EP2129763A1

EP2129763A1 - Product for treating hard surfaces

Info

Publication number: EP2129763A1
Application number: EP08708990A
Authority: EP
Inventors: Nadine Warkotsch; Birgit Middelhauve; Marc-Steffen Schiedel; Matthias LÜKEN
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2007-04-03
Filing date: 2008-02-14
Publication date: 2009-12-09
Anticipated expiration: 2028-02-14
Also published as: PL2129763T3; ES2392368T3; US20100041574A1; EP2129763B1; WO2008119592A1; KR20090128432A; DE102007016389A1

Abstract

The invention relates to the use of a product for treating hard surfaces. Said product comprises compounds of general formula I or II and polymers that are obtainable by reacting said compounds with polymeric substrates, said substrates having functional groups which are selected from hydroxy groups, primary and secondary amino groups. The treated surface is protected from soiling and/or soil release from the surface is facilitated.

Description

"Agents for the treatment of hard surfaces"

The present invention relates to the field of hard surface treating agents, particularly to hard surface cleaners, and to agents which protect surfaces from soiling and / or facilitate the removal of soil contaminants.

Both in the household and in the commercial sector, hard surfaces occur in a variety of configurations, which are exposed to the effects of various types of dirt. By way of example, only the surfaces of wall and floor tiles, window glass, kitchen equipment and sanitary ware are mentioned here. To clean such surfaces surfactant-containing agents are used for a long time, the cleaning effect is based primarily on the ability of surfactants to solubilize dirt particles and thus make it removable from the surface or rinsed off. Depending on the nature of the surface and the nature of the dirt, the dirt on the surface, however, can adhere strongly. This is all the more true if the soiling remains on the surface for a long time and thus the adhesion is further intensified by aging processes. As a result, the dirt can be very difficult to remove and thus cause a great deal of cleaning. Therefore, in recent years with increasing intensity has been looking for means not only to improve the cleaning power of detergents, but to prevent the contamination of surfaces already in the approach or at least complicate.

For example, processes have been developed for a variety of hard materials, with which they are provided with dirt-repellent finishing during the manufacturing process. However, such permanent equipment can only be produced by expensive processes and are generally only available for new materials which are already equipped by the manufacturer.

In addition, however, agents have been found with which surfaces can be retrofitted and equipped in a way that can be carried out in a household so that they less easily pollute or easier to clean, at least for a certain period of use. Of particular practical interest is a facilitation and improvement of cleaning and a prevention of re-soiling in the field of sanitary ware. When cleaning a flush toilet, especially limescale and urine stone as well as faecal matter adhering to the ceramic must be removed. Conventional toilet detergents are often formulated acidic, for example by adding organic acids such as citric acid or sulfamic acid, so that they have a good activity against lime and urine stone. In general, the cleaning performance against fecal dirt is good, although mechanically, so with the aid of a toilet brush, the toilet surface must be acted upon. This mechanical complexity increases even with older, already dried stains, even moist fecal soiling can stubbornly adhere to ceramic materials.

From the patent application WO 2006/005358 copolymers are known which consist of at least one each of an anionic vinyl monomer, a vinyl monomer having a quaternary ammonium group or a tertiary amino group, and a nonionic hydrophilic vinyl monomer or a polyfunctional vinyl monomer. These copolymers are suitable as contamination-inhibiting components in cleaning agents and are effective, for example, against fecal contamination.

However, beyond the single use, longer-lasting cleanliness of the toilet inside against new Fäkalanschmutzung is not to achieve with these cleaners in a completely satisfactory manner.

Another problem may arise from the fact that toilet cleaners for better lime solution are often after application for a long time, often several hours or even overnight, left to act 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.

Hard surfaces, which are always subject to the action of moisture, are often colonized by microorganisms, and it comes to the formation of biofilms. Biofilms consist of a thin layer of mucus (film), in which microorganisms (eg bacteria, algae, fungi, protozoa) are embedded. This can be not only a hygienic but also an aesthetic problem. As an antidote bactericidal substances are often used. However, this is not always unproblematic in view of the ecotoxicological properties of many of these substances and the associated limitations in their application. In addition, biofilms contribute to the formation of unpleasant-smelling substances and are therefore a source of undesirable bad odors, especially in the sanitary sector. In addition, agents for the treatment of hard surfaces must fulfill further requirements. So it is important that after the treatment of the surface their appearance is not affected. This is in particular the preservation of the gloss of surfaces which have a gloss in the original or clean state, and the avoidance of residues of the treatment agent, for example in the form of stripes or streaks.

Finally, there has been a need for methods and means for providing a hard surface with a soil-repelling and / or facilitating the release of dirt, where these effects can be achieved optionally in a stand-alone surface treatment process, or in the course of a conventional cleaning process.

International patent application WO 2005/058863 discloses cyclic carbonates and ureas as well as reaction products of these substances with hydroxyl- or amino-containing polymers. The document further describes methods for modifying surfaces in which such reaction products are contacted with a surface. What effects and what applications are associated with it, however, is not disclosed in the Scriptures.

The object of the invention was therefore to remedy the above-described disadvantages of the prior art, at least partially. In particular, the object was to improve the removability of fecal dirt and biofilms of hard surfaces, in particular toilet ceramics, as well as the prevention of new formation of such soiling on such surfaces.

It has now been found that certain reactive cyclic carbonates and ureas and certain polymers which can be prepared therefrom are particularly suitable for protecting a surface treated therewith from contamination and / or for facilitating the removal of soiling from the surface.

The present invention therefore relates to the use of one or more compounds) of the general formulas I and / or II,

I I in which

R ₂ is alkylene of Ci-Ci; k is a number greater than 0,

X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ and R ¹ is dC ₃₀ alkyl, dC ₃₀ haloalkyl, Ci-C ₃₀ hydroxyalkyl, _Ci-C6 alkyloxy-Ci-C ₃₀ - alkyl, _Ci-C6 alkylcarbonyloxy-Ci-C ₃₀ alkyl, aminoC -Ci-C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) amino-C ₁ -C ₃₀ -alkyl, ammonio-C 1 -C 8 -alkyl, polyoxyalkylene-C 1 -C ₃₀ -alkyl, polysiloxanyl-ci C ₃₀ -alkyl, (meth) acryloyloxy-C 1 -C ₃₀ -alkyl, sulfono-C 1 -C ₃₀ -alkyl, phosphono-C 1 -C ₃₀ -alkyl, di (C 1 -C ₆ -alkyl) -phosphono-C 1 -C ₄ -alkyl ₃₀ -alkyl, phosphonato-C-ι-C ₃₀ -alkyl, di (C-ι-C ₆ -alkyl) phosphonato-C-ι-C ₃ o-alkyl or a saccharide radical, where in formula IX this meaning only then has, if k stands for 1, or

X in the case that k stands for a number of more than 1,

(i) the residue of a polyamine to which the parenthesized part of the formula is linked via (CO) NH groups, or

(ii) a polymeric backbone to which the parenthesized part of the formula is attached via (CO) -, NH-C ₂ -C ₆ -alkylene-O (CO) - or (CO) -OC ₂ -C ₆ -alkylene-O ( CO) groups, or (iii) a polymeric backbone to which the parenthesized formula part is bonded via (CO) polysiloxanyl-C 1 -C ₃₀ -alkyl groups, for treating a hard surface, wherein the treated surface is protected from contamination and / or facilitates the removal of contaminants from the surface, and / or to improve the cleaning performance of a hard surface cleaner.

Another object of the present invention is the use of polymers which are obtainable by reacting a polymeric substrate having functional groups which are selected from hydroxy groups, primary and secondary amino groups, with one or more compound (s) of the general formulas I. and / or II,

I l l wherein

R ₂ is alkylene of Ci-Ci; k is a number greater than 0,

X in the case that k stands for a number of more than 1,

For the purposes of the present invention, hard surfaces are, for example, surfaces of stone or ceramic materials, hard plastics, glass or metal. It can be hard surfaces such as walls, work surfaces, floors or sanitary items. In particular, the invention relates to surfaces of ceramics, preferably sanitary ceramics, and more particularly of toilet bowls. For the purposes of the invention, fouling means, in particular, faecal dirt and / or biofilms.

In particular, the use of the substances used according to the invention improves the cleaning performance of hard surface cleaners and causes them to be perceived as clean for longer.

In particular, if the substances used according to the invention are used as constituents of cleaning agents, they can bring about an improvement in the cleaning performance, which manifests itself both in easier removal of the dirt and in a reduced tendency to re-soiling.

It is assumed that the effectiveness of the substances used according to the invention against the formation of biofilms is due to their bacteriostatic effect, whereby the colonization of the surfaces with microorganisms is inhibited and their adhesion and multiplication on the surfaces is hindered. On the other hand, since no bactericidal effects have been observed for the substances, they are not subject to the disadvantages mentioned in the introduction of bactericides.

It has further been observed that both easier and faster removal of fecal dirt and improved rinsing of the dried (colored) cleaning agent itself is possible when the detergent formulation is added to one of the substances used according to the invention. As a working hypothesis, it is believed that detergents containing such materials, 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. As a rule, this is achieved solely by the mechanical action of the rinsing water, without the need for additional support by the toilet brush. If dyed cleaning formulations are allowed to act on the surface for a longer time and the formulation thereby begins to dry, the colored film formed is nevertheless easily and completely removed during the next rinsing process.

Suitable polymeric substrates include, in particular, polyvinyl alcohols, polyalkyleneamines such as polyethyleneimines, polyvinylamines, polyallylamines, polyethylene glycols, chitosan, polyamide-epichlorohydrin resins, polyaminostyrenes, polysiloxanes terminated terminally or as side groups with aminoalkyl groups, peptides, polypeptides and proteins and mixtures thereof ,

Particularly preferred polymeric substrates are selected from the polyethyleneimines having molecular weights in the range of 5,000 to 100,000, wherein the molecular weight (mol weight average molecular weight), compounds of the formula NH ₂ - [CH ₂ J _m - (Si (CH ₃ ) ₂ O) _n -Si (CH ₃ ) ₂ - [CH ₂ ] _o -R ', where m = 1 to 10, preferably 1 to 5, more preferably 1 to 3, where n = 1 to 50, preferably 30 to 50, where o = 0 to 10, preferably 1 to 5, particularly preferably 1 to 3 and wherein R ' = H, Ci. ₂₂ -alkyl, an amino or ammonium group, and compounds of the formula NH ₂ - [CH (CH 3) -CH ₂ O] r [CH ₂ -CH ₂ O] _m - [CH ₂ -CH (CH ₃ ) O] nR ", where I, m and n are independently from 0 to 50 with the proviso that the sum l + m + n = 5 to 100, in particular 10 to 50, preferably 10 to 30, particularly preferably 10 to 20, and R "= H, one d. ₂₂ -alkyl, C-ι_ ₂₂ aminoalkyl or C-ι_ ₂₂ -Ammoniumalkyl group, and mixtures thereof.

Preferred among the polymers are those obtainable by reacting the polymeric substrate with a compound of the general formula I where k = 1 or II. Preference is furthermore given to those polymers obtainable by reacting the polymeric substrate with equal molar amounts of compound of the general formulas I where k = 1 or II, based on their content of hydroxyl groups, primary and secondary amino groups.

The compound of the formula I is preferably selected from 4-phenyloxycarbonyloxymethyl-2-oxo-1,3-dioxolane, 4- (4-phenyloxycarbonyloxy) -butyl-2-oxo-1,3-doxolane, 2-oxo-i, 3-dioxolan-4-yl-methyl acrylate, 2-oxo-1,3-dioxolan-4-yl-methyl methacrylate, 4- (2-oxo-1,3-dioxolan-4-yl) -butyl acrylate 2-oxo-1,3-dioxolan-4-yl) -butyl methacrylate, 4- (vinylsulfonylethyloxy) -butyl-2-oxo-1,3-dioxolane and mixtures thereof.

Examples of compounds of the general formulas I or II which are suitable according to the invention and of polymers obtainable therefrom by reaction with polymeric substrates are known from international patent application WO 2005/058863. The document further includes examples of methods of making such fabrics.

The use according to the invention can be carried out in the context of a process for the treatment of a hard surface such that one or more of the substances used according to the invention, in particular in the presence of a surfactant, brings into contact with the surface.

The invention likewise provides a process for treating a hard surface, in which the surface is treated with one or more compound (s) of the general formula (I) I and / or II and / or a polymer which is obtained by reacting a polymeric substrate, which has functional groups selected from hydroxy groups, primary and secondary amines. nogruppen are selected, with one or more compound (s) of the general formula (I) I and / or II available, and is brought into contact with a surfactant.

This process can be carried out as a stand-alone treatment process for the surface, in particular to provide it with dirt-repellent properties. In this case, the surface is treated with a preferably aqueous agent which additionally contains at least one surfactant in addition to at least one of the above-described substances used according to the invention. The surfactant is selected so that it can not interact in an undesired manner with the substances used according to the invention.

Preferably, the process according to the invention is carried out in such a way that the one or more compound (s) of the general formula (I) I and / or II and / or the polymer which is obtained by reacting a polymeric substrate which has functional groups which are hydrogenated under Hydro - xygruppen, primary and secondary amino groups are selected, with one or more compound (s) of general formula (I) I and / or II is available, and the surfactant are distributed over the surface area and either after a contact time of 1 to 10 Rinsed for a few minutes or allowed to dry.

In a preferred embodiment of the method in the contacting occurs at a temperature of from 5 to 5O ⁰ C, in particular 15 to 35 ⁰ C.

In a particularly preferred embodiment, the process according to the invention represents a purification process which serves to clean the surface.

The substances used according to the invention, d. H. the compound (s) of general formula (I) and / or II and / or the polymer obtained by reacting a polymeric substrate having functional groups selected from hydroxy groups, primary and secondary amino groups with one or more Compound (s) of the general formula (I) I and / or II are available, are brought in a particularly preferred embodiment of the method according to the invention as a component (s) of an aqueous surfactant-containing cleaning agent with the surface in contact.

Another object of the invention is a means for treating a hard surface containing

(A) one or more compound (s) of the general formula (I) and / or II and / or a polymer which is prepared by reacting a polymeric substrate having functional groups which are selected from hydroxy groups, primary and secondary amino groups , is obtainable with one or more compound (s) of the general formula (I) I and / or II, (b) at least one surfactant and

(C) optionally water and / or other compatible with the other ingredients conventional ingredients of surface treatment or cleaning agents.

Preferably, one or more compounds of the general formula (I) I and / or II and / or a polymer obtained by reacting a polymeric substrate having functional groups selected from hydroxy groups, primary and secondary amino groups , with one or more compound (s) of the general formula (I) I and / or II, in amounts of 0.01 to 50 wt .-%, preferably from 0.2 to 15 wt .-%, and in particular from 0.5 to 5% by weight in the composition, based in each case on the total weight of the composition.

In a particular embodiment of the invention, the agents may contain at least one ingredient selected from the group comprising acids, thickeners and non-aqueous solvents.

The agent according to the invention is preferably a cleaning agent, in particular a cleaning agent for ceramics, more preferably sanitary ceramics.

A further embodiment of the invention relates to the use of an agent, in particular a cleaning agent, which contain one or more compound (s) of the general formula (I) I and / or II and / or a polymer which is obtained by reacting a polymeric substrate which is over having functional groups selected from hydroxy groups, primary and secondary amino groups, with one or more compound (s) of general formula (I) I and / or II, for the treatment of hard surfaces, in particular sanitary ware, for the purpose of improvement the removability of faecal dirt and / or biofilms in flush toilets, to prevent the formation of new soiling, as well as to improve the rinsability of dried detergent residues on hard surfaces, especially sanitary ware.

Such agents can be used in a process for cleaning toilet surfaces, in particular faecal dirt and / or biofilms can be easily removed. A further embodiment of the invention therefore relates to a method for improving the removability of fecal dirt and / or biofilms in flush toilets, in which an agent according to the invention, in particular a detergent according to the invention, is distributed over the surface and either after an exposure time of, for example, 1 to 10 Rinsed for a few minutes or allowed to dry. In addition, the compositions according to the invention may contain customary other constituents of agents, in particular detergents, for the treatment of hard surfaces, provided that they do not interact in an undesired manner with the substances used according to the invention.

As such other ingredients besides acids, thickeners and non-aqueous solvents, for example, film formers, antimicrobial agents, builders, corrosion inhibitors, complexing agents, alkalis, preservatives, bleach, enzymes and fragrances and dyes into consideration. Overall, preferably not more than 30 wt .-% of further ingredients should be included, preferably 0.01 to 30 wt .-%, in particular 0.2 to 15 wt .-%.

The compositions according to the invention contain at least one surfactant which is selected from the anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof.

Suitable anionic surfactants are preferably C ₈ -C ₁₈ -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 -alkyl polyglycol ether sulfates with 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic acid mono- and di-C ₈ -C ₁₈ -alkyl esters. It is also possible to use C ₈ -C ₁₈ -α-olefinsulfonates, sulfonated C ₈ -C ₁₈ -fatty acids, in particular dodecylbenzenesulfonate, C ₈ -C ₂₂ -carboxylic acid ether sulfates, C ₈ -C ₁₈ -alkyl polyglycol ether carboxylates, C ₈ -C ₁₈ N-acyl taurides, C ₈ -C ₁₈ N sarcosinates and C ₈ -C ₈ 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 acid. Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkanesulfonate having about 15 carbon atoms and sodium dioctyl sulfosuccinate. Sodium fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates having 12 to 14 C atoms have proven particularly suitable.

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), C ₈ - are especially nonionic surfactants. C ₁₈ -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 alkylpolyglycosides with 8 to mention 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units. 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 _i ₀ alkyl polyglucosides with 1 to 2 glycoside units used. Suitable amphoteric surfactants are, for example, betaines of the formula (R "')(R' ^V) (R ^V) N ⁺ CH ₂ ^COO" in which R "'is an optionally interrupted by hetero atoms or hetero atom groups alkyl radical 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- dimethylcarboxymethylbetain and Cn-Ciz-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.

One or more nonionic surfactants, preferably C ₈ _i ₈ alkyl ether sulfates, and / or - in a preferred embodiment, the agent surfactant components but contains only one or more anionic surfactants, preferably C ₈ -C ₈ alkyl sulfates and / or C ₈ -C ₈ - Fettalkoholpolyglykolether with 2 to 8 EO and / or C ₈ _i ₀ -Alkylpolyglucoside with 1 to 2 glycoside units.

The compositions of the invention contain surfactants preferably in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight, in each case based on the total weight of the composition.

Compositions of the invention may further contain one or more acids. 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 .-%.

In a further embodiment, an agent according to the invention contains a thickening agent. For this purpose, in principle, all viscosity regulators used in detergents and cleaning agents in the prior art into consideration, such as organic natural thickeners (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 montmorillonites, 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): carbomers), also referred to as carboxyvinyl polymers. Such polyacrylic rylsäuren 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, preferably C-. _4- alkanols formed esters (INCI acrylate 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. Rohm & Haas under the trade names Aculyn ^® and Acusol ^®, and from Degussa (Goldschmidt) under the trade name Tego ^® polymer, for example the anionic non-associative polymers Aculyn ^® 22, Aculyn ^® 28, Aculyn ^® 33 (crosslinked), Acusol ^® 810, Acusol ^® 823 and Acusol ^® 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, which are crosslinked with an allyl ether of sucrose or of pentaerythritol copolymers of C-ιo- ₃₀ alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with CI_ ₄ - Alkanols formed, esters (INCI Acrylates / C10-30 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, Hydroxyethyl, hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate. A particularly preferred polysaccharide thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2-15x10 ⁶ and for example, by Fa. Kelco under the trade names Keltrol ^® and Kelzan ^® or available from Rhodia under the trade name Rhodopol ^®. As thickeners, phyllosilicates can furthermore be used. be set. 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 agent according to the invention contains 0.01 to 30 wt .-%, in particular 0.2 to 15 wt .-% of a thickener, preferably a polysaccharide thickener, for example xanthan gum.

The agents according to the invention may contain solvents, in particular water and / or non-aqueous solvents, preferably water-soluble organic solvents. These include, for example, lower alcohols and / or ether alcohols, where as lower alcohols in the context of this invention straight-chain or branched C |. ₆ alcohols are understood. 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.

The compositions according to the invention can furthermore contain film formers which can contribute to a better wetting of the surface. In principle, all film-forming polymers used in detergents and cleaners in the prior art are suitable for this purpose. However, 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, more preferably 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.

Compositions according to the invention may furthermore comprise one or more antimicrobial active ingredients, preferably in an amount of from 0.01 to 1% by weight, in particular from 0.05 to 0.5% by weight, particularly preferably from 0.1 to 0.3 wt .-%. Suitable examples are antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, 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 and peroxides. Before- 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-octan-amine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecan-dumidamide, 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 ensure scenting of the cleaning 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.

Water-soluble and / or water-insoluble builders can be used in the compositions 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 context of 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.

Suitable corrosion inhibitors are, for example, the following substances named according to INCI: cyclohexylamines, diammonium phosphates, dilithium oxalates, dimethylamino methylpropanol, dipotassium oxalates, dipotassium phosphates, disodium phosphates, disodium pyrophosphates, disodium tetrapropenyl succinates, hexoxyethyl diethylammonium, phosphates, nitromethanes, potassium silicates, sodium aluminates, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.

Chelants, also called sequestering agents, are ingredients that can complex and inactivate 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 com- plex the calcium and magnesium ions of water hardness, which are incompatible with numerous ingredients. 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. For example, the following are suitable according to INCI. Plexifiers: Aminotrimethylene, Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Deaminunnin EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate , EDTA, e- tidronic acid, galactic acid, gluconic acid, glucuronic acid, HEDTA, hydroxypropyl cyclodextrin, methyl cyclodextrin, pentapotassium triphosphates, pentasodium aminotrimethylene phosphonates, pentasodium ethylene diamines, tetramethylene phosphonates, pentasodium pentates, pentasodium triphosphates, 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 Polydimethylglycophenolsulfonate, 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 metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide. In addition, however, it is also possible to use ammonia and / or alkanolamines having up to 9 C atoms in the molecule, preferably the ethanolamines, in particular monoethanolamine.

Preservatives 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, the agents may further contain bleaching agents. 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. In some circumstances, a bleach activator may be included in addition to the bleaching agent.

The agent according to the invention may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They may be added to the composition in any form established in the art. These include liquid or gel agents in particular solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in core-shelled form. Type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are 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 former, low dust and storage stable due to the coating.

In addition, enzyme stabilizers may be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention from damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage. Suitable enzyme stabilizers, in each case depending on the enzyme used, are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, for example substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with reduced C terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, 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. 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 surfaces, especially to toilet ceramics, even with prolonged exposure should not be substantive , The choice of suitable perfume is also limited only by possible interactions with the other detergent components. The preparation of the compositions according to the invention can be carried out in a customary manner by mixing the components contained in the composition in a suitable manner.

Agents according to the invention, which are preferably designed as cleaning agents, find application in the treatment of hard surfaces, in particular sanitary ceramics. They can be used to remove dirt from hard surfaces and to reduce the re-contamination of these surfaces, as well as to allow faster and more thorough cleaning of soiled surfaces.

In a preferred embodiment of the invention means according to the invention are used for improved removal of fecal dirt and / or biofilms from the surfaces of flush toilets and / or for reducing the re-soiling of such surfaces with fecal dirt and / or biofilms. For this purpose, the agent is spread over the surface and either rinsed after an exposure time of preferably 1 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, it is easier to rinse off dried detergent residues.

embodiments

As examples of thickened formulations, three acidic toilet detergents E1 to E3 with different proportions of one of the polymers used 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

Polymer ¹⁾ 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

¹⁾ Reaction product of a compound of formula I with k = 1, R = CH ₂ , X = CO-NH- (CH ₂ CH _Z ) ₁₉ (CH ₂ CH (CH ₃ ) O) CH ₃ with polyethyleneimine (MW = 25,000 )

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 Fäkalschmutz (mixture of bacterial biomass, fiber from 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. While 80% of the faeces contamination were still present when using the comparative formulation V1 not according to the invention, more than half of the fecal dirt could already be removed on surfaces cleaned with the agents E1-E3 with one rinse, after the second rinse the dirt was 100% away. 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 toilet inner wall for all formulations. After rinsing the toilet, in the case of cleaner V1 not according to the invention, 90% of the original surface was covered with a visible blue film of cleaner formulation, whereas no visible film was present when using formulations E1, E2 and E3 according to the invention.

Furthermore, three coating solutions E4 to E6 were prepared as examples of non-thickened formulations, which also contained the polymer used in the invention, and a comparative solution V2.

Composition [wt.%] E4 E5 E6 V2

Polymer ¹ '2 5 5 0

Lauryl ether sulfate + 2EO 3 3 3

C ₈ -ioalkylpolyglycoside 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 ad 100 ad 100 ad 100 ad 100

Also 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 comparison formulation V2 was applied, spread over a surface 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 using the comparative formula not according to the invention V2 95% of the fecal contamination were present, no fecal contamination could be detected on the surfaces cleaned with the agents E4, E5 and E6 according to the invention.

Claims

claims:

1. Use of one or more compound (s) of the general formulas I and / or II,

I l l wherein

R ₂ is alkylene of Ci-Ci; k is a number greater than 0,

X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ and R ^{1 is} C ₁ -C ₃₀ -alkyl, dC ₃ o-haloalkyl, dC ₃ o-hydroxyalkyl, C ₁ -C ₆ -alkyl-C ₁ -C ₃₀ -alkyl, C ₁ -C ₆ -alkylcarbonyloxy-C ₁ -C 5 -cycloalkyl, alkyl, amino-C 1 -C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) -amino-C ₁ -C ₃₀ -alkyl, ammonio-C 1 -C 8 -alkyl, polyoxyalkylene-C C 1 -C ₃₀ -alkyl, polysiloxanyl C 1 -C ₃₀ -alkyl, (meth) acryloyloxy C 1 -C ₃₀ -alkyl, sulfonoC-C ₃₀ -alkyl, phosphono-C 1 -C ₃₀ alkyl, di (C ₁ -C ₆ - alkyl) phosphono-C-ι-C ₃₀ alkyl, phosphonato-Ci-Cso-alkyl, di (C ₁ -C ₆ alkyl) phosphonato-C ₁ -C ₃₀ - alkyl or a saccharide radical, wherein in formula IX this meaning has only if k is 1, or

X in the case that k stands for a number of more than 1,

(i) the remainder of a polyamine to which the formula part in parentheses is attached via (CO) NH-

Groups is bound, or

(ii) a polymeric backbone to which the formula part in parentheses is attached via (CO) -, NH-C ₂ -C ₆ -

Alkylene-O (CO) - or (CO) -OC ₂ -C ₆ alkylene-O (CO) groups is bound, or

(iii) a polymeric backbone to which the formula part in parentheses above (CO) -

Polysiloxanyl-C-C ₃₀ alkyl groups is bound, for the treatment of a hard surface, wherein the treated surface is protected from contamination and / or the separation of contaminants from the surface is facilitated, and / or to improve the cleaning performance a cleaning agent for a hard surface.

2. Use of polymers which are obtainable by reacting a polymeric substrate which has functional groups which are among hydroxy groups, primary and secondary amino groups are selected with one or more compound (s) of the general formulas I and / or II,

I l l wherein

R ₂ is alkylene of Ci-Ci; k is a number greater than 0,

X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ and R ^{1 is} C ₁ -C ₃₀ -alkyl, dC ₃ o-haloalkyl, dC ₃ o-hydroxyalkyl, C ₁ -C ₆ -alkyl-C ₁ -C ₃₀ -alkyl, C ₁ -C ₆ -alkylcarbonyloxy-Ci-CsQ- alkyl, amino-C 1 -C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) -amino-C ₁ -C ₃ 0-alkyl, ammonio-C 1 -C ₃ o- alkyl, polyoxyalkylene C-ι-C ₃ o-alkyl, C-ι-Polysiloxanyl-C ₃ O- alkyl, (meth) acryloyloxy-C-ι-C ₃ O-alkyl, sulfono-C-ι-C ₃ o alkyl, phosphono-C ₁ -C ₃ o-alkyl, di (C ₁ -C ₆ -alkyl) phosphono-C ₁ -C ₃ o-alkyl, phosphonato-C ₁ -C ₃ o-alkyl, di (C ₁ -C ₆ -alkyl) phosphonato-C ₁ -C ₃ -alkyl or a saccharide radical, where in formula IX this meaning has only if k is 1, or

X in the case that k stands for a number of more than 1,

Groups is bound, or

Alkylene-O (CO) - or (CO) -OC ₂ -C ₆ alkylene-O (CO) groups is bound, or

Polysiloxanyl-C-ι-C ₃ o-alkyl groups is bound, for the treatment of a hard surface, wherein the treated surface is protected from contamination and / or the separation of contaminants from the surface is facilitated, and / or to improve the Cleaning performance of a cleaning agent for a hard surface.

3. Use according to claim 1 or 2, characterized in that it is the surface of ceramic, in particular sanitary ware.

4. Use according to one of claims 1 to 3, characterized in that it is at the / the pollution (s) to faecal dirt and / or biofilms.

5. Use according to one of claims 2 to 4, characterized in that the polymeric substrate is selected from the group comprising polyvinyl alcohols, polyalkyleneamines such as polyethyleneimines, polyvinylamines, polyallylamines, polyethylene glycols, chitosan, polyamide-epichlorohydrin resins, polyaminostyrenes, with aminoalkyl groups terminal or as side group substituted polysiloxanes, peptides, polypeptides and proteins and mixtures thereof.

6. Use according to one of claims 2 to 5, characterized in that the polymeric substrate is selected from the polyethyleneimines having molecular weights in the range of 5,000 to 100,000, compounds of the formula NH ₂ - [CH ₂ ] _m - (Si (CH ₃ ) 2θ) n-Si (CH 3) 2- [CH ₂ ] o-R ', where m = 1 to 10, preferably 1 to 5, particularly preferably 1 to 3, where n = 1 to 50, preferably 30 to 50, wherein o is 0 to 10, preferably 1 to 5, more preferably 1 to 3 and wherein R '= H, C-ι- ₂₂ alkyl, an amino or ammonium group, and compounds of the formula NH ₂ - [CH (CH 3) -CH ₂ θ] ι- [CH ₂ -CH ₂ O] _m - [CH 2 -CH (CH 3) O] n R "where I, m and n are independently from 0 to 50 with the proviso that the sum l + m + n = 5 to 100, in particular 10 to 50, preferably 10 to 30, particularly preferably 10 to 20, and R "= H, a C-ι- ₂₂ alkyl, C-ι- ₂₂ -Aminoalkyl- or Ci- ₂₂ -Annunnunnalkylalkyl group, and mixtures thereof.

7. Use according to any one of claims 1 to 6, characterized in that the compound of formula I is selected from 4-phenyloxycarbonyloxymethyl-2-oxo-1, 3-dioxolane, 4- (4-phenyloxycarbonyloxy) bu tyl-2-oxo - 1, 3-d ioxolane, 2-oxo-1, 3-dioxolan-4-yl-methyl acrylate, 2-oxo-1, 3-dioxolan-4-yl-methyl methacrylate, 4- (2-oxo-1, 3 -dioxolan-4-yl) -butyl acrylate, 4- (2-oxo-1,3-dioxolan-4-yl) -butyl methacrylate, 4- (vinylsulfonylethyloxy) -butyl-2-oxo-1,3-dioxolane and mixtures thereof ,

8. A method for treating a hard surface, wherein the surface with one or more compound (s) of the general formula (I) and / or II and / or a polymer which has by reacting a polymeric substrate having functional groups , which are selected from hydroxy groups, primary and secondary amino groups, with one or more compound (s) of the general formula (I) I and / or II available, and is brought into contact with a surfactant.

9. The method according to claim 8, characterized in that the one or more compounds) of the general formula (I) I and / or II and / or the polymer, which by Um- Substitution of a polymeric substrate which has functional groups which are selected from hydroxy groups, primary and secondary amino groups, with one or more compound (s) of general formula (I) I and / or II is available, as well as the surfactant on be spread over the surface area and either rinsed after a contact time of 1 to 10 minutes or allowed to dry.

10. The method according to any one of claims 8 or 9, characterized in that the bringing into contact at a temperature of 5 to 5O ⁰ C, in particular 15 to 35 ⁰ C takes place.

11. The method according to any one of claims 8 to 10, characterized in that it is a cleaning process.

12. The method according to any one of claims 8 to 11, characterized in that the compounds) of the general formula (I) I and / or II and / or the polymer, which by reacting a polymeric substrate having functional groups which under Hydroxy groups, primary and secondary amino groups are selected, with one or more compound (s) of the general formula (I) I and / or II available is brought as part of an aqueous surfactant-containing cleaning agent with the hard surface.

13. A hard surface treatment agent containing

(A) one or more compound (s) of the general formula (I) and / or II and / or a polymer which is prepared by reacting a polymeric substrate having functional groups which are selected from hydroxy groups, primary and secondary amino groups , is obtainable with one or more compound (s) of the general formula (I) I and / or II,

(b) at least one surfactant and

14. Composition according to claim 13, characterized in that it comprises one or more compound (s) of the general formula (I) and / or II and / or a polymer which is obtained by reacting a polymeric substrate which has functional groups are selected from hydroxy groups, primary and secondary amino groups, with one or more compounds) of general formula (I) I and / or II, in amounts of from 0.01 to 50% by weight, preferably from 0.2 to 15 Wt .-%, and in particular from 0.5 to 5 wt .-%, based on the total weight of the composition.

15. Composition according to claim 13 or 14, characterized in that it contains at least one ingredient selected from the group comprising acids, thickeners and nonaqueous solvents.

16. Composition according to one of claims 13 to 15, characterized in that it is a cleaning agent.

17. Composition according to claim 16, characterized in that it is a cleaning agent for ceramics, in particular for sanitary ware is.