EP1781765A1

EP1781765A1 - Cleaning agent exhibiting faecal stain repelling properties

Info

Publication number: EP1781765A1
Application number: EP05775044A
Authority: EP
Inventors: Michael Dreja; Daniela Poethkow; Stefan Frey; Kerstin Ziganke; Alexander Ditze; Brigitte Giesen
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2004-08-23
Filing date: 2005-08-10
Publication date: 2007-05-09
Anticipated expiration: 2025-08-10
Also published as: DE502005010447D1; DE102004040848A1; PL1781765T3; ATE486117T1; WO2006021322A1; EP1781765B1

Abstract

The invention relates to a cleaning agent for hard surfaces, especially sanitary ceramic surfaces, containing at least one polymer-analogous taurine-modified acrylic acid polymer, and/or at least one polymer-analogous taurine-modified acrylic acid copolymer and/or at least one polymer-analogous taurine-modified acrylate polymer and/or copolymer. Said cleaning agent can be used in a method for improving the removeability of faecal stains in flush toilets, the taurine-modified acrylic or acrylate polymer or copolymer being used to modify hard surfaces, by the formation of a thin, shiny, stain-repellent film, and to improve the rinsability of dried residues of the cleaning agent.

Description

"Cleaner with faecal dirt repellent properties"

The present application relates to a cleaning agent for hard surfaces, in particular sanitary ware, which contains polymer-analogous taurine-modified acrylic acid polymers and / or copolymers and / or acrylate polymers and / or acrylate copolymers. These additives improve the cleaning performance against fecal soils by both easier removability and reduced tendency to repellency.

When cleaning a flush toilet, especially limescale and urine stone as well as faecal matter adhering to the ceramic must be removed. Conventional toilet cleaners are often formulated acidic, for example by addition of organic acids such as citric acid or sulfamic acid, so that they have a good activity against lime and urine stone auf¬. As a rule, the cleaning performance against fecal dirt is also good, although it must be acted upon mechanically, ie with the aid of a toilet brush, on the toilet surface. This mechanical complexity increases even with older, already dried stains, even moist fecal soiling can stubbornly adhere to ceramic materials. A longer-lasting cleanliness of the inside of the toilet compared to new fecal soiling beyond the one-time use could not previously be achieved with conventional cleaners.

For better lime solution toilet cleaners are often left after application for a long time, often several hours or even overnight, for acting on the ceramic. The formulations are usually thickened to improve the adhesion to the ceramic. When prolonged exposure then forms on the surface of a film that is usually colored due to the product coloring and after drying is difficult to remove.

Surprisingly, it has now been found that both an easier and faster removal of fecal dirt and an improved rinsing of the dried (colored) detergent itself is possible when the detergent formulation polymer analog with taurine (2-aminoethanesulfonic acid) modified acrylic acid or acrylate polymer or copolymer is added. Detergents containing such a polymer, when used, form a durable, thin film on ceramic surfaces that can swell with water during rinsing. If fecal dirt hits the film, the dirt can be removed during the next rinse without significant mechanical force. With prolonged use of the colored cleaning formulations in toilets and subsequent drying, the formed colored film is easily and completely removed on rinsing again.

The use of such taurine-modified acrylic polymers in detergents and cleaning agents has already been described. For example, WO 97/11144 A1 (BASF) claims the use of polycarboxylic acid halfbamides as an incrustation-inhibiting additive to detergents and cleaners. Incrustations are understood as the deposition of metal salts on textile surfaces and pipelines, etc., the Polycarbonsäurehalbamide should be obtained by reacting anhydride-containing polymers with Aminocar- bonsäuren, aminophosphonic and / or taurine or alkyltaurines.

WO 02/44268 A1, WO 02/44224 A2, WO 02/44230 A2 and WO 02/44267 A2 (all: Clariant) also describe similar polymers and their use in detergents and cleaners, cosmetics, etc. The polymers consist of acryloyldimethyltaurine (2-acrylamido-2-methylpropanesulfonic acid, AMPS) and other comonomers and are said to serve as thickeners.

The prior art does not describe the use of polymer-analogous taurine-modified acrylic and / or acrylate polymers in hard surface cleaners for easier removal of fecal dirt on WC ceramics and for improved rinsability of dried detergents.

Accordingly, the object of the present invention is to improve the removability of fecal dirt and the flushability of dried detergents from hard surfaces, in particular WC ceramics.

The invention relates to a cleaning agent for hard surfaces, in particular sanitary ware, which contains at least one polymer-analogous taurine-modified acrylic acid and / or acrylate polymer and / or copolymer. Through the use of taurine-modified acrylic acid or acrylate (co) polymers, the film formed by the cleaning agent on the toilet ceramic has a dirt-repelling effect on faecal dirt, so that this - even without additional mechani¬ cal help by using the toilet brush - when operated the toilet flush can be easily removed. In addition, residues of the cleaner formulation after drying are better rinsed off.

Further advantages of the inventive cleaning agent are the more homogeneous and complete wetting of the cleaner when applied to hard surfaces, as well as the modification of hard surfaces during cleaning application by the formation of a very thin, glossy film so that cleaned surfaces are perceived by the consumer to be longer than clean.

Further subjects of the invention therefore relate to the use of a cleaning agent which contains at least one polymer-analogous taurine-modified acrylic acid and / or acrylate polymer and / or copolymer for modifying hard surfaces, in particular sanitary ware, to form a thin, glossy film to improve the removability of Faecal contamination in flush toilets and for improving the rinsability of dried detergent residues on hard surfaces, in particular sanitary ware.

The cleaning agent described can be used in a process for cleaning toilet surfaces, in particular faecal dirt can be easily removed. Another subject of the invention therefore relates to a method for improving the removability of fecal soiling in flush toilets, in which a detergent according to the invention is distributed over the surface area and either rinsed after a short exposure time of 2 to 10 minutes or allowed to dry.

In addition to the polymers mentioned, the cleaning agent according to the invention may contain further customary ingredients which can be used in hard surface cleaners. For this purpose, in particular surfactants, film formers, thickeners, acids, solvents, antimicrobial agents and other ingredients such as builder components, alkalis, preservatives, enzymes, excipients, fragrances or dyes are calculated. Substances which also serve as ingredients of cosmetic products are referred to below, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed only after Linne in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names can be found in the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC, 20036, USA , which publishes more than 9,000 INCI names and references to more than 37,000 trade names and technical names, including related distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, for example polymer ethers, and one or more functions, for example surfactants-cleansing agents, which in turn are explained in more detail and in more detail which may also be referred to below.

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

polymers

The composition according to the invention comprises at least one polymer analog taurine-modified acrylic acid polymer and / or at least one polymer analog taurine-modified acrylic acid copolymer and / or at least one polymer analog taurine-modified acrylate polymer and / or copolymer. This (co) polymer is obtainable by polymerization of 2-sulfoethylacrylamide, optionally also copolymerization of 2-sulfoethylacrylamide with acrylic acid or acrylates and other monomers, by conventional methods; Furthermore, a subsequent reaction of a polyacrylic acid or a polyacrylate or a copolymer thereof with taurine is possible. Suitable starting materials are, for example, the Sokalan offered by the company BASF ^® grades, as well as polyacrylic acids and polyacrylates are other manufacturers, for example Carbopol ^® grades from Noveon. The molecular weight of the (co) polymer is preferably between 2,000 and 20,000,000, in particular between 20,000 and 1,000,000. The degree of substitution of the acrylic acid or acrylate polymer or copolymer with taurine is between 0.01 and 1, preferably between 0.2 and 0.8. If the polymer used is a copolymer, this results by copolymerization of acrylic acid and / or acrylate or of 2-sulfoethylacrylamide with one or more further monomers, preferably selected from the group comprising methacrylic acid, methyl methacrylate, alkyl acrylates, alkyl methacrylates, PEG acrylates, (poly) alkoxylated acrylates, ethylenically unsaturated quaternary ammonium compounds, in particular MAPTAC or DADMAC, and mixtures thereof. In this case, the monomers in the polymer may be arranged alternately, randomly or else in blocks, but the copolymer should be composed of at least 50 mol% of acrylic acid or acrylate monomers. The taurine-modified polyacrylic acid and / or polyacrylate copolymer may also be crosslinked.

The content of taurine-modified acrylic acid and / or acrylate polymer and / or copolymer in the cleaning agent according to the invention is preferably from 0.01 to 50% by weight, in particular from 0.2 to 15% by weight.

surfactants

The agent according to the invention can furthermore also contain surface-active substances. As surface-active substances are suitable for the invention

Medium surfactants, in particular from the classes of anionic and nonionic

Surfactants.

Suitable anionic surfactants are preferably C ₈ -C ₈ -alkylbenzenesulfonates, in particular with about 12 C atoms in the alkyl moiety, C ₈ -C ₂ 0-alkanesulfonates, C ₈ -C ₈ -monoalkyl sulfates, C ₈ -C ₁₈ -Alkylpolyglykolethersulfate with 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic mono- and di-C ₈ -C ₁₈ alkyl esters. Can furthermore also C ₈ -C ₁₈ -α-olefinsulfonates, sulfonated C ₈ -C ₁₈ fatty acids, especially dodecyl benzene sulfonate, C ₈ -C ₂₂ -Carbonsäureamidethersulfate, C ₈ -C carboxylates -Alkylpolyglykolethercar- _8, C ₈ -C ₁₈ N-acyl taurides, C ₈ -C ₁₈ N sarcosinates and C ₈ -C ₁₈ alkyl isethionates or mixtures thereof.

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.

Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkanesulfonate having about 15 carbon atoms and sodium dioctylsulfosuccinate. To be particularly suitable Sodium fatty alkyl sulfates and fatty alkyl + 2E0 ether sulfates having 12 to 14 carbon atoms proved.

As nonionic surfactants are especially Cs-Ci _B -Alkoholpolyglykolether, ie ethoxylated and / or propoxylated alcohols having 8 to 18 carbon atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and / or propylene oxide units (PO), C ₈ -Ci ₈ 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 part and 2 to 8 EO, long-chain amine oxides having 14 to 20 C atoms and long-chain Alkyl polyglycosides having 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units to mention. Examples of such surfactants are oleyl-cetyl alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, Kokosalkyldimethylaminoxid and Kokosalkylpolyglucosid with an average of 1, 4 glucose units. Particularly preferred are C ₈ i ₈ fatty alcohol polyglycol ethers having, in particular 2 to 8 EO, for example C ₂ fatty alcohol + 7 EO ether, and C _8-10 - alkyl polyglucosides having 1 to 2 glycoside units used.

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

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

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^VI ) (R ^V ") (R ^VI ") (R ^IX ) N ⁺ X ^" , in which R ^vι to ^Rιx 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.

In a particularly preferred embodiment, however, the surfactant components the agent contains only one or more anionic surfactants, preferably C ₈ -C ₁₈ - alkyl sulfates and / or C ₈ -C ₁₈ alkyl ether sulfates, and / or one or more nonionic Surfactants, preferably C _8-18 fatty alcohol polyglycol ethers having 2 to 8 EO and / or C _8-10 alkyl polyglucosides having 1 to 2 glycoside units.

The composition according to the invention preferably contains surfactants in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.

film formers

Another 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.

thickener

In order to enable a longer adherence of the cleaning agent to the surface to be cleaned, it may also be advantageous to increase the viscosity of the agent by using a thickening agent. 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 , Clay minerals such as montmorillonite, zeolites, silicas).

Examples of 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): Carbomer), also known as Carboxyvinyl polymers. Such polyacrylic acids are obtainable inter alia from Fa. 3V Sigma under the tradename Polygel ^® such as Polygel ^® DA, and by the company. BFGoodrich under the tradename 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). Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C _1-4 -alkanols (INCI acrylates copolymer), such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and, for example, by the company Rohm & Haas under the trade names Aculyn ^®. and Acusol ^® and are available from Degussa (Goldschmidt) under the trade name Tego ^® polymer obtainable, for example the anionic nicht¬ associative polymers Aculyn ^® 22, Aculyn ^® 28, Aculyn ^® (crosslinked) 33, Acusol ^® 810, Acusol ^® 823 and Acusol ^® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C _10-30 alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci _-4 Alkanols formed, esters (INCI Acrylates / C 10-30 alkyl acrylate crosspolymer) include and which are available, for example, from the company BFGoodrich under the trade name Carbopol ^® , eg the hydrophobic Carbopol ^® ETD 2623 and Carbopol ^® 1382 (INCI Acrylates / C 10 -30 alkyl acrylate Crosspolymer) and Carbopol AQUA ^® 30 (formerly Carbopol ^® EX 473).

Further thickeners 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, for example propoxylated guar, and also their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl or hydroxyethyl -, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate. A particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, that of Xanthomonas campestris and some other species is produced under aerobic conditions with a molecular weight of 2-15x10 ⁶ and is available for example from Kelco under the trade names Keltrol ^® and Kelzan ^® or from the company Rhodia under the trade name Rhodopol ^® .

As thickeners, it is also possible to use phyllosilicates. These 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.

In a preferred embodiment, 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.

acids

Detergents according to the invention may further contain one or more acids for enhancing the cleaning performance against lime and urine stone. Suitable acids are 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 or amidosulfonic acid. In addition, however, it is also possible to use the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or mixtures thereof. Particular preference is given to acids selected from the group comprising amidosulfonic acid, citric acid, lactic acid and formic acid. They are preferably used in amounts of 0.01 to 30 wt .-%, particularly preferably 0.2 to 15 wt .-%.

solvent

Another preferred component of agents according to the invention are solvents, in particular water-soluble organic solvents. These 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 _1-6 alcohols.

The alcohols used are in particular ethanol, isopropanol and n-propanol. As 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, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether, of which in turn Ethylene glycol monobutyl ether and propylene glycol monobutyl ether are preferred. In a preferred embodiment, however, ethanol is used as the solvent. Solvents may be included in the detergent in amounts of 0.01 to 30% by weight, preferably 0.2 to 15% by weight.

Antimicrobial agents

A particular form of cleaning is disinfection and sanitation. In a corresponding particular embodiment of the invention, the cleaning agent therefore comprises 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 .-%.

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

For example, antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention Derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores 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 - ^ - chlorophenyl-N-CS ^ -dichlorphenyQ-urea, N, N '- (1, 10 decandiyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride ₁ N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecane diimidamide, antimicrobial quaternary surface active compounds, guanidines. 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 provide for a scent of the cleansing agent. However, 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.

Other ingredients

In addition to the components mentioned so far, the composition according to the invention may contain further ingredients, including builder components, corrosion inhibitors, complexing agents, alkalis, preservatives, bleaches, enzymes, fragrances and dyes. Overall, not more than 30 wt .-% of further ingredients should be included, preferably 0.01 to 30 wt .-%, in particular 0.2 to 15 wt .-%.

If desired, 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 residue on hard surfaces. Typical builders which may be present in the context of the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, 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.

Suitable corrosion inhibitors (INCI Corrosion Inhibitors) are, for example, the following according to INCI substances: 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 oxalates, sodium silicates, stearamidopropyl dimethicones, tetrapotassium pyrophosphates, tetrasodium pyrophosphates, triisopropanolamines.

Chelating agents (INCI), also called sequestering agents, are ingredients that are capable of complexing and inactivating metal ions to prevent their adverse effects on the stability or appearance of the agents, such as cloudiness. 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: aminotrimethylene, phosphonic acid, beta-alanines diacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrates, diammonium EDTA, diethylenetriamines pentamethylene phosphonic acid, dipotassium EDTA, disodium azacycloheptanes diphosphonates , Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycino Phenol Sulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

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

Preservatives may also be included in compositions of the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.

According to the invention, 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. Under certain circumstances, 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. Type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, it is additionally possible to apply further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating. In addition, enzyme stabilizers may be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention from damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage. As enzyme stabilizers are, in each case depending on the enzyme used, particularly suitable: 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 reduced C terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ such as succinic acid, other dicarboxylic acids or salts of said acids; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known in the art. Preference is given to using combinations of stabilizers, for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

As further ingredients, the agent according to the invention may finally contain one or more fragrances and / or one or more dyes (INCI Colorants). As dyes both water-soluble and oil-soluble dyes can be used, on the one hand the compatibility with other ingredients, such as bleaches, is observed and on the other hand, the dye used against the toilet ceramic should not act substantively even with prolonged exposure. The choice of suitable perfume is also limited only by possible interactions with the other detergent components.

The cleaning agent according to the invention finds application in the treatment of hard surfaces, in particular sanitary ware. On the one hand, it can be used to modify hard surfaces to form a thin, glossy film that, on the one hand, repels dirt and, on the other hand, helps the consumer perceive the cleaned surface as clean for longer. Furthermore, the taurine-modified acrylic acid and acrylate (co) polymers used can be used to improve the removability of fecal dirt in dishwashing toilets. Likewise, their use to improve the rinsability of dried detergent residues on hard surfaces, in particular of sanitary ware is possible. Finally, the agent according to the invention can also be used in a process for improving the removability of faecal dirt in flush toilets. In this process, the agent is spread over the surface and either rinsed after a short exposure time of 2 to 10 minutes or left to dry. After treating the surface in this manner, fecal soiling is easier to remove, often without the aid of mechanical aids, such as a toilet brush. In addition, any dried-up detergent residues can be rinsed off more easily.

embodiments

Three acidic WC cleaners E1 to E3 with different proportions of the taurine-modified polyacrylate according to the invention were formulated. On the other hand, a comparative formulation V1 was free of this polymer.

Composition [% by weight] E1 E2 E3 V1

Taurine-modified polyacrylaf 1 3 10 0

C12 fatty alcohol ethoxylate + 7 EO 3 3 3 3

Octyl sulfate 2 2 2 2

Keltrol ASX-T (xanthan gum) 0.3 0.3 0.3 0.3

Citric acid 5 5 5 5

Blue dye 0.1 0.1 0.1 0.1

Ethanol 3 3 3 3

Perfume 0,2 0,2 0,2 0,2

Water ad 100 ad 100 ad 100 ad 100 a: Sokalan PA 110 S, carboxyl groups 50% polymer-analogously modified with taurine (= 2-aminoethanesulfonic acid, CAS No. 91105-79-2)

With these formulations, tests were carried out for cleaning performance against faecal dirt and for rinsing. In each case, a commercial toilet type V & B was thoroughly cleaned, rinsed and allowed to dry thoroughly using a toilet brush and Ata scrub milk.

To test the cleaning performance, one of the toilet-cleaner formulations E1-E3 according to the invention or the comparison formulation V1 was then applied, distributed over a wide area, allowed to act for 5 minutes and rinsed off. Thereafter, an artificial fecal dirt (mixture of bacterial biomass, fiber of vegetable cell wall material, glycerol and an aqueous solution, according to the patent DE 103 57 232 B3 was applied, allowed to dry for 30 minutes and rinsed off. of the fecal soiling, 70% of the fecal dirt could already be removed on surfaces cleaned with the agent E1 according to the invention with one rinse, after the second rinse the dirt was 100% removed E3 cleaned surfaces no fecal dirt could be detected after a rinse.

To test the rinsability, one of the toilet-cleaner formulations E1-E3 according to the invention or the comparative formulation V1 was applied after the pre-cleaning described above, distributed over a wide area and allowed to act for three hours. Thereafter, a flat blue film was observed on the Toiletten¬ inner wall for all formulations. After rinsing the toilet, 90% of the original surface was covered with a visible blue film of cleaner formulation in the case of cleaner V1 not according to the invention, whereas no visible film was present when using the formulations E1, E2 and E3 according to the invention.

Furthermore, three coating solutions E4 to E6 were prepared, which also contained the inventive taurine-modified polyacrylate, and a comparative solution V2

Composition [wt.%] E4 E5 E6 V2

Taurine-modified polyacrylaf 2 5 5 0

Lauryl ether sulfate + 2EO 3 3 3

APG 220 UPW 3

PEG 40,000 MW 1

Citric acid 0.5 0.5 0.5 0.5

Ethanol 8 8 8 8

Perfume 0.05 0.05 0.05 0.05

Water ac / 100 ac / 100 ac / 100 ac / 100 a: Sokalan PA 110 S, carboxyl groups 70% polymer-analog modified with taurine (= 2-aminoethanesulfonic acid, CAS No. 91105-79-2)

Even with these coating solutions, tests were carried out for cleaning performance against fecal dirt and for rinsing. Again, a commercial toilet type V & B was thoroughly cleaned, rinsed and allowed to dry using a toilet brush and Ata scouring milk. Subsequently, one of the toilet cleaner formulations E4-E6 according to the invention or the comparative formulation V2 was applied, distributed over a wide area and allowed to dry. Thereafter, an artificial Fäkalschmutz (mixture of bacterial biomass, fiber from plant cell wall material, glycerol and an aqueous solution, according to the patent DE 103 57 232 B3 applied, allowed to dry for 30 minutes and rinsed. While 95% of the fecal dirt were still present when using the comparative formulation V2 not according to the invention, no faecal soil could be detected on the surfaces cleaned with the agents E4, E5 and E6 according to the invention.

Claims

claims

1. Cleaning agent for hard surfaces, in particular sanitary ware, characterized in that it contains at least one polymer analog taurine-modified acrylic acid polymer and / or at least one polymer analog taurine-modified acrylic acid copolymer and / or at least one polymer analog taurine-modified acrylate polymer and / or copolymer.

2. Cleaning agent according to claim 1, characterized in that the molecular weight of the acrylic acid or acrylate polymer or copolymer is between 2,000 and 20,000,000, preferably between 20,000 and 1,000,000.

3. Cleaning agent according to one of claims 1 or 2, characterized in that the degree of substitution of the acrylic acid or acrylate polymer or copolymer with taurine is between 0.01 and 1, preferably between 0.2 and 0.8.

4. Cleaning agent according to one of claims 1 to 3, characterized in that its content of taurine-modified acrylic acid and / or acrylate polymer and / or - copolymer is 0.01 to 50 wt .-%, preferably 0.2 to 15 wt. %.

5. Cleaning agent according to one of the preceding claims, characterized in that it comprises a taurine-modified acrylic acid and / or acrylate copolymer with one or more further monomers, preferably selected from the group comprising methacrylic acid, methyl methacrylate, alkyl acrylates, alkyl methacrylates, PEG acrylates, (poly) alkoxylated acrylates, ethylenically unsaturated quaternary ammonium compounds, in particular MAPTAC or DADMAC, and mixtures thereof, wherein the copolymer is composed of at least 50 mol% of acrylic acid monomers.

6. Cleaning agent according to claim 5, characterized in that the taurine-modified polyacrylic acid and / or polyacrylate copolymer can be cross-linked.

7. Cleaning agent according to one of the preceding claims, characterized in that it may contain 0.01 to 30 wt .-%, preferably 0.2 to 15 wt .-%, surfactants.

8. Cleaning agent according to one of the preceding claims, characterized in that it may contain 0.01 to 30 wt .-%, preferably 0.2 to 15 wt .-%, film-forming agent.

9. Cleaning agent according to claim 8, characterized in that the film former is selected from the group comprising polyethylene glycol, polyethylene glycol derivatives and mixtures thereof, preferably having a molecular weight between 200 and 20,000,000, more preferably between 5,000 and 200,000.

10. Cleaning agent according to one of the preceding claims, characterized in that it may contain 0.01 to 30 wt .-%, preferably 0.2 to 15 wt .-%, thickener.

11. Cleaning agent according to one of the preceding claims, characterized in that it may contain 0.01 to 30 wt .-%, preferably 0.2 to 15 wt .-%, acids.

12. Cleaning agent according to one of the preceding claims, characterized in that it may contain 0.01 to 30 wt .-%, preferably 0.2 to 15 wt .-%, solvent.

13. Cleaning agent according to one of the preceding claims, characterized in that it may contain one or more antimicrobial agents, preferably those 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.

14. Cleaning agent according to one of the preceding claims, characterized in that it contains 0.01 to 30 wt .-%, preferably 0.2 to 15 wt .-%, further ingredients, preferably selected from the group comprising builder components, corrosion inhibitors, complexing agents, Alkalis, preservatives, bleaches, enzymes, perfumes and dyes.

15. Use of a cleaning agent according to any one of claims 1 to 14 for modifying hard surfaces, in particular sanitary ware, wherein a thin, glossy film is formed.

16. Use according to claim 15, characterized in that the film acts dirt repellent.

17. Use of polymer-analogously taurine-modified acrylic acid and / or acrylate polymers and / or copolymers for improving the removability of fecal dirt in flush toilets.

18. Use of polymer-analogously taurine-modified acrylic acid and / or acrylate polymers and / or copolymers for improving the rinsability of dried detergent residues on hard surfaces, in particular sanitary ware.

19. A method for improving the removability of fecal soiling in flush toilets, characterized in that an agent according to any one of claims 1 to 14 is distributed over the surface area and either rinsed after a brief exposure time of 2 to 10 minutes or allowed to dry.