WO2010108834A1 - Système composé d'un produit de nettoyage et d'un dispositif de distribution - Google Patents

Système composé d'un produit de nettoyage et d'un dispositif de distribution Download PDF

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Publication number
WO2010108834A1
WO2010108834A1 PCT/EP2010/053461 EP2010053461W WO2010108834A1 WO 2010108834 A1 WO2010108834 A1 WO 2010108834A1 EP 2010053461 W EP2010053461 W EP 2010053461W WO 2010108834 A1 WO2010108834 A1 WO 2010108834A1
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WO
WIPO (PCT)
Prior art keywords
acid
oil
raw materials
perfume
dispensing device
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Application number
PCT/EP2010/053461
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German (de)
English (en)
Inventor
Michael Dreja
Brigitte Giesen
Ralph Butter-Jentsch
Original Assignee
Henkel Ag & Co. Kgaa
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Filing date
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Publication of WO2010108834A1 publication Critical patent/WO2010108834A1/fr

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D1/146—Sulfuric 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/72—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0056—Lavatory cleansing blocks
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D9/00—Sanitary or other accessories for lavatories ; Devices for cleaning or disinfecting the toilet room or the toilet bowl; Devices for eliminating smells
    • E03D9/02—Devices adding a disinfecting, deodorising, or cleaning agent to the water while flushing
    • E03D9/03—Devices adding a disinfecting, deodorising, or cleaning agent to the water while flushing consisting of a separate container with an outlet through which the agent is introduced into the flushing water, e.g. by suction ; Devices for agents in direct contact with flushing water
    • E03D9/032—Devices connected to or dispensing into the bowl
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D9/00—Sanitary or other accessories for lavatories ; Devices for cleaning or disinfecting the toilet room or the toilet bowl; Devices for eliminating smells
    • E03D9/02—Devices adding a disinfecting, deodorising, or cleaning agent to the water while flushing
    • E03D2009/024—Devices adding a disinfecting, deodorising, or cleaning agent to the water while flushing using a solid substance

Definitions

  • the invention relates to a system comprising a toilet cleaner formulation with at least one acid and / or its salt, a surfactant and a perfume and a dispenser of a recyclable and / or renewable and / or biodegradable plastic.
  • solid, liquid and gel cleaning formulations for flushing toilets can be brought to their place of action by means of special dispensing devices.
  • toilet bowls in which the cleaning formulation is contained in a storage container which is fastened by a holder to the toilet bowl
  • These cups are usually made of plastic and are both disposable and refillable
  • the detergents used generally contain surfactants as well as fragrances and acids, which serve to remove limescale, while the fragrances on the one hand give the product itself a pleasant fragrance, but on the other hand also counteract unpleasant odors at the place of use.
  • the subject matter of this invention is a system comprising a WC cleaner formulation with at least one acid or its salt, a surfactant and a perfume, and a toilet bowl made of a recyclable and / or renewable and / or biodegradable plastic.
  • the WC cleaner formulation is preferably at least 50% of ingredients based on renewable raw materials, preferably at least 70% of the ingredients are produced on the basis of renewable raw materials, more preferably over 90%.
  • the toilet cleaner formulation is in solid, liquid or gel form.
  • liquid-crystalline detergent formulations and compositions in the form of a foam, a dispersion, emulsion or microemulsion of the subject of this invention are particularly preferred.
  • flush toilets can be subjected to cleaning or else scented.
  • Another object of this invention is therefore a method for cleaning and / or scenting flush toilets using the system according to the invention.
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
  • the cleaning formulation according to the invention contains one or more surface-active substances, preferably those based on renewable raw materials.
  • Suitable surface-active substances for the agents according to the invention are surfactants, in particular from the classes of anionic and nonionic surfactants.
  • Suitable anionic surfactants are preferably C 8 -C 8 -alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C 8 -C 2 0-alkanesulfonates, C 8 -C 8 -monoalkyl sulfates, C 8 -C 8 - Alkylpolyglykolethersulfate with 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic mono- and di-C 8 -C 8 alkyl esters.
  • EO ethylene oxide units
  • C 8 -C 8 may - ⁇ - olefinsulfonates, sulfonated C 8 -C 8 fatty acids, especially dodecyl benzene sulfonate, C 8 -C 22 - Carbonklareamidethersulfate, C 8 -C 8 -Alkylpolyglykolethercarboxylate, C 8 -C 8 -N-acyl taurides , C 8 - C 18 -N sarcosinates and C 8 -C 8 -alkyl isethionates or mixtures thereof. It is always preferred that the carbon chains are derived from natural sources, such as vegetable oils and fats.
  • 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.
  • surfactants examples include sodium cocoalkyl sulfate, sodium sec-alkanesulfonate having about 15 carbon atoms and sodium dioctylsulfosuccinate.
  • Sodium-fatty alkylsulfates and fatty alkyl + 2EO ether sulfates containing 12 to 14 carbon atoms have proven to be particularly suitable.
  • Particularly suitable nonionic surfactants are C 8 -C 18 -alcohol polyglycol ethers, ie ethoxylated and / or propoxylated alcohols having 8 to 18 C atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and / or propylene oxide units (PO), Cs-C -is-carboxylic acid polyglycol esters having 2 to 15 EO, for example tallow fatty acid + 6-EO esters, ethoxylated fatty acid amides having 12 to 18 C atoms in the fatty acid moiety and 2 to 8 EO, long-chain amine oxides having 14 to 20 C atoms and long-chain alkylpolyglycosides with 8 to mention 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units.
  • C 8 -C 18 -alcohol polyglycol ethers ie ethoxylated and / or propoxylated alcohols having 8 to
  • surfactants examples include oleyl-cetyl-alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, Kokosalkyldimethylaminoxid and Kokosalkylpolyglucosid with an average of 1, 4 glucose units.
  • 8 -io alkyl polyglucosides with 1 to 2 glycoside units used fatty alcohol polyglycol ethers having, in particular 2 to 8 EO, for example C 12 fatty alcohol + 7 EO ether, and C - Surfactants are also particularly preferred here based on oleochemicals such as C i 8. 8
  • 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 '") (R IV ) (R V ) N + CH 2 COO - , in which R'" 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 Cio-C- 8- Alkyl-dimethylcarboxymethylbetaine and Cn-Ciz-alkylamidopropyl-dimethylcarboxymethylbetaine.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R VI ) (R V ") (R VI ") (R IX ) N + X " , in which R v ⁇ to R ⁇ x for four identical or different, in particular two long, and two short-chain, alkyl radicals and X 'are an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • the agent contains as surfactant components only one or more anionic surfactants, preferably C 8 -C 8 -alkyl sulfates and / or C 8 -C 8 -alkyl ether sulfates, and / or one or more nonionic surfactants, preferably C 8 _i 8 - fatty alcohol polyglycol ethers having 2 to 8 EO and / or C 8 _i 0 -Alkylpolyglucoside having 1 to 2 glycoside units. It is further very particularly preferred that the surfactants are made from renewable raw materials.
  • composition according to the invention preferably contains surfactants in amounts of from 5 to 50% by weight, in particular from 10 to 40% by weight.
  • Cleaning formulations according to the invention also contain one or more acids and / or salts thereof for enhancing 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 formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and mixtures thereof.
  • 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.
  • the acids and / or their salts are particularly preferably selected from the group comprising citric acid, lactic acid, formic acid, their salts and mixtures thereof. They are preferably used in amounts of 0.01 to 10 wt .-%, particularly preferably 0.2 to 5 wt .-%.
  • 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 .-%.
  • a perfume component d-limonene may be contained.
  • the perfume contains natural fragrance mixtures, as they are mainly accessible from plant sources. Therefore, in a particularly preferred embodiment, the perfume is 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.
  • 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.
  • a fragrance 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. Most fragrances have molecular weights of up to about 200 daltons, while molar masses 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, Chamomile Oil, Camphor Oil, Kanaga Oil, Cardamom Oil, Cassia Oil, Pine Needle Oil, Kopa ⁇ vabalsam Oil, Coriander Oil, Spearmint Oil, Cumin Oil, Cumin Oil, Lemongrass Oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli oil, Niaouli oil, Olibanum oil
  • fragrances of natural or synthetic origin can be used in the context of the present invention advantageously as adherent fragrances or fragrance mixtures in the perfume oils.
  • These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, borneol, bornyl acetate, ⁇ -bromostyrene, n -Decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl
  • 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.
  • composition according to the invention may contain further ingredients, including other acids, salts, surfactants, film formers, thickeners, solvents, antimicrobial agents, builders, corrosion inhibitors, complexing agents, alkalis, preservatives, bleaches, enzymes, fragrances and dyes and mixtures the same.
  • further ingredients including other acids, salts, surfactants, film formers, thickeners, solvents, antimicrobial agents, builders, corrosion inhibitors, complexing agents, alkalis, preservatives, bleaches, enzymes, fragrances and dyes and mixtures the same.
  • further ingredients including other acids, salts, surfactants, film formers, thickeners, solvents, antimicrobial agents, builders, corrosion inhibitors, complexing agents, alkalis, preservatives, bleaches, enzymes, fragrances and dyes and mixtures the same.
  • not more than 30 wt .-% of further ingredients should be included, preferably 0.01 to 30 wt .-%, in particular 0.2 to 15 wt
  • a preferred component of the cleaning agent according to the invention is a film former which contributes to better wetting and surface modification.
  • All the film-forming polymers used in detergents and cleaners in the prior art can be used for this purpose, but the film former is preferably selected from the group comprising polyethylene glycol, polyethylene glycol derivatives and mixtures thereof, preferably having a molecular weight between 200 and 20,000,000 between 5,000 and 200,000.
  • the film former is advantageously used in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.
  • a thickener Both in order to allow longer adherence of the cleaning agent to the surface to be cleaned, as well as to optimize the rheology of liquid or gel detergent, it may also be advantageous to increase the viscosity of the agent by using a thickener.
  • Suitable for this purpose are all viscosity regulators customarily used in detergents and cleaners, 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 products (carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and the like, core flour ethers), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids,
  • polyacrylic and polymethacrylic compounds include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (US Pat. CTFA): carbomers), also referred to as carboxyvinyl polymers.
  • polyacrylic acids are obtainable inter alia from Fa. 3V Sigma under the tradename Polygel ® such as Polygel ® DA, and by the company.
  • Carbopol ® such as Carbopol ® 940 (molecular weight about 4,000,000), Carbopol ® 941 (molecular weight approximately 1,250,000) or Carbopol ® 934 (molecular weight approximately 3,000,000).
  • carbopol ® 940 molecular weight about 4,000,000
  • Carbopol ® 941 molecular weight approximately 1,250,000
  • Carbopol ® 934 molecular weight approximately 3,000,000.
  • acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with C
  • 4- alkanols formed esters (INCI Acrylates Copolymer), which include about the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3 ), and which are obtainable for example from Messrs.
  • thickening agents are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, e.g. propoxylated guar, as well as their mixtures.
  • polysaccharide thickeners such as starches or cellulose derivatives, may be used alternatively, but preferably in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, e.g.
  • a particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum produced by Xanthomonas campestris and some other species under aerobic conditions having a molecular weight of 2-15x10 6 and for example, from the company. Kelco under the trade name Keltrol and Kelzan or by the company Rhodia under the trade name Rhodopol ® is available.
  • phyllosilicates include, for example, available under the trade name Laponite ® magnesium or sodium magnesium phyllosilicates from Solvay Alkali, in particular the Laponite ® RD or Laponite ® RDS, and the magnesium silicates Süd-Chemie, especially the Optigel ® SH.
  • the cleaning agent according to the invention contains from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight, of a thickener, preferably a polysaccharide thickener, for example xanthan gum.
  • solvents in particular water-soluble organic solvents.
  • solvents include, for example, lower alcohols and / or ether alcohols, which are understood as lower alcohols in the context of this invention straight-chain or branched C- ⁇ - 6 alcohols.
  • the alcohols used are in particular ethanol, isopropanol and n-propanol.
  • ether alcohols are sufficiently water-soluble compounds having up to 10 carbon atoms in the molecule into consideration. Examples of such ether alcohols are ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol monobutyl ether,
  • the cleaning agent therefore contains one or more antimicrobial agents, preferably in an amount of 0.01 to 1% by weight, preferably 0.02 to 0.8 wt .-%, in particular 0.05 to 0.5 wt .-%, particularly preferably 0.1 to 0.3 wt .-%, most preferably 0.2 wt .-%.
  • disinfection, sanitation, antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention.
  • sanitation in the strict sense of medical practice the killing of - in theory all - infectious germs means sanitation is to be understood as the elimination of all saprophytic germs, which are normally harmless to humans.
  • 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.
  • 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 and peroxides.
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylenebis (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-
  • Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, it is also possible to use antimicrobial-effective essential oils which at the same time ensure scenting of the cleansing agent.
  • particularly preferred antimicrobial agents are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite and mixtures thereof.
  • water-soluble and / or water-insoluble builders may be used in the cleaning agents 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. corrosion inhibitors
  • Suitable corrosion inhibitors are, for example, the following named according to INCI: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphates, Nitromethanes, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.
  • 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 called complexing agents: Aminotri- methylene phosphonic acid, beta-alanines diacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriamine pentamethylene phosphonic acid, dipotassium EDTA, disodium Azacycloheptane Diphosphonates, Disodium EDTA, Disodium Pyrophosphates, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphates, Pentasodium Aminotrimethylene Phosphonates, Pentasodium Ethylenediamine Tetramethylene Phosphonates, Pentasodium Pentetate
  • alkalis 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.
  • ammonia and / or alkanolamines having up to 9 C atoms in the molecule preferably the ethanolamines, in particular monoethanolamine.
  • Preservatives may also be included in compositions of the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.
  • bleaching agents can be added to the cleaning agent.
  • Suitable bleaching agents include peroxides, peracids and / or perborates, particularly preferred is hydrogen peroxide.
  • Sodium hypochlorite on the other hand, is less suitable for acidic detergents due to the release of toxic chlorine gas vapors, but can be used in alkaline detergents.
  • a bleach activator may be required in addition to the bleaching agent.
  • 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. In the case of liquid or gel-containing compositions, these include, in particular, solutions of the enzymes, advantageously as concentrated as possible, sparing 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.
  • enzymes preferably proteases, lipases, amylases, hydrolases and / or cellulases.
  • an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. advantageously, are such granules, for example, by applying polymeric film-forming, low-dust and storage stable due to the coating.
  • enzyme-stabilizing agents may be present in enzyme-containing agents to protect an enzyme contained in an agent according to the invention from damage such as inactivation, denaturation or disintegration, 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,
  • 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.
  • the agent according to the invention may finally contain one or more fragrances and / or one or more dyes (INCI Colorants).
  • 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 act substantively even with prolonged exposure.
  • the dyes are preferably present in an amount of 0.0001 to 0.1 wt .-%, in particular 0.0005 to 0.05 wt .-%, particularly preferably 0.001 to 0.01 wt .-%, contained.
  • the cleaner formulation according to the invention is used in a toilet bowl made of a recyclable and / or renewable and / or biodegradable plastic used.
  • This dispenser serves to deliver the solid, liquid or gel detergent formulation into the toilet bowl. It consists essentially of one holder suspendable at the edge of the toilet bowl and a container attached to the holder, which receives the detergent formulation according to the invention.
  • the container may have one or more chambers, so that even different formulations can be dispensed simultaneously in the toilet bowl. Each chamber has a dispensing device, by means of which the formulation contained in the chamber emerge from the container and into which the dispenser overflowing rinse water can be discharged.
  • This dispensing device is designed in the usual way.
  • conventional toilet bowls are manufactured by injection molding from a petrochemical-based plastic, usually polypropylene (PP).
  • PP polypropylene
  • a plastic material obtained from renewable raw materials and / or biodegradable and / or recyclable is used to produce the toilet bowls according to the invention.
  • a biologically based polypropylene which can be obtained from ethanol from natural sources, such as sugar cane, is suitable (Braskem).
  • the toilet bowl according to the invention may also be made of polylactic acid (poly (lactic acid), PLA).
  • polylactic acid poly (lactic acid), PLA
  • PLA poly(lactic acid), PLA)
  • PLA polyhydroxybutyric acid
  • PHB polyhydroxybutyric acid
  • This polyester is a biopolymer obtained by fermentation from sugar, starch or alcohols with properties similar to those of polypropylene and is also biodegradable.
  • PHB is commercially available from Biomer.
  • starch-based polymers available under the trade name Bioplast from Biotec for producing dispensing devices according to the invention.
  • suitable plastics are manufactured by Cereplast, for example Biopropylene TM, a hybrid material in which 50% of the petrochemical portion is replaced by polymers derived from corn, tapioca, wheat or potato starch.
  • Recyclable plastics which can also be used in the context of this invention, are thermoplastics that are suitable for use in injection molding, ie a not too brittle.
  • PP polypropylene
  • these include, for example, polyethylene terephthalate (PET) or polystyrene (PS).
  • PET polyethylene terephthalate
  • PS polystyrene
  • hooks and baskets may be made of different materials that the skilled artisan will select appropriately.
  • the hook can be made of polypropylene and the basket of the brittle PLA.
  • Detergents E1 to E9 according to the invention and comparative agents V1 to V3 were formulated.
  • compositions are shown in Tables 1 to 3 below. All quantities are in wt .-%.
  • the raw materials marked with an asterisk (*) are obtained wholly or partly from renewable sources.
  • the pH values were determined electrochemically in the concentrate.
  • the formulations of the present invention all had a native source carbon content of 76 to 93%, while the comparative formulations related only 15 to 28% of the contained carbon from renewable resources. All formulations showed good foaming power, good leaching properties and satisfactory rinsing behavior. The storage stability (4 weeks at 4O 0 C and 12 weeks at 23 0 C) was also satisfactory in all cases. Thus, without sacrificing cleaning performance, foaming power, rinsing behavior or storage stability, the raw materials used hitherto can be replaced on a petrochemical basis by environmentally friendly raw materials from renewable sources.
  • the foaming power was determined by the foam behavior test according to Wagner. For this purpose, in each case 0.1 g of the solid, liquid or gel-form detergent formulation in 500 ml tap water (17 ° dH) was foamed in a 100 ml graduated cylinder with 40 strokes at a speed of 100 rpm. The foam volume formed was determined after one, three and ten minutes. To determine the lime-dissolving power of gel-like cleaning agents, in each case one pre-weighed white Carrara marble plates measuring 75 * 150 * 5 mm were completely immersed in the gel in a Plexiglas cuvette and left there for 10 s. Thereafter, the plate was removed and placed vertically in such a designated tripod that adhering product could run off. After 10 minutes, the plate was rinsed with water and determined after drying at 105 0 C, the weight loss.
  • the measurement of the Ab concurs s performed on an automatically controlled toilet facility, which gave at intervals of 1 hour the contents of the water box, filling the box again with 9 I of tap water at 17 ° dH and a water temperature of 15 to 16 0 C.
  • a filling of a dispensing device according to DE 195 20 145 was hung in the toilets and determined after how many rinses the agent was completely consumed. Each determination was made five times and the mean was formed.
  • the storage stability was determined by storage in electrically controlled heating chambers. The funds were initially for four weeks at 4O 0 C and then stored at 23 0 C twelve weeks. This was followed by a visual inspection of the stored goods.
  • the viscosity was additionally determined. The measurement was performed with a Brookfield RVT rotational viscosimeter with Helipath- means and TA spindle at 1 U / min and 23 0 C. preferably have detergent formulations according to the invention has a viscosity from 0.4 to 400,000 mPas.
  • the gel-like agents E1 to E3 had viscosities in the range of about 70,000 to 180,000 mPas, the liquid formulations E4 to E6 possessed viscosities in an amount of about 2,000 to 4,000 mPas.
  • the formulations according to the invention were introduced into dispensing devices which consisted of a recyclable and / or renewable and / or biodegradable plastic.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Epidemiology (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un système composé d'une formulation nettoyante pour WC comprenant au moins un acide et/ou son sel, un tensioactif et un parfum, ainsi que d'un dispositif de distribution constitué d'un plastique recyclable, renouvelable et/ou biodégradable. Ce système peut être utilisé pour le nettoyage de cuvettes de WC et/ou pour parfumer ces dernières et présente un profil environnemental amélioré en comparaison des produits traditionnels.
PCT/EP2010/053461 2009-03-25 2010-03-17 Système composé d'un produit de nettoyage et d'un dispositif de distribution WO2010108834A1 (fr)

Applications Claiming Priority (2)

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DE200910001841 DE102009001841A1 (de) 2009-03-25 2009-03-25 System aus Reinigungsmittel und Abgabevorrichtung
DE102009001841.7 2009-03-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104762141A (zh) * 2014-01-05 2015-07-08 上海弥乐化工新材料有限公司 一种固体洁厕剂及其制备方法
US20230049070A1 (en) * 2021-07-29 2023-02-16 Henkel IP & Holding GmbH Dissolvable Toilet Brush Formulations

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Publication number Priority date Publication date Assignee Title
US5188755A (en) * 1991-10-10 1993-02-23 Block Drug Company Surface erodible controlled releasing, free standing cleansing block and cleaning method for the domestic water closet
EP0619366A1 (fr) * 1993-04-05 1994-10-12 The Procter & Gamble Company Blocs pour toilettes contenant de l'oxygène actif
DE19520145A1 (de) 1995-06-01 1996-12-05 Henkel Kgaa WC-Körbchen für flüssige oder pastöse Wirkstoffzubereitungen
DE19715872A1 (de) * 1997-04-16 1998-10-22 Henkel Kgaa Gelförmiges Reinigungsmittel für Spültoiletten
EP1029911A1 (fr) * 1999-02-17 2000-08-23 Cognis Deutschland GmbH Gel pour le nettoyage des toilettes
DE102004035655A1 (de) * 2004-07-22 2006-02-16 Henkel Kgaa Verfahren zur Herstellung von Mehrphasen-Sticks für die WC-Reinigung
WO2006058894A1 (fr) * 2004-12-04 2006-06-08 Symrise Gmbh & Co. Kg Bloc invisible pour wc
WO2009024743A1 (fr) * 2007-08-17 2009-02-26 Reckitt Benckiser Inc. Compositions acides de traitement des toilettes, écologiquement acceptables

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5188755A (en) * 1991-10-10 1993-02-23 Block Drug Company Surface erodible controlled releasing, free standing cleansing block and cleaning method for the domestic water closet
EP0619366A1 (fr) * 1993-04-05 1994-10-12 The Procter & Gamble Company Blocs pour toilettes contenant de l'oxygène actif
DE19520145A1 (de) 1995-06-01 1996-12-05 Henkel Kgaa WC-Körbchen für flüssige oder pastöse Wirkstoffzubereitungen
DE19715872A1 (de) * 1997-04-16 1998-10-22 Henkel Kgaa Gelförmiges Reinigungsmittel für Spültoiletten
EP1029911A1 (fr) * 1999-02-17 2000-08-23 Cognis Deutschland GmbH Gel pour le nettoyage des toilettes
DE102004035655A1 (de) * 2004-07-22 2006-02-16 Henkel Kgaa Verfahren zur Herstellung von Mehrphasen-Sticks für die WC-Reinigung
WO2006058894A1 (fr) * 2004-12-04 2006-06-08 Symrise Gmbh & Co. Kg Bloc invisible pour wc
WO2009024743A1 (fr) * 2007-08-17 2009-02-26 Reckitt Benckiser Inc. Compositions acides de traitement des toilettes, écologiquement acceptables

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Title
WASSER; HONIG; MEERSALZ: "International Cosmetic Ingredient Dictionary and Handbook", vol. 1101, 1997, THE COSMETIC, TOILETRY, AND FRAGRANCE ASSOCIATION

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104762141A (zh) * 2014-01-05 2015-07-08 上海弥乐化工新材料有限公司 一种固体洁厕剂及其制备方法
CN104762141B (zh) * 2014-01-05 2018-10-23 上海弥乐化工新材料有限公司 一种固体洁厕剂及其制备方法
US20230049070A1 (en) * 2021-07-29 2023-02-16 Henkel IP & Holding GmbH Dissolvable Toilet Brush Formulations

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