EP2638137B1 - Ball-shaped toilet blocks based on anionic surfactants - Google Patents

Description

The invention relates to a toilet cleaning block containing perfume, at least one alkylbenzenesulfonate and at least one olefinsulfonate and perfume , characterized in that the block contains one or more antimicrobial agents and not more than 2.5 wt .-% of nonionic surfactants and in a rolling machine or is formed of a press to a rotationally symmetrical, especially spherical body, and a system of at least one such a toilet cleaning block, and a delivery device. Furthermore, a method for its production is disclosed.

WC cleaning pieces, also known as WC bricks, have long been used for cleaning, disinfecting and scenting toilets under the edge of the pool (so-called rim blocks) as well as in the water tank (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-type or liquid scenters, some of which are offered in multi-compartment containers, thus allowing the combination of a cleaning agent which is dispensed upon actuation of the toilet flush with a permanent room fragrance.

In addition, however, the solid toilet blocks are still relevant. So far, these have mainly been produced by extrusion and then cut to give cuboid WC rim blocks, which were then inserted into corresponding baskets.

A disadvantage of these Rimblocks is that they swell by the penetrating into the basket rinse water, rinsed unevenly and lose their shape. After a short time, therefore, an unaesthetic block remains.

Another aspect that is becoming increasingly important in the WC area is hygiene. Consumers are increasingly asking for products that, in addition to the cleansing, also have a disinfecting effect. Chlorine carriers are suitable as disinfectants for solid WC bricks, but they are not stable in every formulation. So is in the off DE 102009003088 known composition containing a perfume, at least one nonionic surfactant and at least one alkylbenzenesulfonate and at least one olefinsulfonate, with additional use of a chlorine-containing disinfectant such as Dichloriscyanurat already short After production, a markedly reduced chlorine content is recorded, and after a relatively short period of use the chlorine content is only detectable in traces.

It was therefore desirable to formulate a shapely and aesthetic toilet block, which is rinsed evenly during its entire life and as little as possible swells. At the same time antimicrobial agents, especially chlorine-containing disinfectants should be stable incorporated.

Surprisingly, it has now been found that a formulation which contains perfume, at least one alkylbenzenesulfonate and at least one olefinsulfonate and does not contain more than 2.5% by weight of nonionic surfactants permits the stable incorporation of chlorine-containing antimicrobial agents. These WC bricks do not swell and always have a minimal surface due to their round shape. The rinsing therefore takes place uniformly, so that the original shape is retained even after a large number of rinsing off operations.

The invention therefore provides a toilet cleaning block containing perfume, at least one alkylbenzenesulfonate and at least one olefinsulfonate, characterized in that the block contains one or more antimicrobial agents and not more than 2.5 wt .-% of nonionic surfactants and in a roll machine or a press is formed into a rotationally symmetrical body. In particular, the production of spherical WC cleaning block with high sphericity is possible.

The toilet cleaning block according to the invention is usually used in a dispenser, such as a so-called toilet bowl. Another object of this invention is therefore a system comprising at least one toilet cleaning block according to the invention and a dispensing device.

The WC cleaning block of the present invention may be prepared in a process comprising the steps of mixing the ingredients, extruding the mixture, cutting the extruded strand into portions of defined mass, and deforming into rotationally symmetric bodies.

1. a) Mischen der Inhaltsstoffe,
2. b) Extrusion des Gemischs,
3. c) Schneiden des extrudierten Strangs in Portionsstücke einer definierten Masse,
4. d) Verformung zu rotationssymmetrischen Körpern; wird in der vorliegenden Beschreibung offenbart.

A method of making a rotationally symmetrical WC cleaning block containing perfume, nonionic surfactant, alkyl benzene sulfonate and olefin sulfonate comprising the steps

1. a) mixing the ingredients,
2. b) extrusion of the mixture,
3. c) cutting the extruded strand into portion pieces of a defined mass,
4. d) deformation to rotationally symmetrical bodies; is disclosed in the present specification .

The inventive system of the toilet cleaning block and the dispensing device can also be used in a method for cleaning and / or scenting and / or disinfecting Spül toilets such that the filled with the toilet block cleaning device is suspended in the toilet bowl and the Pressing the toilet flush dissolved ingredients of the toilet cleaning block get into the rinse water and there unfold their cleansing and / or fragrant and / or disinfecting effect.
Yet another subject of the invention is therefore a method for cleaning and / or scenting and / or disinfecting Spül toilets using a system of a toilet cleaning block according to the invention and a dispenser.

Substances which also serve as ingredients of cosmetic products are referred to below, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed only after Linne in Latin, 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), The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC, 20036, USA , which publishes more than 9,000 INCI names and references to more than 37,000 trade names and technical names, including related distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns the ingredients one or more chemical classes (Chemical Classes), for example, Polymeric ether, and one or more functions (functions), for example Surfactants - Cleansing Agents to, in turn, are explained in detail and subsequently to the possibly also referred to.

The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service .

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 bis 18 carbon atoms, most preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them. In particular, for example, according to the ROELEN's oxo synthesis available oxo alcohols or their derivatives having preferably 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, more preferably 9 to 17 carbon atoms, most preferably 11 to 15 carbon atoms, for example 9 to 11, 12 to 15 or 13 to 15 carbon atoms, respectively used.

Perfume

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 .-%. As a perfume component, d-limonene may be contained. In a particularly preferred embodiment, the toilet cleaning block according to the invention contains a perfume of essential oils (also referred to as essential oils). Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil, for example, can be used as such in the context of this invention. Also suitable are Muskateller sage oil, chamomile oil, lavender oil, clove oil, balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note or body" and "base note "(end note or dry out) divided.

Adhesive-resistant fragrances which are advantageously usable in the perfume oils in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, Bay oil, Champacablütenöl, Edeltannenöl, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce alder oil, galbanum oil, geranium oil, Ginger Grass Oil, Guajac Wood Oil, Gurjun Balm Oil, Helichrysum Oil, Ho Oil, Ginger Oil, Iris Oil, Cajeput Oil, Calam Oil, Camomile Oil, Camphor Oil, Kanaga Oil, Cardamom Oil, Cassia Oil, Pine Needle Oil, Kopaïva Balsam Oil, Coriander Oil, Spearmint Oil, Cumin Oil, Cumin Oil, Lemongrass Oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli oil, Niaouli oil, Olibanum oil, Origanum oil, Palmarosa oil, Patchouli oil, Peru balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Star aniseed oil, Thuja oil, Thyme oil, Verbena oil, Vetiver oil, Juniper berry oil, Vermouth oil, Wintergreen l, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil and cypress oil.

But the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention advantageously as adherent fragrances or

Fragrance mixtures are used in the perfume oils. These compounds include the following compounds and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, borneol, bornyl acetate, α-bromostyrene, n -Decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole , Jasmon, camphor, Karvakrol, Karvon, p-cresolmethyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone, methylchavikole, p-methylquinoline, methyl-β-naphthyl ketone, methyl-n-nonylacetaldehyde , Methyl n-nonyl ketone, muskon, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitroben zol, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyl acetal, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymene, Thymol, γ-undelactone, vaniline, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester.

Among the more volatile fragrances, which are advantageously used in the perfume oil in the context of the present invention, in particular the lower-boiling fragrances include natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

surfactants

The toilet cleaning block according to the invention contains at least one alkylbenzenesulfonate and at least one olefinsulfonate. In addition, other surfactants, in particular anionic surfactants may be included.

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

Other anionic surfactants

Other anionic surfactants which may be used in the WC cleaning block according to the invention are aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-C ₈ -C ₁₈ -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

Preferred in the context of the present invention are the fatty alcohol sulfates and / or fatty alcohol ether sulfates, in particular the fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, while fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols. As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. Another embodiment of the alkoxylation is the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Preferred fatty alcohol ether sulfates are the sulfates of lower ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO. In a preferred embodiment, the WC cleaning block according to the invention contains at least one fatty alcohol sulfate in an amount of up to 20 wt .-%, preferably 4 to 12 wt .-%, particularly preferably 7 to 10 wt .-%.

The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, eg Dodecylbenzenesulfonic.

Nonionic surfactants

For reasons of processability, it may be desirable for the inventive WC cleaning block to further contain nonionic surfactant. Suitable nonionic surfactants in the context of this invention are alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, Alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also suitable are block polymers of ethylene oxide and propylene oxide as well as fatty acid alkanolamides and fatty acid polyglycol ethers. Further important classes of nonionic surfactants which can be used according to the invention are the amine oxides and the sugar surfactants, in particular the alkyl polyglucosides.
The WC cleaning block according to the invention contains not more than 2.5% by weight of nonionic surfactants, advantageously those in particulate form. This is particularly important in the formulation of toilet cleaning blocks with chlorine-containing disinfectants, as these two components can react with each other. In a preferred embodiment, the WC cleaning block according to the invention is free of nonionic surfactants.

In addition to the previously mentioned types of surfactant, the agent according to the invention may also contain cationic surfactants and / or amphoteric surfactants.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyl-dimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix are} four identical or different, in particular two long and two short-chain, alkyl radicals and X- for an anion, in particular a halide ion, are, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Preference is given to quaternary ammonium compounds having an antimicrobial effect. In a particularly preferred embodiment, however, the WC cleaning block according to the invention is free of cationic surfactants.

Antimicrobial agents

A special form of cleaning provide disinfection and sanitation. Let D contains toilet cleaning block of the present invention, one or more antimicrobial active ingredients, preferably in an amount of up to 40 wt .-%, preferably 0.01 to 25 parts by weight %, in particular 0.1 to 5 wt .-%.

The terms disinfection, sanitation, antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention. While disinfection in the strict sense of the medical practice means the killing of - in theory all - infectious germs, under sanitation the greatest possible elimination of all - including the for the People usually harmless saprophytic - to understand germs. Here, the extent of disinfection or sanitation depends on the antimicrobial effect of the applied agent, which decreases with decreasing content of antimicrobial agent or increasing dilution of the agent for use.

For example, antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention Derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores, active chlorine releasing agents Compounds and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2 '. -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-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines, trichloroisocyanuric acid and sodium dichloroisocyanurate (DCI, 1,3-dichloro-5H-1,3,5-triazine-2,4,6-trione sodium salt). Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, antimicrobially effective essential oils can be used, which at the same time provide for a scenting of the cleaning agent. However, particularly preferred antimicrobial active ingredients are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular sodium percarbonate or phthalimidoperoxyhexanoic acid, alkali metal hypochlorite, trichloroisocyanuric acid, sodium dichloroisocyanurate and mixtures thereof. The WC cleaning block according to the invention very particularly preferably contains sodium dichloroisocyanurate.

Other ingredients

In addition to the components mentioned so far, the WC cleaning block according to the invention may comprise further ingredients usually used in toilet cleaning blocks, preferably selected from the group comprising acids, bases, salts, thickeners, preservatives, complexing agents, polymers, dyes, fragrances, perfume boosters, fillers, Builders, bleaching agents, corrosion inhibitors, Abspülregulatoren, enzymes, microorganisms, agents for biofilm removal, active ingredients for the inhibition of calcification, active ingredients for Reduction of soil adhesion, processability enhancing agents, tack reducing agents and mixtures thereof. Overall, not more than 60 wt .-% of further ingredients should be included, preferably 0.01 to 60 wt .-%, in particular 0.2 to 15 wt .-%.

acids

Toilet cleaning blocks according to the invention may contain one or more acids and / or salts thereof to enhance the cleaning performance against lime and urine stone. The acids are preferably produced from renewable raw materials. Suitable acids are therefore in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and mixtures thereof. In addition, however, it is also possible to use amidosulfonic acid. The acids and / or their salts are particularly preferably selected from the group comprising citric acid, lactic acid, sulfamic acid, their salts and mixtures thereof. They are preferably used in amounts of 0.01 to 10 wt .-%, particularly preferably 0.2 to 5 wt .-%. In a very particularly preferred embodiment, however, the WC cleaning block according to the invention is free of acids.

In addition, in a preferred embodiment, the composition contains inorganic salts, preferably alkali metal or alkaline earth metal salts, in particular carbonates, sulfates, halides or phosphates, and mixtures thereof. Particular preference is given to using sodium sulfate and / or sodium carbonate. Sodium sulfate may be present in an amount of up to 60 wt .-%, preferably 0.01 to 60 wt .-%, particularly preferably 20 to 60 wt .-%, in particular 35 to 55 wt .-%. Sodium carbonate and further salts may be present in an amount of up to 30% by weight, preferably up to 10% by weight, more preferably up to 5% by weight.

bases

In agents according to the invention, it is also possible for alkalis to be present. Suitable bases in agents according to the invention are preferably those from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide. In addition, however, it is also possible to use ammonia and / or alkanolamines having up to 9 C atoms in the molecule, preferably the ethanolamines, in particular monoethanolamine.

preservatives

Preservatives may also be included in toilet cleaning blocks according to the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.

complexing

INCI chelating agents, also called sequestrants, are ingredients that are capable of complexing and inactivating metal ions to prevent their detrimental effects on the stability or appearance of the agents, such as clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents. In addition, the complexing agents support the cleaning effect.

Suitable examples are the following according to INCI complexing agents: Aminotrimethylene Phosphonic Acid, Beta Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane diphosphonates , Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, S orodium dihydroxyethylglycinate, sodium EDTMP, sodium glutamate, sodium gluconate, sodium glycereth-1 polyphosphate, sodium hexametaphosphate, sodium metaphosphate, sodium metasilicate, sodium phytate, sodium polydimethylglycinophenolsulfonate, sodium trimetaphosphate, TEA-EDTA, TEA polyphosphate, tetrahydroxyethyl ethylene diamine, tetrahydroxypropyl ethylene diamine, 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

The toilet cleaning block according to the invention may further contain polymers. These can be used, for example, to reduce calcification and the tendency to re-soiling. Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol.

Fragrances and dyes

As further ingredients, the WC cleaning block according to the invention may contain one or more fragrances and / or one or more dyes ( INCI Colorants). As dyes both water-soluble and oil-soluble dyes can be used, on the one hand, the compatibility with other ingredients, such as bleaches, is observed and on the other hand, the dye used against the toilet ceramic should not be substantive even after prolonged exposure. The dyes are preferably present in an amount of 0.0001 to 0.1 wt .-%, in particular 0.0005 to 0.05 wt .-%, particularly preferably 0.001 to 0.01 wt .-%, contained.

Builder

If desired, water-soluble and / or water-insoluble builders can be used in the WC cleaning blocks according to the invention. Water-soluble builders are preferred because they tend to be less likely to leave insoluble residues on hard surfaces. Typical builders which may be present in the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the citric acid and its salts, the carbonates, phosphates and silicates. Water-insoluble builders include the zeolites, which may also be used, as well as mixtures of the aforementioned builders.

bleach

According to the invention, bleaching agents can be added to the cleaning agent. Suitable bleaching agents include peroxides, peracids and / or perborates, more preferably sodium percarbonate or phthalimidoperoxyhexanoic acid. On the other hand, chlorine-containing bleaching agents, such as trichloroisocyanuric acid or sodium dichloroisocyanurate, are less suitable for acid-formulated cleaning agents due to the release of toxic chlorine gas vapors, but they can be used in alkaline cleaning agents. Under certain circumstances, a bleach activator may be required in addition to the bleaching agent.

corrosion inhibitors

Suitable corrosion inhibitors ( INCI Corrosion Inhibitors) are, for example, the following named according to INCI substances: cyclohexylamine, diammonium phosphates, dilithium oxalates, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphate, Nitromethane, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl dimethicone, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, triisopropanolamine.

Abspülregulatoren

The designated as Abspülregulatoren substances serve primarily to control the consumption of funds during use so that the intended life is met. Suitable regulators are preferably solid long-chain fatty acids, such as stearic acid, but also salts of such fatty acids, fatty acid ethanolamides, such as coconut fatty acid monoethanolamide, or solid polyethylene glycols, such as those having molecular weights between 10,000 and 50,000.

Active ingredients to reduce stickiness

In order to improve the processability in the production of the toilet cleaning block according to the invention, a sticking-in reducing agent may be added. Thus, the addition of dolomite powder or titanium dioxide powder with a fine particle size distribution improves the processing behavior during spheroidization and significantly reduces abrasion or stickiness.

The results with such active ingredients are better than with other conventional measures, for example coating the balls with a lubricant, dusting or coating the forming rollers with Teflon.

enzymes

The agent may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They can be added to the composition according to the invention in any form established according to the prior art. These include solutions of the enzymes, preferably concentrated as possible, low in water and / or added with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in core-shelled form. Type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are known per se Methods, for example, by shaking or rolling granulation or applied in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating. In addition, enzyme stabilizers may be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention from damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage. Suitable enzyme stabilizers, in each case depending on the enzyme used, are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, for example substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known in the art. Preference is given to using combinations of stabilizers, for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

Multi-layer toilet cleaning blocks

From the prior art, for example EP 791047B1 , It is known to produce toilet cleaning blocks of different composition masses, wherein one of the masses of the other masses is completely or partially enclosed. Thus, for example, the inner mass may have a higher ParFum concentration than the outer, in order to ensure a constant fragrance impression with decreasing ball mass during the service life, or the inner mass contains a different fragrance than the outer. In addition, other active ingredients can be incorporated into different layers, which are released depending on the Abspülgrad at different times. Such a layered structure is also possible in the toilet cleaning block according to the invention.

sphericity

The WC cleaning block preferably has a sphericity Ψ between 0.8 and 1, particularly preferably between 0.85 and 1, very particularly preferably between 0.9 and 1.

wobei V_p das Volumen des Körpers und A_p seine Oberfläche bezeichnetThe sphericity Ψ of a body K is the ratio of the surface of the body to the surface of a sphere of equal volume: $$\mathrm{\Psi }=\frac{{\pi }^{\frac{1}{3}}{\left(6V_p\right)}^{\frac{2}{3}}}{A_p}.$$

where V _p denotes the volume of the body and A _p denotes its surface

Due to the almost ideal spherical configuration of the toilet cleaning block, a uniform rinsing of the toilet cleaning block is effected in such a way that the toilet cleaning block substantially maintains its spherical shape during or after the rinsing operations and a corresponding removal of the toilet cleaning block. It has been found that, in particular, a high sphericity Ψ of the WC cleaning block at the beginning of the rinsing-water application is decisive for maintaining the spherical shape during and after the rinsing-off operations. The formability of the mass and thus the possibility for optimal rounding can be adjusted by the addition of a small amount of liquid. In particular, water, dipropylene glycol or paraffin in an amount of 0.1 to 1 wt .-% can be used as liquids.

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

The toilet cleaning block is placed in a dispenser, which is attached with a holder on the toilet bowl edge. For a basket with Spülwasserverteilelement, as they are already known in the art, such as in DE 102008037723 On the other hand, one or more open plates, on which one or more WC cleaning blocks are fixed, are used. Together, inventive toilet cleaning block and dispensing device form a system. This can be used accordingly in a method for cleaning and / or scenting and / or disinfecting flushing toilets such that the filled with the toilet cleaning block dispenser is hung in the toilet bowl and dissolved in operating the toilet flushing ingredients of the toilet cleaning block in reach the rinse water and there unfold their cleansing and / or fragrant and / or disinfecting effect. Appropriate systems are in DE 102009003088 described.

1. a) Mischen der Inhaltsstoffe,
2. b) Extrusion des Gemischs,
3. c) Schneiden des extrudierten Strangs in Portionsstücke einer definierten Masse,
4. d) Verformung zu rotationssymmetrischen Körpern

umfasst. Dabei erfolgt die Verformung d) vorzugsweise in einer Kugelrollmaschine oder einer Presse. Weitere geeignete Formgebungsverfahren sind Gießen und Kalandrieren. Die Schritte a) und b) können auch kombiniert werden, also Mischen der Inhaltsstoffe im Extruder. Die Verfahrensschritte laufen gegebenenfalls bei unterschiedlichen Temperaturen ab, so dass zwischen den Schritten noch Heiz- oder Kühlschritte zwischengeschaltet sein können. Diese liegen im Ermessen des Fachmanns.The WC cleaning block according to the invention is produced in a process comprising the steps

1. a) mixing the ingredients,
2. b) extrusion of the mixture,
3. c) cutting the extruded strand into portion pieces of a defined mass,
4. d) deformation to rotationally symmetrical bodies

includes. The deformation d) is preferably carried out in a ball rolling machine or a press. Other suitable molding processes include casting and calendering. The steps a) and b) can also be combined, ie mixing of the ingredients in the extruder. If appropriate, the method steps take place at different temperatures, so that heating or cooling steps can still be interposed between the steps. These are at the discretion of the person skilled in the art.

In a preferred embodiment, a further process step is carried out following one of the steps b) or c), in which the extruded strand is provided with a lubricant. For this purpose, a permanent offset with the lubricant sponge in the form of an impeller is guided over the extruded strand that the surface is fully or partially, preferably 10 to 40%, applied with lubricant. The addition of the lubricant improves the subsequent spheroidal shaping.
As alternatives for the use of a sponge for strand lubrication, for example, simple dripping or spraying on, also dip wheels, plunge baths for belts or strands, etc. It can also be combined with different methods, such as diving a wheel through a lubricant bath and then rolling on the strand with the dripping.
In addition to the extruded strand and the rollers can be provided with the lubricant.

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

It is particularly preferred if the WC cleaning block receives a spherical shape with a sphericity Ψ between 0.8 and 1, particularly preferably between 0.85 and 1, very particularly preferably between 0.9 and 1.

embodiments

Three WC cleaning blocks according to the invention with formulations E1 to E4 and one comparative formulation V1 were prepared. The compositions are shown in the table below, all amounts in wt .-% of the active ingredient. E1 E2 E3 E4 V1 C _10-13 -lin. Alkylbenzenesulfonate Na 10 22 19 10 26 C _14-16 olefinsulfonate Na 20 10 10 20 18 C ₁₂ - fatty alcohol sulfate Na 10 9 10 7 - Sodium dichloroisocyanurate 2 hydrate 3.2 2.5 3.0 2 14.4 Trisodium citrate dihydrate 1.0 2.0 1.0 1 1 cellulose - - 1.0 - - sodium - - 5.0 - - sodium - 1.0 - - - Perfume 4.0 4.0 4.0 4 4.5 Titanium dioxide 0.5 - - 0.5 - C _16-18 fatty alcohol ethoxylate 25 EO - - - 2 8th Paraffin oil thin - - - 1 - sodium sulphate Ad 100 Ad 100 Ad 100 Ad 100 Ad 100

The too high content of the nonionic surfactant in the comparative formulation resulted in a large reduction of the chlorine content. Immediately after the preparation, the content dropped to 9.7%, after a service life of 48 hours and 43 rinses were still 3.4% of the chlorine carrier detectable. By contrast, the formulations according to the invention had lower decreases in the chlorine content, even in the case of the low-niotenside-containing formulation E4.

Claims (12)

1. A toilet cleaning block comprising perfume, at least one alkylbenzene sulfonate and at least one olefin sulfonate, characterized in that the block comprises one or more antimicrobial active ingredients and no more than 2.5 wt.% nonionic surfactants and is shaped in a rolling machine or press to form a spherical object.
2. The toilet cleaning block according to claim 1, wherein it comprises 10 to 70 wt.%, preferably 20 to 65 wt.%, particularly preferably 20 to 30 wt.%, alkylbenzene sulfonate.
3. The toilet cleaning block according to one of claims 1 and 2, wherein it comprises 10 to 30 wt.%, preferably 15 to 30 wt.%, particularly preferably 15 to 25 wt.%, olefin sulfonate.
4. The toilet cleaning block according to one of claims 1 to 3, wherein it comprises at least one further anionic surfactant.
5. The toilet cleaning block according to claim 4, wherein the at least one anionic surfactant is preferably a fatty alcohol sulfate and is preferably comprised in quantities of up to 20 wt.%, particularly preferably 4 to 12 wt.%, in particular 7 to 10 wt.%.
6. The toilet cleaning block according to one of the preceding claims, wherein it is free from nonionic surfactants.
7. The toilet cleaning block according to one of the preceding claims, wherein it comprises further surfactants, preferably selected from the group encompassing fatty alcohol ether sulfates, alkane sulfonates and mixtures thereof.
8. The toilet cleaning block according to one of the preceding claims, wherein the antimicrobial active ingredient or ingredients are preferably selected from the group encompassing salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular sodium percarbonate or phthalimido-peroxy-hexanoic acid, alkali metal hypochlorite, sodium dichloroisocyanurate and mixtures thereof, sodium dichloroisocyanurate being most particularly preferred.
9. The toilet cleaning block according to one of the preceding claims, wherein it comprises one or more further ingredients conventionally used in toilet cleaning blocks, preferably selected from the group encompassing acids, bases, salts, thickeners, preservatives, complexing agents, dyes, scents, perfume boosters, fillers, builders, bleaching agents, corrosion inhibitors, flush regulators, enzymes, microorganisms, active ingredients for biofilm removal, active ingredients for inhibiting limescale deposits, active ingredients for reducing soil adhesion and mixtures thereof.
10. The toilet cleaning block according to one of the preceding claims, wherein the toilet cleaning block has the shape of a ball with a sphericity Ψ of between 0.8 and 1, particularly preferably between 0.85 and 1, most particularly preferably between 0.9 and 1.
11. A system of at least one toilet cleaning block according to one of the preceding claims and a dispensing device.
12. A method for cleaning and/or perfuming and/or disinfecting flush toilets using a system according to claim 11.