 Trisodium citrate dihydrate 1,00 0,80 0,80 Farbstoff <1 <1 <1 Perfume Out of The Blue 2017 <1 <1 <1 Mirapol Surf S 600 - - 0,1 Dipropylene glycol 0 0,3 0,3 Filler (Na2-Sulfat) Rest Rest Rest Glanz + - + Tensidgehalt - - +

[0076] Only the composition according to the invention was able to provide good gloss and had a low total surfactant content.< / ix> < / vi> < / ix> < / viii> < / vii> < / vi> < / v> < / iv> < / iii> < / v> < / iv> < / iii>

Claims

1. Use of a system comprising a dispensing device and at least two toilet blocks arranged in a row side by side for improving gloss in a toilet bowl, wherein the toilet block comprises a surfactant system and comprises a polymer, and wherein the surfactant system is present in an amount of less than 50 % by weight in the total composition, and wherein the polymer is an acrylate based polymer.

2. Use according to claim 1, wherein the toilet block has a substantially spherical geometry.

3. Use according to any one of the preceding claims, wherein the composition comprises an anionic surfactant in an amount of less than 40 % by weight.

4. Use according to any one of the preceding claims, wherein the composition comprises a non-ionic surfactant in an amount of less than 8 % by weight.