HK1187362B - Ball-shaped toilet blocks based on anionic surfactants - Google Patents

Description

Spherical toilet cleaning block based on anionic surfactants

Technical Field

The invention relates to a toilet cleaning block, wherein the toilet cleaning block comprises perfume, at least one alkylbenzene sulfonate and at least one olefin sulfonate, and at least one other anionic surfactant, and the toilet cleaning block can be shaped in a roller press or press (press) to form a rotationally symmetric, in particular spherical, object; the invention also relates to a method for producing such a toilet cleaning block and to a system comprising at least one such toilet cleaning block and a dispensing device.

Background

Lavatory cleansing blocks, also known as lavatory cleansing blocks (toiletblock), have long been used for lavatory cleansing, disinfecting and perfuming under the rim of the lavatory bowl (so-called rim cleansing block) and in the cistern (cistern cleansing block or cistern cleansing block). In recent years, the importance of aesthetics and performance has increased. This has prompted the development of, for example, liquid or gel-state fresheners, which in some cases are sold in multi-chamber containers, thereby enabling the detergents released when flushing toilets to be combined with a long lasting room perfuming function.

However, solid toilet cleaning blocks are still suitable. To date, these solid toilet cleaning blocks have been made primarily by extrusion and then cutting to the required size to obtain a generally rectangular toilet rim cleaning block which is then used in an appropriate cage.

The disadvantage of these rim blocks is that they swell due to the flushing water flowing into the cage, so that they are flushed out unevenly and lose their original shape. Thus, even after a short time, an unattractive mass is formed.

Another aspect that has become increasingly important in the field of toilets is hygiene (hygiene). There is an increasing consumer demand for products that provide both disinfecting and cleaning benefits. For solid toilet blocks, chlorine carriers are one of the suitable disinfectants, but these cannot be incorporated into every formulation in a stable manner. Compositions known, for example, from DE102009003088 comprise perfume, at least one nonionic surfactant together with at least one alkylbenzene sulfonate and at least one olefin sulfonate, and additionally use chlorine-containing disinfectants (such as dichloroisocyanurate); a significant reduction in chlorine content was noted shortly after preparation of the composition and after a relatively short period of use, chlorine content could only be detected in trace amounts.

It is therefore desirable to formulate an aesthetically pleasing toilet cleansing block having a pleasing shape that is evenly flushed out and swells as little as possible over its entire life. At the same time, it should be possible to combine antimicrobial active ingredients, in particular chlorine-containing disinfectants, in a stable manner.

Disclosure of Invention

Surprisingly, it has now been found that formulations comprising perfume, at least one alkylbenzene sulphonate and at least one olefin sulphonate and not more than 2.5 wt% of a non-ionic surfactant can even stably incorporate chlorine-containing antimicrobial active components. These toilet cleaning blocks do not swell and, because they are round, they always present a minimum surface area. They are thus flushed out uniformly, whereby the original shape is retained even after a number of flushes.

The invention therefore provides a toilet cleaning block comprising perfume, at least one alkylbenzene sulphonate and at least one olefin sulphonate, the toilet cleaning block comprising not more than 2.5 wt% of a non-ionic surfactant and being capable of being formed into a rotationally symmetrical object in a roller press or a press. In particular, it is possible to manufacture a spherical toilet cleaning block having a high sphericity.

The toilet cleaning block of the present invention is typically used in a dispensing device, such as a so-called edge cleaning block cage. The invention therefore also provides a system comprising at least one toilet cleaning block according to the invention and a dispensing device.

The toilet cleaning block of the present invention can be manufactured in a method comprising the steps of: mixing the components, extruding the mixture, cutting the extruded strand into pieces of defined mass, and forming into a rotationally symmetrical object.

The present invention therefore also provides a method of manufacturing a rotationally symmetric toilet cleaning block comprising perfume, non-ionic surfactant, alkyl benzene sulphonate and olefin sulphonate, wherein the method comprises the steps of:

a) the components are mixed and then mixed together,

b) the mixture is extruded and the mixture is extruded,

c) the extruded strands are cut into pieces of defined mass,

d) shaped as a rotationally symmetric object.

The inventive system comprising a toilet cleaning block and a dispensing device can additionally be used in a method for cleaning and/or perfuming and/or disinfecting a toilet with a water-pumping device, since the dispensing device filled with the toilet cleaning block is suspended in the toilet bowl, and then when the toilet is flushed, the components dissolved in the toilet cleaning block pass into the flushing water and can exert their cleaning and/or perfuming and/or disinfecting action there.

The present invention therefore also provides a method of cleaning and/or fragrancing and/or disinfecting a lavatory having a water-closet bowl, the method employing a system comprising the lavatory cleansing block of the present invention and a dispensing device.

Detailed Description

Substances which are also components in cosmetic preparations may be mentioned below under the name of international cosmetic ingredient nomenclature (INCI, international nomenclatureof cosmetic ingredients). Chemical compounds have the english INCI name, plant components are listed by the Linnesystem (Linnesystem) in latin alone, and so-called trivial names such as "water", "honey" or "sea salt" are also listed in latin. The INCI name can be obtained from international cosmetic ingredient dictionary and handbook-seven edition (1997) published by the nwsuie 300, 1101 street the cosmetic, Toiletry, and france association (ctfa) in washington, d.c. 20036, usa, and contains over 9,000 INCI names and references to over 37,000 trade and technical names, including over 31 countries of the relevant distributors. The International cosmetic ingredients dictionary handbook classifies components into one or more chemical classes, such as Polymerics, and one or more functions, such as Surfactants-cleaning agents, which are defined in more detail and are also cited below.

Reference to CAS denotes the following numerical sequence number chemical abstracts service name.

Within the scope of the present invention, unless otherwise specified, a fatty acid or fatty alcohol, or a derivative thereof, represents a branched or linear carboxylic acid or alcohol, or a derivative thereof, preferably having from 6 to 22 carbon atoms, in particular having from 8 to 20 carbon atoms, particularly preferably having from 10 to 18 carbon atoms, very particularly preferably having from 12 to 16 carbon atoms, for example having from 12 to 14 carbon atoms. The former are preferred for ecological reasons, in particular because they are plant-based and thus based on sustainable raw materials, but the teaching of the present invention is not limited thereto. In particular, it is thus possible to use oxo alcohols or derivatives thereof (obtainable, for example, by oxo synthesis of ROELEN) preferably having from 7 to 19 carbon atoms, in particular from 9 to 19 carbon atoms, particularly preferably from 9 to 17 carbon atoms, very preferably from 11 to 15 carbon atoms, for example from 9 to 11, from 12 to 15 or from 13 to 15 carbon atoms.

Perfume

The substrate comprises one or more fragrances (gent) in an amount of preferably 0.01 to 10 wt.%, in particular 0.05 to 8 wt.%, particularly preferably 0.1 to 5 wt.%. As a perfume ingredient herein, d-limonene can be included. In a particularly preferred embodiment, the toilet cleaning block of the present invention comprises a perfume comprising an essential oil (also known as essential oil). For example, pine oil, lemon oil, jasmine oil, patchouli oil, rose oil, or ylang-ylang oil can be used as such an essential oil in the present invention. Also suitable are sage oil, chamomile oil, lavender oil, clove oil, melissa oil, peppermint oil, cinnamon leaf oil, linden flower oil, juniper oil, vetiver oil, frankincense oil, galbanum oil and labdanum oil, as well as neroli oil, orange peel oil and sandalwood oil.

For one to feel, the perfume must be volatile, where the molar mass plays an important role, together with the kind of functional groups and the structure of the chemical compounds. For example, most fragrances have molar masses of up to about 200 daltons, with more exceptions being given by molar masses above 300 daltons. The fragrance of a perfume containing several fragrances varies during volatilization due to the different volatility of the fragrances, and the effects of the fragrances are divided into "top note", "middle note or body note" and "bottom note or tail note".

Fragrance-enduring essences (tenacioufragrance) which can be advantageously used in the essential oils within the scope of the present invention are, for example, essential oils such as angelica root oil, fennel oil, arnica oil, basil oil, bay oil, ylang-ylang oil, collybia oil, elemi oil, eucalyptus oil, fennel oil, spruce oil, galbanum oil, geranium oil, ginger oil, guaiacum oil, gutta percha oil, helichrysum oil, aromatic oil, ginger oil, orris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, ylang oil, cardamom oil, cinnamon oil, pine needle oil, copaiba oil, coriander oil, spearmint oil, tarragon oil, cumin oil, vanilla oil, muskrainia oil, musk oil, clove oil, neroli oil, niaouli oil, origanum oil, sage oil, sweet pepper oil, patchouli oil, orange oil, peppermint oil, rose oil, patchouli oil, orange oil, rose, Pine oil, rosemary oil, sandalwood oil, celery oil, anise oil, ramie oil, thyme oil, verbena oil, vetiver oil, juniper oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon leaf oil, and cypress oil.

However, high-boiling or solid fragrances of natural or synthetic origin can also be advantageously used in essential oils within the scope of the present invention as fragrance-enduring fragrances or fragrance mixtures. These compounds include the following compounds and mixtures thereof: pelargonide, alpha-amylcinnamaldehyde, anise ether, anisaldehyde, anisyl alcohol, anisole, methyl anthranilate, methylphenylketone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, camphanol, bornyl acetate, alpha-bromostyrene, n-decanal, n-dodecanal, eugenol methyl ether, eucalyptol, farnesol, fenchyl ketone, fenchyl acetate, geraniol formate, erucin, methyl heptynecarboxylate, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, irilone, isoeugenol, isosafrole, jasmone, camphor, carvacrol, carvone, p-cresol, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilate, methyl eugenol, ethyl benzoate, benzyl, P-methylacetophenone, methyl zanthoxylum, p-methylquinoline, methyl- β -naphthalenone, methyl-n-nonyl acetaldehyde, methyl-n-nonyl ketone, musk ketone, β -naphthyl ether, β -naphthyl methyl ether, nerol, nitrobenzene, n-nonanal, nonanol, n-octanal, p-hydroxyacetophenone, cyclopentadecanolide, β -phenylethyl alcohol, phenylacetaldehyde dimethyl acetal, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, 3-methylindole, terpineol, thymol, γ -undecanoate, vanillin, veratraldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, and benzyl cinnamate.

The more volatile flavours that can be advantageously used in the essential oils within the scope of the present invention include in particular low boiling flavours 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, linalyl propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral and citronellal.

Surface active agent

The toilet cleaning block of the present invention comprises at least one alkylbenzene sulfonate and at least one olefin sulfonate. In addition, other surfactants, in particular anionic surfactants, can be included.

Of the alkylbenzene sulfonates, those having about 12C atoms in the alkyl moiety, e.g. linear C, are particularly preferred_10-13Sodium alkyl benzene sulfonate. Preferred olefin sulfonates have a carbon chain length of from 14 to 16. The toilet cleaning block of the invention preferably comprises from 10 to 70% by weight, preferably from 20 to 65% by weight, particularly preferably from 20 to 30% by weight, of alkylbenzene sulphonate; and preferably from 10 to 30% by weight, preferably from 15 to 30% by weight, particularly preferably from 15 to 25% by weight, of olefin sulfonate.

Other anionic surfactants

As other anionic surfactants, can be used in the present inventionAmong the clear toilet cleaning blocks are: fatty sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates; and aliphatic sulfonates such as alkylsulfonates, ether sulfonates, n-alkylether sulfonates, ester sulfonates and lignosulfonates. Also within the scope of the invention, fatty acid cyanamide (fattyacidcyanamide); sulfosuccinates (sulfosuccinates), in particular sulfosuccinic acid monoc₈-C₁₈-alkyl ester and sulfosuccinic acid bis-C₈-C₁₈-an alkyl ester; sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, amidoalkanesulfonates (fatty acid taurates), fatty acid sarcosinates, ethercarboxylic acids and alkyl (ether) phosphates, and also alpha-sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfates.

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 the products of the sulfation reaction of suitable alcohols, while fatty alcohol ether sulfates are the products of the sulfation reaction of alkoxylated alcohols. Those skilled in the art know that alkoxylated alcohols are typically the reaction product of an alkylene oxide, preferably ethylene oxide, and an alcohol, which in the present invention is preferably a long chain alcohol. Generally, depending on the reaction conditions, n moles of ethylene oxide react with 1 mole of alcohol to form a complex mixture containing addition products having different degrees of ethoxylation. Another embodiment of the alkoxylation consists in using mixtures of alkylene oxides, preferably mixtures comprising ethylene oxide and propylene oxide. Preferred fatty alcohol ether sulphates are sulphates of fatty alcohols having a low degree of ethoxylation, which sulphates have from 1 to 4 ethylene oxide units (EO), in particular from 1 to 2 EO, for example 1.3 EO. In a preferred embodiment, the toilet cleansing block of the invention comprises up to 20% by weight, preferably from 4 to 12% by weight, particularly preferably from 7 to 10% by weight, of at least one fatty alcohol sulfate.

The anionic surfactants are preferably used in the form of the sodium salts, but may also be included in the form of other alkali metal or alkaline earth metal salts, for example magnesium salts, but also ammonium or monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium salts and, for sulfonates, also in the form of their corresponding acids, for example dodecylbenzenesulfonic acid.

Nonionic surfactant

Because of processability, it is desirable that the toilet cleansing block of the present invention further comprises a nonionic surfactant. Suitable nonionic surfactants within the scope of the present 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 also fatty acid polyglycol esters. Also suitable are block copolymers of ethylene oxide and propylene oxide, and fatty acid alkanolamides and fatty acid polyglycol ethers. Other important classes of nonionic surfactants that can be used according to the invention are amine oxide and saccharide surfactants, in particular alkyl polyglucosides.

The toilet cleansing block of the present invention comprises no more than 2.5% by weight of nonionic surfactant, advantageously those in particulate form. This is particularly important in formulations with toilet cleaning blocks with chlorine-containing disinfectants, since these two components are able to react with one another. In a preferred embodiment, the toilet cleansing block of the present invention is free of nonionic surfactants.

In addition to the above types of surfactants, the substrate of the present invention can also contain cationic surfactants and/or amphoteric surfactants.

Suitable amphoteric surfactants are, for example, those of the formula (R)ⁱⁱⁱ)(R^iv)(R^v)N⁺CH₂COO^-In which R isⁱⁱⁱRepresents a radical having from 8 to 25 carbon atoms, preferably from 10 to 25 carbon atoms, optionally interrupted by a heteroatom or a heteroatom groupAn alkyl group of 21 carbon atoms; and R is^ivAnd R^vRepresents alkyl radicals having 1 to 3 carbon atoms, in particular C, of the same or different type₁₀-C₁₈Alkyl dimethyl carboxymethyl betaines and C₁₁-C₁₇Alkylamidopropyl dimethylcarboxymethylbetaine.

Suitable cationic surfactants are in particular those of the formula (R)^vi)(R^vii)(R^viii)(R^ix)N⁺X^-Wherein R is^viTo R^ixRepresents four identical or different alkyl groups, in particular two long-chain alkyl groups and two short-chain alkyl groups; and X^-Represents an anion, in particular a halide; the cationic surfactant is, for example, didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride, and mixtures thereof. Quaternary ammonium compounds having an antimicrobial action are preferred. However, in a particularly preferred embodiment, the toilet cleansing block of the present invention does not contain a cationic surfactant.

Antimicrobial active ingredient

The specific form of cleaning is represented by disinfection and hygiene. In a corresponding embodiment of the invention, the toilet cleansing block therefore comprises one or more antimicrobial active ingredients, preferably in an amount of up to 40% by weight, preferably from 0.01 to 25% by weight, in particular from 0.1 to 5% by weight.

The terms disinfecting, sanitizing, antimicrobial and antimicrobial active ingredients within the teaching of the present invention have the conventional technical meaning. Whereas disinfection in the narrow sense of medical practice means (theoretically total) killing of infectious microorganisms, hygiene is to be understood as the best possible killing of all microorganisms, even saprophytic microorganisms which are generally harmless to humans. The degree of disinfection or hygiene here depends on the antimicrobial action of the agents used, which decreases with decreasing content of antimicrobial active ingredient or increasing dilution of the applied agent.

Suitable according to the invention are, for example, antimicrobial active components selected from the group consisting of: alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, amides, phenols, phenol derivatives, biphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals (oxogenated nitrogenated aldaramids), 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-propynylbutylcarbamate, iodine, iodophors, compounds that release active chlorine and peroxides. Preferred antimicrobial active components are preferably selected from: 1, 3-butanediol, phenoxyethanol, 1, 2-propanediol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2' -methylenebis (6-bromo-4-chlorophenol), 2,4,4' -trichloro-2 ' -hydroxydiphenyl ether, N- (4-chlorophenyl) -N- (3, 4-dichlorophenyl) urine, N ' - (1, 10-decanediylbis-1-pyridinyl-4-ylidene) bis (1-octylamine) dihydrochloride, N ' -bis (4-chlorophenyl) -3, 12-diimino-2, 4,11, 13-tetrazazetanediiminamide (diimidide), Antimicrobial quaternary surface active compounds, guanidine, trichloroisocyanuric acid and sodium dichloroisocyanurate (DCI, 1, 3-dichloro-5H-1, 3, 5-triazine-2, 4, 6-trione sodium salt). Preferred antimicrobially active quaternary salt compounds contain ammonium, sulfonium, phosphonium, iodonium or arsonium groups. In addition, essential oils with antimicrobial activity that also provide the perfuming function of the cleanser can also be used. However, particularly preferred antimicrobial active components are selected from: salicylic acid; quaternary surfactants, especially benzalkonium chloride; peroxides, in particular sodium percarbonate or phthalimido peroxy caproic acid; an alkali metal hypochlorite; trichloroisocyanuric acid; sodium dichloroisocyanurate and mixtures thereof. Most particularly preferably, the toilet cleansing bar of the present invention comprises sodium dichloroisocyanurate.

Other Components

In addition to the above components, the toilet cleansing block of the invention can comprise further components conventionally used in toilet cleansing blocks, preferably selected from: acids, bases, salts, thickeners, preservatives, complexing agents, polymers, dyes, fragrances, fragrance synergists, fillers, builders, bleaches, corrosion inhibitors, rinse conditioners, enzymes, microorganisms, active ingredients for biofilm removal, active ingredients for preventing scale deposition, active ingredients for reducing adhesion of soils, active ingredients for improving processability, active ingredients for reducing adhesion, and mixtures thereof. All other components should be included in an amount of not more than 60% by weight, preferably from 0.01 to 60% by weight, in particular from 0.2 to 15% by weight.

Acid(s)

The toilet cleaning block of the present invention can contain one or more acids and/or salts thereof to improve the cleaning performance with respect to scale and urine scale. The acid is preferably manufactured from raw materials that are sustainable. 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 sulfamic acid. Particularly preferred are acids and/or salts thereof selected from: citric acid, lactic acid, sulfamic acid, salts of the foregoing acids, and mixtures thereof. They are preferably used in amounts of 0.01 to 10% by weight, particularly preferably 0.2 to 5% by weight. However, in the most particularly preferred embodiment, the toilet cleaning block of the present invention is acid-free.

Furthermore, in a preferred embodiment, the substrate comprises an inorganic salt, preferably an alkali or alkaline earth metal salt, in particular a carbonate, sulphate, halide or phosphate, and mixtures thereof. Particular preference is given to using sodium sulfate and/or sodium carbonate. Sodium sulphate may be included in an amount of up to 60 wt%, preferably 0.01 to 60 wt%, particularly preferably 20 to 60 wt%, especially 35 to 55 wt%. Sodium carbonate and other salts may be included in amounts of up to 30 wt%, preferably up to 10 wt%, particularly preferably up to 5 wt%.

Alkali

The substrate of the present invention may further contain a base. As the base in the substrate of the present invention, preferably used are those selected from hydroxides and carbonates of alkali metals and alkaline earth metals, in particular sodium carbonate or sodium hydroxide. However, it is also possible to use ammonia and/or alkanolamines with up to 9C atoms in the molecule (preferably ethanolamine, in particular monoethanolamine).

Preservative

Preservatives may likewise be included in the toilet cleaning block of the present invention. The substances mentioned in the antimicrobial active components can be used essentially as preservatives.

Complexing agents

Complexing agents (INCI chelators), also known as sequestering agents, are components that are capable of complexing and inactivating metal ions to avoid their adverse effects on the stability or appearance of the substrate, such as turbidity. On the one hand, it is important to complex calcium and magnesium ions which are incompatible with the numerous components, originating from the hardness of water. On the other hand, complexation of ions of heavy metals (such as iron or copper) delays the oxidative decomposition of the final substrate. Furthermore, the complexing agent supports the cleaning action.

The following complexing agents listed according to INCI are suitable examples:

aminotrimethylenephosphonic acid, beta-propylalanine diacetic acid, disodium EDTA, citric acid, cyclodextrin, cyclohexanediaminetetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriaminepentamethylenephosphonic acid, dipotassium EDTA, azepane disodium diphosphonate, disodium EDTA, disodium pyrophosphate, EDTA, etidronic acid, galactaric acid, gluconic acid, glucuronic acid, HEDTA, hydroxypropyl cyclodextrin, methylcyclodextrin, pentapotassium triphosphate, pentasodium aminotrimethylenephosphonate, pentasodium ethylenediaminetetramethylenephosphonate, pentasodium pentetate (pentaasodi pentate), pentasodium triphosphate, triaminepentaacetic acid (pentaacetic acid), phytic acid, potassium citrate, EDTMP potassium, potassium gluconate, potassium polyphosphate, potassium nitrilotris (methylene) triphosphonate oxide (potassium Possitriumphosphonomethyliminoxide), ribonic acid, sodium chitosan methylenephosphonate (Sodiumpolysuccinate), sodium citrate, sodium diethylenetriaminepentamethylenephosphonate, Dihydroxyethyl glycine sodium, EDTMP sodium, sodium glucoheptonate, sodium gluconate, glyceryl polyether-1 sodium Polyphosphate (SodiumGlycereth-1Polyphosphate), sodium hexametaphosphate, sodium metaphosphate, sodium metasilicate, sodium phytate, sodium polydimethylglycylphenol sulfonate, sodium trimetaphosphate, TEA-EDTA, TEA-Polyphosphate, tetrahydroxyethylendiamine, tetrahydroxypropylethylenediamine, tetrapotassium hydroxyethylphosphate, tetrapotassium pyrophosphate, tetrasodium EDTA, tetrasodium hydroxyethylphosphate, tetrasodium pyrophosphate, tripotassium EDTA, trisodium dicarboxymethylalanine, trisodium EDTA, trisodium HEDTA trisodium, NTA trisodium and trisodium phosphate.

Polymer and method of making same

The toilet cleaning block of the present invention may additionally comprise a polymer. These polymers can be used, for example, to reduce scale formation and the tendency to re-contaminate.

In this regard, preferred polymers are acrylic polymers such as those commercially available from Rhodia under the trade name Mirapol.

Scenting agents and dyes

As further components, the toilet cleansing block of the present invention may comprise one or more fragrances and/or one or more dyes (INCI colorants). As dyes, both water-soluble and oil-soluble dyes can be used herein, on the one hand in view of their compatibility with other components, such as bleaches, and on the other hand, the dyes used should not have a substantial effect on the toilet ceramic even under prolonged exposure. The amount of the dye contained is preferably 0.0001 to 0.1% by weight, in particular 0.0005 to 0.05% by weight, particularly preferably 0.001 to 0.01% by weight.

Builder

Water soluble and/or water insoluble builders may optionally be used in the toilet cleaning block of the invention. Water-soluble builders are preferred herein because they generally have a lower tendency to leave insoluble residues on hard surfaces. Conventional builders that may be present within the scope of the present invention are: low molecular weight polycarboxylic acids and their salts, homo-and co-polymeric polycarboxylic acids and their salts, citric acid and its salts, carbonates, phosphates and silicates. Water-insoluble builders include the zeolites which may also be used, which may form mixtures with the builder materials mentioned above.

Bleaching agent

According to the invention, a bleaching agent may be added to the cleaning agent. Suitable bleaching agents include peroxides, peracids and/or perborates; particularly preferred is sodium percarbonate or phthalimido peroxycaproic acid. Chlorine-containing bleaches, such as trichloroisocyanuric acid or sodium dichloroisocyanurate, on the other hand, are less suitable for acidic formulated cleaners due to the emission of toxic chlorine vapors, but can be used in alkaline cleaners. In some cases, a bleach activator may be desirable in addition to a bleaching agent.

Corrosion inhibitor

Suitable corrosion inhibitors (INCI corrosion inhibitors) are, for example, the following listed according to INCI: cyclohexylamine, diammonium hydrogen phosphate, dilithium oxalate, dimethylaminomethylpropanol, dipotassium oxalate, dipotassium phosphate, disodium pyrophosphate, disodium tetrapropenylsuccinate, hexyloxydiethylammonium (hexoxyethylammonionium), phosphate, nitromethane, potassium silicate, sodium aluminate, sodium hexametaphosphate, sodium metasilicate, sodium molybdate, sodium nitrite, sodium oxalate, sodium silicate, stearamidopropyl dimethicone, tetrapotassium pyrophosphate, tetrasodium pyrophosphate, and triisopropanolamine.

Flush control agent

Substances known as flush modifiers are used primarily to control the consumption of the agent during use to achieve the intended life span. Suitable regulators are preferably solid long chain fatty acids, such as stearic acid; and salts of these fatty acids, fatty acid ethanolamides, such as coconut oil fatty acid monoethanolamide; or solid polyethylene glycols, such as those having a molecular weight between 10000 and 50000.

Active ingredients for reducing tack

To improve processability, an active ingredient for reducing tackiness can be added during the manufacture of the toilet cleansing block of the present invention. For example, the addition of dolomite powder or titanium dioxide powder with a fine particle size distribution improves the processing characteristics when forming spheres and significantly reduces the abrasiveness or tackiness.

The results with such active ingredients are better than with other conventional measures, such as coating the balls with a lubricant, coating with polytetrafluoroethylene dust or coating the forming rollers.

Enzymes

The substrate may also comprise enzymes, preferably proteases, lipases, amylases, hydrolases and/or cellulases. These enzymes may be added to the substrates of the invention in any form established according to the prior art. These forms comprise solutions of the enzymes, which are advantageously as concentrated as possible, have a low water content and/or are added with stabilizers. Alternatively, the enzymes may be encapsulated by: for example by spray drying or extrusion of the enzyme solution together with the preferred natural polymer; or in the form of capsules, such as those in which the enzyme is embedded in the form of a solidified gel; or in the form of a core-shell type, wherein the enzyme-containing core is coated with a protective layer which is impermeable to water, air and/or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaches or dyes, may also be applied in the additional layer. Such capsules are manufactured using known methods, for example: by vibratory granulation or roller compaction, or by a fluidized bed process. Advantageously, these types of particles are very low in dust content, for example by applying polymeric film formers, and are storage stable as a result of the coating.

In addition, an enzyme stabilizer may be present in the substrate comprising the enzyme in order to protect the enzyme comprised in the substrate of the invention from damage, e.g. inactivation, denaturation or decomposition, such as by e.g. physical action, oxidation or decomposition of the eggDissociation of white matter. Enzyme stabilizers used depending on the enzyme used in each case, the following are particularly suitable as enzyme stabilizers: benzamidine hydrochloride, borax, boric acid, acid (boronicacid) or salts or esters thereof, primary derivatives with aryl groups such as substituted phenyl acid or salts or esters thereof; peptide aldehydes (oligopeptides with reduced C-terminus); aminoalcohols, such as monoethanolamine, diethanolamine, triethanolamine, and monopropanolamine, dipropanolamine, tripropanolamine, and mixtures thereof; up to C₁₂Aliphatic carboxylic acids such as succinic acid, other dicarboxylic acids or salts of the above acids; a capped fatty acid amide alkoxylate; aliphatic lower alcohols and polyhydric primary alcohols, such as glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are well known in the art. Combinations of stabilizers are preferably used, for example combinations comprising polyols, boric acid and/or borax, combinations comprising boric acid or borates, reducing salts and succinic acid or other dicarboxylic acids, or combinations comprising boric acid or boric acid hydrochloric acid with polyols or polyamino compounds and with reducing salts.

Multi-layer toilet cleaning block

Known from the prior art, for example from EP791047B 1: toilet cleaning blocks are manufactured from materials having different compositions, wherein one of the materials is completely or partially encapsulated by another material or materials. Thus, for example, the inner material may have a higher concentration of perfume than the outer material to ensure a constant fragrance effect over the life of the product as the weight of the ball decreases, or the inner material may contain a different perfume to the outer material. Furthermore, other active components may also be incorporated in different layers, so that they are released at different times depending on the degree of flushing. This type of multi-layer construction is also possible for the toilet cleaning block of the invention.

Degree of sphericity

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

The sphericity Ψ of the object K is the ratio of the surface area of a sphere of the same volume to the surface area of the object.

Wherein V_pIs the volume of an object, and A_pIs its surface area.

With a toilet cleaning block, having an almost perfect spherical shape allows the toilet cleaning block to be flushed out evenly, so that the toilet cleaning block can remain substantially spherical, even during and after the flushing process and with a corresponding erosion of the toilet cleaning block. It has been demonstrated that: the high sphericity Ψ of the toilet cleaning block prior to impingement by the flush water is particularly important to maintain the sphericity during and after the flush event. The formability of the material and thus its ability to form an optimal circular shape can be adjusted by adding a small amount of liquid. In particular water, dipropylene glycol or paraffin can be used in liquid form in amounts of 0.1 to 1% by weight.

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

Inserting the lavatory block into a dispensing device secured to the rim of a toilet bowl with a clamp. On the one hand, cages with flushing water spreading elements are suitable for this purpose, as described in the prior art, for example, in DE102008037723, which can accommodate one or more toilet cleaning blocks. Alternatively, one or more open trays may be used, with one or more lavatory blocks suitably secured to the tray. The toilet cleaning block and the dispensing device of the present invention together form a system. The system can accordingly be used in a method of cleaning and/or perfuming and/or disinfecting a toilet having a water-withdrawal device, in that a dispensing device filled with the toilet cleaning block is suspended in the toilet bowl, and then when the toilet is flushed, the components dissolved in the toilet cleaning block pass into the flushing water and are able to exert their cleaning and/or perfuming and/or disinfecting action there. A corresponding system is described in DE 102009003088.

The toilet cleaning block of the present invention is manufactured in a method comprising the steps of:

a) the components are mixed and then mixed together,

b) the mixture is extruded and the mixture is extruded,

c) the extruded strands are cut into pieces of defined mass,

d) shaped as a rotationally symmetric object.

The forming step d) preferably takes place in a bulb roll press or a press. Other suitable forming methods are casting and calendering. Steps a) and b) may also be combined, i.e. the components are mixed in an extruder. These steps may optionally be performed at different temperatures, and therefore heating or cooling steps may be inserted between the steps. These can be determined as appropriate by the person skilled in the art.

In a preferred embodiment, following one of steps b) or c), a further step is carried out in which the extruded noodles are provided with a lubricant. For this purpose, a wheel-shaped sponge charged with lubricant for a long time is guided through the extruded strip so that its surface is completely or partially covered with lubricant, preferably at a level of 10 to 40%. The addition of lubricant here improves the subsequent ball formation.

Suitable alternatives to using a sponge for lubricating the strip are: such as simple dropping or spraying, and dipping wheels, dipping baths for ribbons or strips, etc. Different methods may also be combined, such as dipping the wheel through a lubricant bath and then rolling it along the strip while dripping.

In addition to the extruded strands, the rollers may also be provided with a lubricant.

Suitable lubricants are in particular substances which are used in the formulations according to the invention, for example as surfactants or rinse conditioners. Particularly preferred are lubricants selected from the group consisting of dipropylene glycol, paraffin wax, nonionic surfactants, polyethylene glycol and mixtures thereof, especially dipropylene glycol.

It is particularly preferred if the toilet cleaning block is shaped as 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.

Exemplary embodiments

Four toilet cleaning blocks according to the invention were prepared with formulations E1 to E4, and a comparative formulation V1 was prepared. The compositions can be taken from the following table, where all quantitative data are given in% by weight of active substance.

	E1	E2	E3	E4	V1
						C10-13Linear sodium alkyl benzene sulfonate	10	22	19	10	26
C14-16Olefin sulfonic acid sodium salt	20	10	10	20	18
						C12Sodium fatty alcohol sulfate Na	10	9	10	7	--
Sodium dichloroisocyanurate dihydrate	3.2	2.5	3.0	2	14.4
						Citric acid trisodium dihydrate	1.0	2.0	1.0	1	1
Cellulose, process for producing the same, and process for producing the same	--	--	1.0	--	--
						Sodium silicate	--	--	5.0	--	--
Sodium carbonate	--	1.0	--	--	--
						Perfume	4.0	4.0	4.0	4	4.5
Titanium dioxide	0.5	--	--	0.5	--
						C16-18Fatty alcoholsEthoxylate 25EO	--	--	--	2	8

Low viscosity paraffin oil	--	--	--	1	--
						Sodium sulfate	To 100	To 100	To 100	To 100	To 100

The content of nonionic surfactant in the comparative formulation was too high, resulting in a significant reduction in chlorine content. Immediately after preparation, the content had dropped to 9.7%, and after using 48 hours and 43 rinses with water, 3.4% of the chlorine carrier could be detected. On the other hand, the formulations of the present invention exhibited a smaller reduction in chlorine content, even for formulation E4, which had a low nonionic surfactant content.

Claims (28)

1. A toilet cleaning block comprising a perfume, from 10 to 70 wt% of at least one alkylbenzene sulfonate and from 10 to 30 wt% of at least one olefin sulfonate, wherein the toilet cleaning block comprises one or more chlorine-containing disinfectants selected from the group consisting of 2-benzyl-4-chlorophenol, 2 '-methylenebis (6-bromo-4-chlorophenol), 2,4,4' -trichloro-2 '-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- (3, 4-dichlorophenyl) urine, N' - (1, 10-decanediyl di-1-pyridinyl-4-ylidene) bis (1-octylamine) dihydrochloride and not more than 2.5 wt% of a nonionic surfactant and is shaped in a roll press or a press to form spheres, Trichloroisocyanuric acid, sodium dichloroisocyanurate, alkali metal hypochlorite, and mixtures thereof.

2. The lavatory cleansing block of claim 1, wherein the lavatory cleansing block comprises 20 to 65 wt.% alkylbenzene sulfonate.

3. The toilet cleaning block of claim 2, wherein the toilet cleaning block comprises 20 to 30 wt% alkylbenzene sulfonate.

4. The toilet cleansing block of claim 1, wherein the toilet cleansing block comprises 15 to 30 wt% of an olefin sulfonate.

5. The lavatory cleansing block of claim 4 wherein the lavatory cleansing block comprises 15 to 25 wt% olefin sulfonate.

6. The toilet cleansing block of claim 1 or 2, wherein the toilet cleansing block comprises at least one additional anionic surfactant.

7. The toilet cleansing block of claim 6, wherein the at least one anionic surfactant is a fatty alcohol sulfate.

8. The toilet cleansing block of claim 7, wherein the anionic surfactant is present in an amount of up to 20% by weight.

9. The toilet cleansing block of claim 8, wherein the anionic surfactant is present in an amount of 4 to 12 wt.%.

10. The toilet cleansing block of claim 9, wherein the anionic surfactant is present in an amount of 7 to 10 wt.%.

11. The toilet cleansing block of claim 1 or 2, wherein the toilet cleansing block is free of nonionic surfactants.

12. The toilet cleansing block of claim 1 or 2, wherein the toilet cleansing block comprises an additional surfactant.

13. The toilet cleaning block of claim 12, wherein the additional surfactant is selected from the group consisting of fatty alcohol ether sulfates, alkane sulfonates, and mixtures thereof.

14. The toilet cleaning block of claim 1 or 2, wherein the one or more chlorine-containing disinfectants is selected from the group consisting of alkali metal hypochlorite, sodium dichloroisocyanurate, and mixtures thereof.

15. The toilet cleaning block of claim 14, wherein the one or more chlorine-containing disinfectants is sodium dichloroisocyanurate.

16. The lavatory cleansing block of claim 1 or 2, wherein the lavatory cleansing block comprises one or more other components conventionally used in lavatory cleansing blocks.

17. The toilet cleaning block of claim 16, wherein the other component is selected from the group consisting of acids, bases, salts, thickeners, preservatives, complexing agents, dyes, fragrances, fragrance enhancers, fillers, builders, bleaches, corrosion inhibitors, rinse conditioners, enzymes, microorganisms, active components for biofilm removal, active components for preventing scale deposition, active components for reducing soil adhesion, and mixtures thereof.

18. The toilet cleaning block of claim 1 or 2, wherein the toilet cleaning block has a spherical shape with a sphericity Ψ between 0.8 and 1.

19. The lavatory cleansing block of claim 18, wherein the lavatory cleansing block has a sphericity having a sphericity Ψ between 0.85 and 1.

20. The toilet cleaning block of claim 19, wherein the toilet cleaning block has a spherical shape with a sphericity Ψ between 0.9 and 1.

21. System comprising at least one toilet cleaning block according to any one of the preceding claims and a dispensing device.

22. A method of manufacturing a rotationally symmetric toilet cleansing block comprising perfume, alkyl benzene sulphonate and olefin sulphonate and being free of non-ionic surfactant, wherein the method comprises the steps of:

a) the components are mixed and then mixed together,

b) the mixture is extruded and the mixture is extruded,

c) the extruded strands are cut into pieces of defined mass,

d) shaped as a rotationally symmetric object.

23. The method of claim 22, wherein subsequent to one of steps b) or c), a lubricant is provided to the extruded noodles.

24. The method of claim 22 or 23, wherein the toilet cleaning block is shaped as a ball having a sphericity Ψ between 0.8 and 1.

25. The method of claim 24, wherein the toilet cleaning block is shaped as a ball having a sphericity Ψ between 0.85 and 1.

26. The method of claim 25, wherein the toilet cleaning block is shaped as a ball having a sphericity Ψ between 0.9 and 1.

27. The process of claim 22 or 23, wherein the forming step d) occurs in a bulb roll press or a press.

28. A method of cleaning and/or fragrancing and/or sanitizing toilets which have water-closet facilities wherein the system of claim 21 is employed.