EP4467633A1 - Produit sanitaire auto-adhésif comprenant un alkylpolyglycoside - Google Patents

Produit sanitaire auto-adhésif comprenant un alkylpolyglycoside Download PDF

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Publication number
EP4467633A1
EP4467633A1 EP23175476.3A EP23175476A EP4467633A1 EP 4467633 A1 EP4467633 A1 EP 4467633A1 EP 23175476 A EP23175476 A EP 23175476A EP 4467633 A1 EP4467633 A1 EP 4467633A1
Authority
EP
European Patent Office
Prior art keywords
self
sanitary agent
agent
acid
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23175476.3A
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German (de)
English (en)
Inventor
Marianne Schmeling
Daniela Poethkow
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP23175476.3A priority Critical patent/EP4467633A1/fr
Priority to PCT/EP2024/063947 priority patent/WO2024240760A1/fr
Publication of EP4467633A1 publication Critical patent/EP4467633A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the invention relates to an adhesive sanitary agent for cleaning and/or disinfecting and/or for releasing fragrances for sanitary objects such as toilet bowls.
  • Toilet cleaning agents in chunks have long been used in the toilet bowl under the edge (so-called rim blocks) and in the water tank (in-tank blocks or cistern blocks).
  • the formulations usually contain surfactants, disinfectants and bleaches, salts, acids, complexing agents, fillers, colorants and fragrances, flush regulators and/or other components.
  • the ingredients are usually mixed, compressed and then extruded into strands. The strands are then cut to the desired length and, if necessary, inserted into toilet baskets.
  • the toilet bowl can be cleaned and/or disinfected, for example. It can also be used to inhibit unpleasant odors or to scent it with a perfume.
  • the ingredients required for these different effects are not always compatible with one another.
  • Sensitive substances such as dyes can be attacked by antimicrobial bleaching agents, for example; acids or complexing agents used to prevent limescale, rust or urine deposits are often not compatible with perfumes, for example.
  • toilet sticks which are positioned in a toilet basket under the rim of a toilet
  • self-adhesive toilet cleaning products have been available for some time now. These are stuck into the toilet bowl by the user, where they then stick and are rinsed away by the flush water.
  • sanitary products are viscous, generally pasty products that are applied from a suitable container directly to the surface of the sanitary object, where they adhere and can only be rinsed off after a large number of flushing processes.
  • Such adhesive sanitary products are from the WO 99/66017 They contain surfactants, water and fragrances as well as adhesion promoters and are usually designed as solid gels.
  • solid gels can also contain glycols and glycol derivatives.
  • the known adhesive sanitary agents can be applied using a suitable device, adhere to the surface of the sanitary object and are only completely dissolved after a large number of flushes.
  • a solid gel is usually a dispersed system that consists of at least two components.
  • the solid component forms a sponge-like, three-dimensional network whose pores are filled with a liquid (lyogel) or a gas (xerogel).
  • the liquid component is thus immobilized in the solid.
  • the liquid component is usually water.
  • the solid component is usually formed by molecular "adhesion promoters" that have a hydrophilic part and a hydrophobic part and, through suitable hydrogen bonds, form the three-dimensional network whose pores are filled with the liquid component.
  • the present invention is based on the object of providing a non-gel-like sanitary agent which is nevertheless suitable for adhering to a smooth surface.
  • a self-adhesive sanitary agent comprising alkyl polyglycoside.
  • alkyl polyglycoside enables adhesion to a sanitary object.
  • APG can mediate the adhesion of non-gel-like agents.
  • the term "self-adhesive sanitary agent” is to be understood to mean that the agent can be applied directly to the surface of the sanitary object and adheres there and can only be rinsed off after a large number of rinsing processes, preferably at least 10 rinsing processes.
  • Alkyl polyglycosides are also used as surfactants. They are non-ionic surfactants and belong to the sugar surfactants. They are used as surface-active components in detergents, dishwashing detergents and cleaning agents. Alkyl polyglycosides consist entirely of the renewable raw materials sugar, obtained from sugar cane and sugar beet, and fatty alcohols, obtained from palm oils. They are biodegradable and have low toxicity.
  • the APG is not only able to ensure the adhesion of the sanitary agent to the surface, but also contributes to the cleaning performance.
  • composition according to the invention is able to maintain the consistency of the adhesive sanitary agent even over a large number of flushes, so that the applied agent retains a smooth, essentially surface even with a low flushing frequency.
  • the agent according to the invention also avoids the drying of the surface observed with the known agents with the formation of residues that are difficult to dissolve.
  • composition according to the invention also has a positive effect on the service life of the product, because these compounds improve the dissolving behavior of the sanitary product and thus reduce the required amount of perfume to be used.
  • a self-adhesive sanitary product wherein the self-adhesive sanitary product is not a solid gel.
  • the sanitary product is designed as a solid molding compound and thus has a visual impression that is preferred by many consumers over a partially transparent gel. The rinsing behavior of the molding compound also differs from that observed with solid gels.
  • the sanitary agent is not transparent, i.e. essentially completely opaque.
  • the sanitary agent differs from solid gels, which are generally at least partially transparent.
  • a self-adhesive sanitary agent wherein the alkyl polyglycoside is present in an amount of at most 24 wt.%.
  • a self-adhesive sanitary agent wherein the alkyl polyglycoside is present in an amount of at least 2 wt.%.
  • a self-adhesive sanitary agent wherein the alkyl polyglycoside is present in an amount of 1 wt.% to less than 24 wt.%, preferably 2 to less than 24 wt.%, more preferably 4 wt.% to 20 wt.%, and particularly preferably from 9 to 15 wt.%.
  • a self-adhesive sanitary agent comprising at least one anionic surfactant.
  • a self-adhesive sanitary agent wherein the at least one anionic surfactant comprises an olefin sulfonate.
  • a self-adhesive sanitary agent wherein the olefin sulfonate is present in an amount of at least 2 wt.% to 30 wt.%, preferably 7 wt.% to 15 wt.%.
  • a self-adhesive sanitary agent comprising at least one further anionic surfactant.
  • a self-adhesive sanitary agent wherein the at least one further anionic surfactant is an alkylbenzenesulfonate.
  • a self-adhesive sanitary agent wherein the alkylbenzenesulfonate is present in an amount of at least 5 wt.% to 40 wt.%, preferably 10 wt.% to 30 wt.%.
  • a self-adhesive sanitary agent comprising at least one further non-ionic surfactant.
  • a self-adhesive sanitary agent wherein the at least one further non-ionic surfactant is a fatty alcohol ethoxylate.
  • a self-adhesive sanitary agent wherein the alkylbenzenesulfonate is present in an amount of at least 2 wt.% to 10 wt.%.
  • the use of the self-adhesive sanitary agent according to one of the preceding claims is described, wherein the sanitary agent is applied to a surface of a sanitary object.
  • the sanitary agents according to the invention can only be rinsed off the surface after a large number of rinsing processes.
  • the agent according to the invention is an ointment-like, pasty, preferably non-gel-like, non-transparent agent.
  • the agents are essentially dimensionally stable, so that they do not "run down” or "drip” and thus remain on the surface.
  • the agents according to the invention can be applied in different ways and forms.
  • the agent can also contain non-ionic surfactants.
  • the molecules of the non-ionic surfactant are relatively long-chain, essentially elongated molecules that are at least partially hydrophilic and thus comprise at least one hydrophilic residue or group that interacts with water.
  • the non-ionic surfactants should be unbranched molecules to enable the desired network formation.
  • the non-ionic surfactant can be either totally hydrophilic or partially hydrophilic and partially hydrophobic.
  • Organic molecules with a hydrophilic and a hydrophobic end can be used as non-ionic surfactants.
  • polyalkoxy groups preferably polyethoxy, polypropoxy or polybutoxy or mixed polyalkoxy groups such as poly(ethoxypropoxy) groups
  • hydrophilic radicals can be used as hydrophilic radicals. It is particularly preferred to use a polyethoxy radical comprising between 5 and 55 ethoxy groups, preferably between 10 and 30 and particularly preferably 10 to 20 ethoxy groups, as the hydrophilic end.
  • non-ionic surfactants also have a hydrophobic end
  • straight-chain alkyl radicals are particularly suitable for the hydrophobic radical, with even-numbered alkyl radicals being particularly preferred due to their better biodegradability.
  • alkyl groups are selected as hydrophobic radicals, alkyl radicals with at least twelve carbon atoms are preferred. Particularly good results were achieved with an alkyl chain length between 16 and 30 carbon atoms, in particular 16, 18, 20 and 22 carbon atoms.
  • the non-ionic surfactants can also comprise alkylbenzene residues, for example dodecylbenzene or similar residues, as is the case with the non-ionic surfactant sodium dodecylbenzenesulfonate.
  • Preferred non-ionic surfactants are polyalkoxyalkanes, preferably a mixture of alkyl (C10-C20) ethoxylate with 15 to 35 EO or alkyl (C16-C18) ethoxylate with 15 to 35 EO and alkyl (C16-C18) ethoxylate with 25 EO, but also alkyl sulfonates such as sodium dodecylbenzenesulfonate or alkyl carbonates or alkyl sulfates are conceivable.
  • non-ionic surfactants alkyl(C22) ethoxylate (25EO) and alkyl(C16-C18) ethoxylate (25EO) affects the cleaning ability.
  • the combined use of these non-ionic surfactants makes the agent easier to process.
  • the non-ionic surfactants By reducing the number of alkoxy groups, the non-ionic surfactants become more lipophilic, which can, for example, increase the solubility of perfume and thus the intensity of the fragrance.
  • Molecules that generally act as thickeners in aqueous systems can also be used as non-ionic surfactants.
  • the concentration of the non-ionic surfactant to be used depends on its hydrophilicity and its network-forming capacity. It can be, for example, 1 to 3% by weight, 10 to 40% by weight, preferably between 15 and 35% by weight and particularly preferably between 20 and 30% by weight, which is particularly preferred when using polyalkoxyalkanes.
  • the sanitary agent can comprise other conventional components, for example perfume oil, disinfectants, preservatives, such as isothiazolone derivatives or foam stabilizers, such as coconut fatty acid amidopropyl betaine or coconut fatty acid amidopropyl dimethylamine oxide, coconut fatty acid mono/diethanolamide or alkyl polyether glycerol ether sulfates, but also dyes and/or lime or urine stone dissolving substances, in particular acids.
  • perfume oil for example perfume oil, disinfectants, preservatives, such as isothiazolone derivatives or foam stabilizers, such as coconut fatty acid amidopropyl betaine or coconut fatty acid amidopropyl dimethylamine oxide, coconut fatty acid mono/diethanolamide or alkyl polyether glycerol ether sulfates, but also dyes and/or lime or urine stone dissolving substances, in particular acids.
  • salts such as sodium sulfate can also be added to the formulation to increase the dissolution rate.
  • the salt content can be up to 10% by weight, preferably up to 5% by weight.
  • the agent according to the invention can be applied and renewed in a hygienic manner without touching potentially contaminated devices connected to the toilet bowl.
  • a significant advantage of the product according to the invention is that it can be portioned according to the consumer's wishes. If the consumer wants a more intense fragrance or if the toilet is used frequently, the dosage can be increased accordingly.
  • the agent according to the invention can also be applied in a simple manner simultaneously to different places on the sanitary object, for example in order to achieve a uniform cleaning effect on both the right and left side of a toilet bowl.
  • the agent according to the invention can also be applied in different compositions to a sanitary object at different locations. This makes it possible, for example, for two ingredients that are incompatible with one another, such as halogen-releasing agents and oxidation-sensitive perfumes, to be used together to clean and/or scent the toilet by separating them locally.
  • the adhesion achieved is so good on the sanitary object, even when applied to a vertical surface, that the agent does not come off even under the additional force of flushing water streams.
  • the sanitary products according to the invention can only be rinsed off after a large number of flushing processes.
  • the number of flushing processes naturally depends on the composition of the respective sanitary product, the amount applied and the geometry of the sanitary product applied.
  • Fragrances and/or scents can also be added to the product to improve the air in the room, although it is also possible to add only fragrances and scents to a toilet bowl.
  • the sanitary product can also be used for other sanitary items such as urinals, pissoirs, but also for hand-wash basins or the like.
  • the agent according to the invention is an ointment-like, pasty, non-gel-like, non-transparent agent.
  • the agents are essentially dimensionally stable, so that they do not "run down” or "drip".
  • the agents can preferably be introduced into the toilet bowl via tubes, similar to toothpaste tubes, syringes or cartridges, and remain there for a large number of consecutive flushes.
  • the toilet cleaning block according to the invention can contain other ingredients that are usually 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, bleaches, corrosion inhibitors, rinse regulators, enzymes, microorganisms, active ingredients for biofilm removal, active ingredients for inhibiting limescale deposits, active ingredients for reducing dirt adhesion, active ingredients for improving processability, active ingredients for reducing stickiness and mixtures thereof.
  • other ingredients preferably 0.01 to 60% by weight, in particular 0.2 to 15% by weight.
  • Toilet cleaning blocks according to the invention can contain one or more acids and/or their salts to increase the cleaning performance against limescale and urine scale.
  • the acids are preferably made from renewable raw materials.
  • 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 and mixtures thereof are therefore particularly suitable as acids.
  • the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or 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% by weight, particularly preferably 0.2 to 5% by weight.
  • the agent contains inorganic salts, preferably alkali or alkaline earth metal salts, in particular carbonates, sulfates, halides or phosphates and mixtures thereof.
  • Sodium sulfate and/or sodium carbonate are particularly preferably used.
  • Sodium sulfate can be present in an amount of up to 60% by weight, preferably 0.01 to 60% by weight, particularly preferably 20 to 60% by weight, in particular 35 to 55% by weight.
  • Sodium carbonate and other Salts may be present in an amount of up to 30 wt.%, preferably up to 10 wt.%, particularly preferably up to 5 wt.%.
  • Agents according to the invention can also contain alkalis.
  • Bases used in agents according to the invention are preferably those from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide.
  • ammonia and/or alkanolamines with up to 9 carbon atoms in the molecule can also be used, preferably ethanolamines, in particular monoethanolamine.
  • 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.
  • disinfection, sanitation, antimicrobial effect and antimicrobial agent have the usual technical meaning within the framework 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 to be understood as the elimination of all germs as far as possible - including saprophytic germs that are normally harmless to humans. The extent of the disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing content of antimicrobial agent or increasing dilution of the agent for use.
  • 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, 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.
  • antimicrobial active ingredients from the groups of alcohols, aldehydes, antimicrobial acids or their salt
  • Preferred antimicrobial active ingredients 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-diimin
  • Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group.
  • Antimicrobially effective essential oils can also be used, which also provide a scent for the cleaning agent.
  • Particularly preferred antimicrobial active ingredients are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite, sodium dichloroisocyanurate and mixtures thereof.
  • Preservatives can also be contained in toilet cleaning blocks according to the invention. Essentially, the substances mentioned under antimicrobial active ingredients can be used as such.
  • Complexing agents also known as sequestering agents, are ingredients that can complex and inactivate metal ions in order to prevent their adverse effects on the stability or appearance of the products, such as cloudiness. On the one hand, it is important to complex the calcium and magnesium ions of water hardness, which are incompatible with many ingredients. On the other hand, the complexing of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished products. In addition, the complexing agents support the cleaning effect.
  • the following complexing agents designated according to INCI are suitable: 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, Pentas, Pen
  • the toilet cleaning block according to the invention can also contain polymers. These can serve, for example, to reduce limescale formation and the tendency to become soiled again.
  • Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol.
  • 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 on the one hand the compatibility with other ingredients, for example bleaching agents, must be taken into account and on the other hand the dye used should not have a substantive effect on the toilet ceramic, even after prolonged exposure.
  • the dyes are preferably contained in an amount of 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.
  • Water-soluble and/or water-insoluble builders can optionally be used in the toilet cleaning blocks according to the invention. Water-soluble builders are preferred because they generally have less of a 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.
  • bleaching agents can be added to the cleaning agent.
  • Suitable bleaching agents include peroxides, peracids and/or perborates, with hydrogen peroxide being particularly preferred.
  • Sodium hypochlorite is less suitable for acidic cleaning agents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents.
  • a bleach activator may also be required in addition to the bleaching agent.
  • Suitable corrosion inhibitors are, for example, the following substances named according to INC I: 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 pyrophosphates, triisopropanolamines.
  • Viscosity regulators which include, for example, organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein), organic modified natural substances (carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and the like, kernel flour ethers), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, layered silicates, clay minerals such as montmorillonites, zeolites, silicic acids), can be used optionally.
  • organic natural thickeners agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour,
  • Preferred thickeners are polysaccharides and heteropolysaccharides, in particular polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar, and their mixtures.
  • polysaccharide gums for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan, ramsan, dextran or xanthan and their derivatives, e.g. propoxylated guar, and their mixtures.
  • Other polysaccharide thickeners such as starches or cellulose derivatives, can be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g.
  • hydroxyethyl starch starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl-methyl or hydroxyethylmethyl cellulose or cellulose acetate.
  • substances that are usually used as pressure-sensitive adhesives can also be used as adhesion promoters. These include, for example, adhesive polymers.
  • the substances known as rinse regulators are primarily used to control the consumption of the agents during use so that the intended service life is maintained.
  • Solid long-chain fatty acids such as stearic acid
  • fatty acid ethanolamides such as coconut fatty acid monoethanolamide
  • solid polyethylene glycols such as those with molecular weights between 10,000 and 50,000.
  • the agent can 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 in the art. These include solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed 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 enclosed as if in a solidified gel or in those of the core-shell type in which an enzyme-containing core is covered with a protective layer that is impermeable to water, air and/or chemicals.
  • enzymes preferably proteases, lipases, amylases, hydrolases and/or cellulases.
  • active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes.
  • granules are low in dust, for example by applying polymeric film formers, and are storage-stable due to the coating.
  • enzyme stabilizers can 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 decomposition, for example due to physical influences, oxidation or proteolytic cleavage.
  • the following are particularly suitable as enzyme stabilizers, depending on the enzyme used: 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 glycerine
  • stabilizers are known from the prior art.
  • 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.
  • Table 1 shows the compositions C1: component C1 fragrances 3 APG, alkyl polyglucoside - LAS, alkylbenzenesulfonate 18.7 olefin sulfonate-Na C14-C16 9 trisodium citrate dihydrate 0.7 Fatty alcohol ethoxylate C16-C18 25 EO 5 sodium sulfate 63.60
  • Composition C1 showed no stickiness at all. Adhesion to smooth surfaces such as a toilet sink was not possible.
  • Table 2 shows the compositions E1, E2 and E3 and the results of the strength and stickiness measurements carried out on these compositions: component E1 E2 E3 fragrances 4 4 4 APG, alkyl polyglucoside 3 6 24 LAS, alkylbenzenesulfonate 22 22 22 olefin sulfonate-Na C14-C16 11 11 11 11 trisodium citrate dihydrate 0.7 0.7 0.7 Fatty alcohol ethoxylate C16-C18 25 EO 5 5 5 sodium sulfate 54.30 51.30 33.30 E1 E2 E3 strength 52.60 15.80 1.00 stickiness 30.50 13.20 0.90
  • compositions E1, E2 and E3 are self-adhesive compositions capable of adhering to the sanitary article independently. Unlike the compositions known from the prior art, the compositions described are not solid gels. Rather, they are stable molded body masses, which are preferred over solid gels. Surprisingly, it was found that these moldings are able to adhere independently to the sanitary article, which is due to the presence of APG. Of the tests shown, examples E1 and E2 are preferred over E3. E3 was just able to show adhesion to the surface. According to a preferred embodiment, APG is therefore present in amounts of at most 24 wt.%, preferably in an amount of less than 24 wt.%.
  • APG is present in amounts of at least 1 wt.% to less than 24 wt.% E2 is in turn preferred over E1 because strength and tack have more balanced values that are more suitable for use on a toilet surface. According to a further preferred embodiment, APG is present in amounts of at least 4 wt.% to less than 24 wt.%, more preferably from at least 4 wt.% to less than 20 wt.%.
  • Table 3 shows the particularly preferred compositions E4, E5 and E6 and the results of the strength and stickiness measurements carried out on these compositions: component E4 E5 E6 fragrances 4 4 4 APG, alkyl polyglucoside 10 12 14 LAS, alkylbenzenesulfonate 22 22 22 olefin sulfonate-Na C14-C16 11 11 11 trisodium citrate dihydrate 0.7 0.7 0.7 Fatty alcohol ethoxylate C16-C18 25 EO 5 5 5 sodium sulfate 47.30 45.30 43.30 E4 E5 E6 strength 10.50 9.50 6.80 stickiness 8.90 7.60 6.10
  • compositions E4, E5 and E6 are particularly preferred, as the results of the strength and stickiness measurements carried out on these compositions show particularly balanced values.
  • the compositions adhere particularly well to surfaces and show a good consistency (not too sticky) and adequate rinsability.
  • Compositions E4, E5 and E6 are therefore stable molding masses which are more stable than solid Gels are preferred.
  • APG in particular in preferred amounts of at least 7% by weight to less than 24% by weight, more preferably 9 to less than 24% by weight and even more preferably 9 to 17% by weight, and particularly preferably 9 to 15% by weight.
  • anionic surfactant contributes to better foaming and improved cleaning performance.
  • olefin sulfonate contributes to better formability.
  • olefin sulfonate works advantageously with the APG, which provides the adhesion and consistency of the composition.
  • the strength (or hardness) and stickiness were determined experimentally: The hardness and stickiness measurements were carried out using a ball pressure test. A TA.XTPIus 100 Connect was used for hardness and stickiness measurements. The penetration depth for the steel ball to be inserted into the sample was set at 5 mm. The steel ball was then inserted into the sample at a constant speed of 0.1 mm/s, and the force required to do this was measured to determine the strength. The force that had to be applied to pull the ball out of the sample again corresponded to the stickiness measurement.

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EP23175476.3A 2023-05-25 2023-05-25 Produit sanitaire auto-adhésif comprenant un alkylpolyglycoside Pending EP4467633A1 (fr)

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EP23175476.3A EP4467633A1 (fr) 2023-05-25 2023-05-25 Produit sanitaire auto-adhésif comprenant un alkylpolyglycoside
PCT/EP2024/063947 WO2024240760A1 (fr) 2023-05-25 2024-05-21 Produit sanitaire auto-adhésif comprenant du polyglycoside d'alkyle

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999066017A1 (fr) 1998-06-12 1999-12-23 Buck-Chemie Gmbh & Co. Produit d'assainissement adhesif
DE102011004771A1 (de) * 2011-02-25 2012-08-30 Henkel Ag & Co. Kgaa WC-Gel
DE102012224159A1 (de) * 2012-12-21 2014-06-26 Henkel Ag & Co. Kgaa Selbsthaftender Reinigungsmittelstreifen für harte Oberflächen
WO2016004150A1 (fr) * 2014-07-01 2016-01-07 S.C. Johnson & Son, Inc. Blocs de nettoyage auto-adhésifs et articles de nettoyage, et procédés de fabrication de tels blocs et articles
US20160289941A1 (en) * 2013-11-18 2016-10-06 S. C. Johnson & Son, Inc. Cleaning apparatus and method of using and applying self-adhesive material for cleaning a surface

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999066017A1 (fr) 1998-06-12 1999-12-23 Buck-Chemie Gmbh & Co. Produit d'assainissement adhesif
DE102011004771A1 (de) * 2011-02-25 2012-08-30 Henkel Ag & Co. Kgaa WC-Gel
DE102012224159A1 (de) * 2012-12-21 2014-06-26 Henkel Ag & Co. Kgaa Selbsthaftender Reinigungsmittelstreifen für harte Oberflächen
US20160289941A1 (en) * 2013-11-18 2016-10-06 S. C. Johnson & Son, Inc. Cleaning apparatus and method of using and applying self-adhesive material for cleaning a surface
WO2016004150A1 (fr) * 2014-07-01 2016-01-07 S.C. Johnson & Son, Inc. Blocs de nettoyage auto-adhésifs et articles de nettoyage, et procédés de fabrication de tels blocs et articles

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