EP2129760B1 - Product for treating hard surfaces - Google Patents

Description

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 lime and urine stone as well as fecal residues adhering to the ceramic must be used about fecal dirt well, although mechanically, so with the help 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.

steht, worin B für einen Alkylenrest mit 2 bis 30 C-Atomen steht, R' für Wasserstoff oder ein Alkylradikal mit 1 bis 30 C-Atomen steht und E fehlt oder ein Alkylenrest mit 1 bis 5 C-Atomen ist, und M H, eine Alkylgruppe mit 1 bis 4 C-Atomen oder ein Kation ist, p ein gemittelter Wert von 0 bis 1000 ist und q ein gemittelter Wert von 1 bis 100 ist und das Zahlenverhältnis der Endgruppen Z und W zur Summe der Endgruppen X und Y von 0/100 bis 75/100 beträgt. Aus der Patentanmeldung WO 2006/005358 A1 sind Copolymere bekannt, die aus mindestens je einem anionischen Vinylmonomer, einem Vinylmonomer mit einer quaternären Ammoniumgruppe oder einer tertiären Aminogruppe, und einem nichtionischen hydrophilen Vinylmonomer oder einem polyfunktionellen Vinylmonomer bestehen. Diese Copolymere eignen sich als verschmutzungshemmende Komponenten in Reinigungsmitteln und sind beispielsweise gegenüber Fäkalanschmutzungen wirksam.The international patent application WO 03/095530 A1 relates to household care products with dicarboxy-functional polyorganosiloxanes of the formula X (R ⁴ R ⁵ SiO) p (R ⁶ A Si O) q Y in which X is a triorganosiloxyl end group of the formula R ¹ R ² R ³ SiO- or -OH , Y is a triorganosilyl end group of the formula -SiR ³ R ² R ¹ or is -H, R ¹ to R ^{6 are} a linear or branched C ¹ -C 8 alkyl or phenyl radical, A is a dicarboxylic acid radical of the formula

wherein B is an alkylene radical having 2 to 30 carbon atoms, R 'is hydrogen or an alkyl radical having 1 to 30 carbon atoms and E is absent or an alkylene radical having 1 to 5 carbon atoms, and MH, a Is an alkyl group having 1 to 4 carbon atoms or a cation, p is an averaged value of 0 to 1000 and q is an averaged value of 1 to 100 and the numerical ratio of the end groups Z and W to the sum of the end groups X and Y is 0 / 100 to 75/100. From the patent application WO 2006/005358 A1 For example, copolymers are known which consist of at least one anionic vinyl monomer, one vinyl monomer having a quaternary ammonium group or one tertiary amino group, and a nonionic hydrophilic vinyl monomer or a polyfunctional vinyl monomer. These copolymers are useful as anti-soiling components in detergents and are effective, for example, against fecal contamination.

However, as far as possible beyond the one-time use, longer-lasting cleanliness of the interior of the toilet against new fecal soiling can not be achieved in a completely satisfactory manner even with these cleaners.

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, Mushrooms, 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 is impaired. In particular, this involves 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.

Object of the present invention, it was now to remedy the above-described disadvantages of the prior art, at least partially. In particular, the object was to improve the removability of faecal dirt and biofilms of hard surfaces, especially toilet ceramics, as well as the prevention of new formation of such soiling on such surfaces.

It has now been found that certain polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds, but also the precursor compounds of the reactive cyclic carbonate and urea type which can be used in their preparation, are particularly suitable for protecting a surface treated therewith from contamination and / or to facilitate the removal of contaminants from the surface.

• Y ausgewählt wird aus zwei- bis mehrwertigen, insbesondere vierwertigen, geradkettigen, cyclischen oder verzweigten, gesättigten, ungesättigten oder aromatischen, substituierten oder unsubstituierten Kohlenwasserstoffresten mit bis zu 1000 Kohlenstoffatomen (wobei die Kohlenstoffatome einer gegebenenfalls enthaltenen Polyorganosiloxaneinheit nicht mitgezählt werden), die eine oder mehrere Gruppen, ausgewählt aus -O-, -(CO)-, -NH-, -NR²-, -(N⁺R²R³)-und einer Polyorganosiloxaneinheit mit 2 bis 1000 Siliciumatomen enthalten können,
• R¹ Wasserstoff oder ein geradkettiger, cyclischer oder verzweigter, gesättigter, ungesättigter oder aromatischer Kohlenwasserstoffrest mit bis zu 40 Kohlenstoffatomen ist, der eine oder mehrere Gruppen, ausgewählt aus -O-, -(CO)-, -NH- und -NR²- enthalten kann,
• R² ein geradkettiger, cyclischer oder verzweigter, gesättigter, ungesättigter oder aromatischer Kohlenwasserstoffrest mit bis zu 40 Kohlenstoffatomen ist, der eine oder mehrere Gruppen, ausgewählt aus -O-, -(CO)- und -NH- enthalten kann,
• R³ ein geradkettiger, cyclischer oder verzweigter, gesättigter, ungesättigter oder aromatischer Kohlenwasserstoffrest mit bis zu 100 Kohlenstoffatomen ist, der eine oder mehrere Gruppen, ausgewählt aus -O-, -(CO)- und -NH- enthalten kann, oder ein zweiwertiger Rest ist, der cyclische Strukturen innerhalb des Restes Y ausbildet,

oder einer oder beide zu Y nachbarständige Reste A mit dem zwischen ihnen stehenden Rest Y einen stickstoffhaltigen heterocyclischen Rest bilden können,
und in der gesamten Verbindung nicht alle in Formel (I) angegebenen Reste A bzw. Y bzw. R¹ bzw. R² bzw. R³ gleich sein müssen mit der Maßgabe, dass in der gesamten Verbindung mindestens einer der Reste Y eine Polyorganosiloxaneinheit mit 2 bis 1000 Siliciumatomen umfasst, oder deren Säureadditionsverbindungen und/oder Salzen zur Behandlung einer harten Oberfläche, wobei die behandelte Oberfläche vor Verschmutzung geschützt und/oder die Ablösung von Verschmutzungen von der Oberfläche erleichtert wird, und/oder zur Verbesserung der Reinigungsleistung eines Reinigungsmittels für eine harte Oberfläche.The present invention therefore provides the use of one or more polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds containing at least one structural element of the formula (I):

-YA- (C = O) -A- (I),

where each A independently is selected from S, O and NR ¹ ,

• Y is selected from bivalent to polyvalent, especially tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon radicals having up to 1000 carbon atoms (excluding the carbon atoms of any polyorganosiloxane unit optionally included) containing one or more May contain groups selected from -O-, - (CO) -, -NH-, -NR ² -, - (N ⁺ R ² R ³ ) - and a polyorganosiloxane unit having 2 to 1000 silicon atoms,
• R ^{1 is} hydrogen or a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms and having one or more groups selected from -O-, - (CO) -, -NH- and -NR ² - can contain
• R ^{2 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 40 carbon atoms and which may contain one or more groups selected from -O-, - (CO) - and -NH-,
• R ^{3 is} a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 100 carbon atoms, which may contain one or more groups selected from -O-, - (CO) - and -NH-, or a bivalent radical is that forms cyclic structures within the remainder Y,

or one or both of the radicals A which may be adjacent to Y may form, with the radical Y between them, a nitrogen-containing heterocyclic radical,
and in the entire compound not all radicals A or Y or R ¹ or R ² or R ³ given in formula (I) must be identical, with the proviso that in the entire compound at least one of the radicals Y is a polyorganosiloxane unit 2 to 1000 silicon atoms, or their acid addition compounds and / or salts for the treatment of a hard surface, wherein the treated surface is protected from contamination and / or the removal of contaminants from the surface is facilitated, and / or for improving the cleaning performance of a cleaning agent for a hard surface.

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.

The use of the substances used in accordance with the invention improves, in particular, the cleaning performance of hard surface cleaners and causes the treated or cleaned surfaces to be perceived as clean for longer.

In particular, when using the substances used in the invention as part of cleaning agents, they can bring about an improvement in the cleaning performance, which manifests itself in both an easier removability of the pollution, as well as in a reduced tendency to re-soiling.

It has been observed that both the easier and faster removal of fecal dirt and an improved rinsing of the dried (colored) detergent itself is possible when the detergent formulation of one of the substances used in the invention is added. 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.

Compounds of the general formula (I) can be obtained by reacting diisocyanates, bis-chloroformic acid esters or amides or phosgene with thiols, alcohols or amines containing the structural element Y. In order to obtain polymeric structures, these starting compounds having the structural element Y have at least 2 of the said functional groups. Suitable end groups are compounds which otherwise correspond to the structural element Y but are only monofunctional.

Among the preferred polycarbonate and / or polyurethane-polyorganosiloxane compounds are those which contain at least one structural element of the formula (II) or (III):

-AYA- (CO) -OZ- (CHOH) -ZO- (CO) - (II),

-AYA- (CO) -O- (CHCH ₂ OH) -ZO- (CO) - (III),

in which A and Y have the meanings mentioned above and
Z is selected from the divalent, straight-chain, cyclic or branched, saturated or unsaturated, optionally substituted hydrocarbon radicals having 1 to 12 carbon atoms. These structural elements can be obtained by ring opening of cyclic carbonates (carbonic acid esters of vicinal diols) with the thiols, alcohols or amines containing the structural element Y.

The polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound preferably has the structural element of the formula (I) several times in succession, the multiply occurring in each case corresponding radicals A or Y or Z or R ¹ or R ² or R ^{3 may be the} same or different.

The term acid addition compound means a salt-like compound obtained by protonation of basic groups in the molecule, in particular those which may be present Amino groups, for example by reaction with inorganic or organic acids can be obtained. The acid addition compounds may be used as such or may optionally form under conditions of use of the compounds defined above.

If the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound contains moieties - (N ⁺ R ² R ³ ) -, common counter anion ions, such as halide, hydroxide, sulfate, carbonate, are present in order to ensure charge neutrality.

When in the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds present polyorganosiloxane structural element is preferably the structure - (SiR ⁴ ₂ O) _p - (SiR ⁴ ₂₎ -, wherein R ⁴ is a straight chain, cyclical or branched, saturated, unsaturated or aromatic hydrocarbon radical having up to 20 carbon atoms, and p = 1 to 999. The polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds preferably contain on average at least two, in particular at least three, of said polyorganosiloxane structural elements. R ⁴ is preferably a straight-chain or cyclic or branched, saturated or unsaturated or aromatic C ₁ - to C ₂₀ -, in particular C ₁ -C ₉ hydrocarbon radical, particularly preferably methyl or phenyl, and p is preferably 1 to 199, particularly preferably 1 to 99. In a preferred embodiment, all radicals R ^{4 are the} same.

Preferred polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds used according to the invention are linear, ie all Y units in the structural element of the formula (I) are in each case divalent radicals. However, branched compounds according to the invention are also included in which at least one of the radicals Y is trivalent or polyvalent, preferably tetravalent, so that branched structures having linear repeat structures of structural elements of the formula (I) are formed.

In a further embodiment, in the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound used according to the invention, at least one of the Y units according to the structural element of the formula (I) has a grouping -NR ² - and / or at least one of the Y units according to structural element of the formula (I) a grouping - (N ⁺ R ² R ³ ) - on. R ² and R ³ are preferably methyl groups.

A further embodiment relates to the multiple regular occurrence of -O-groupings in at least one of the units Y, R ¹ , R ² and / or R ³ according to the structural element of the formula (I), preferably in the form of oligoethoxy and / or oligopropoxy groups their degrees of oligomerization are preferably in the range of 2 to 60.

In a further preferred embodiment, at least one of the units Y, R ¹ , R ² and / or R ³ according to the structural element of the formula (I) contains oligoethylenimine groups whose degrees of oligomerization are in particular in the range from 10 to 15 000.

Reactive cyclic carbonates and ureas, processes for their preparation and their reaction with polymeric substrates are described in the international patent application WO 2005/058863 described.

The use according to the invention can be carried out as part of a process for the treatment of a hard surface such that one or more of the active ingredients used in the invention (the polycarbonate, polyurethane and / or polyurea polyorganosiloxane compound), in particular in the presence of a surfactant, with the Contact surface.

The invention likewise provides a process for treating a hard surface, in which the surface is brought into contact with one or more of the active substances mentioned and 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.

The process according to the invention is preferably carried out in such a way that the one or more of the active substances mentioned and also the surfactant are distributed over the surface and either rinsed off after a contact time of 1 to 10 minutes or left to dry.

In a preferred embodiment of the method, the bringing into contact takes place at a temperature of 5 to 50 ° C, in particular 15 to 35 ° C.

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

In a particularly preferred embodiment of the method according to the invention, the active ingredients used according to the invention are brought into contact with the surface as constituent (s) of an aqueous surfactant-containing cleaning agent.

A further subject of the invention is a hard surface treatment agent comprising a polycarbonate and / or polyurea-polyorganosiloxane compound containing at least one structural element of the formula (I):

-YA- (C = O) -A- (I),

where A and Y satisfy the definitions given above, or their acid addition compound and / or salt,
in particular in amounts of from 0.01 to 50% by weight, preferably from 0.2 to 15% by weight, and particularly preferably from 0.5 to 5% by weight, based on the total weight of the composition,
at least one surfactant and
optionally water and / or further, compatible with the other constituents conventional ingredients of surface treatment or cleaning agents.

Preferably, the one or more of said active ingredients is in amounts of from 0.01 to 50% by weight, preferably from 0.2 to 15% by weight, and more preferably from 0.5 to 5% by weight in the Contain agents, each based on the total weight of the agent.

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 agents, in particular detergents, which contain one or more of the active substances mentioned, for the treatment of hard surfaces, in particular sanitary ware, for the purpose of improving the removability of fecal dirt and / or biofilms in flush toilets, for the prevention of New formation of such 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.

Suitable other constituents besides acids, thickeners and nonaqueous solvents are, for example, film formers, antimicrobial agents, builders, corrosion inhibitors, complexing agents, alkalis, preservatives, bleaches, enzymes and fragrances and dyes. 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 ₂₀ -alkanesulfonates, C ₈ -C ₁₈ -monoalkyl sulfates, C ₈ -C ₁₈ -alkyl polyglycol ether sulfates 2 to 6 ethylene oxide units (EO) in the ether portion and sulfosuccinic mono- and di-C ₈ -C ₁₈ alkyl esters. Furthermore, C ₈ -C ₁₈ -α-olefinsulfonates, sulfonated C ₈ -C ₁₈ -fatty acids, in particular dodecylbenzenesulfonate, C ₈ -C ₂₂ -Carbonsäureamidethersulfate, C ₈ -C ₁₈ -Alkylpolyglykolethercarboxylate, C ₈ -C ₁₈ -N-Acyltauride , 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 metal 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 dioctylsulfosuccinate. 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 _8-18 -fatty alcohol polyglycol ethers having, in particular 2 to 8 EO; for example, C ₁₂ fatty alcohol + 7-EO ether, and C _8-10 alkyl polyglucosides having 1 to 2 glycoside units used.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -Alkyldimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyl-dimethylcarboxymethylbetain.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix are} 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 preferred embodiment, however, the surfactant component comprises 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 compositions according to the invention preferably comprise surfactants 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 (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose 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 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 from Degussa (Goldschmidt) under the trade name Tego ^® polymer are available, for example the anionic non-associative PolymereAculyn ^® 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, 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 C _1-4 alkanols formed, esters (INCI acrylates / C10-30 alkyl acrylate crosspolymer) and which are obtainable for example from the company. BFGoodrich under the tradename Carbopol ^®, Carbopol ^® example hydrophobized ETD 2623 and Carbopol ^® 1382 (INCI acrylates / C10 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 2-15 × 10 ^6, and for example, by Fa. Kelco under the trade names Keltrol ^® and Kelzan ^® or from the company Rhodia under the trade name Rhodopol ^{® is} available. 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 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 of a polysaccharide thickener, for example xanthan gum.

The compositions 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, 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.

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. Preferably, however, 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. 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 agents, preferably in an amount of from 0.01 to 1% by weight, in particular from 0.05 to 0.5 wt .-%, 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 derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl 4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octan-amine) dihydrochloride, N, N'-bis ( 4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, antimicrobially effective essential oils can be used, which at the same time provide for a scenting 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.

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 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 are capable of complexing and inactivating metal ions to prevent their adverse effects on the stability or appearance of the agents, for example clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents. In addition, the complexing agents support the cleaning effect. Suitable examples are the following according to INCI called complexing agents: 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, S orodium dihydroxyethylglycinate, sodium EDTMP, sodium glutamate, sodium gluconate, sodium glycereth-1 polyphosphate, sodium hexametaphosphate, sodium metaphosphate, sodium metasilicate, sodium phytate, sodium polydimethylglycinophenolsulfonate, sodium trimetaphosphate, TEA-EDTA, TEA polyphosphate, tetrahydroxyethyl ethylene diamine, tetrahydroxypropyl ethylene diamine, 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. 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, 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-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. 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 should not be substantive to the surfaces, especially compared to toilet ceramics, even with prolonged exposure , 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, any dried-up detergent residues can be rinsed off more easily.

embodiments

As examples of thickened formulations, three acidic toilet detergents E1 to E3 with different proportions of one of the active compounds used according to the invention were formulated. On the other hand, a comparative formulation V1 was free of this active substance. Composition [% by weight] E1 E2 E3 V1 active substance 1 3 10 0 C12 fatty alcohol ethoxylate + 7 EO 3 3 3 3 octyl 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

With these formulations, tests were carried out for cleaning performance against fecal 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 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 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 comparison 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 flushing the toilet were in the case of the inventive cleaner V1 still 90% of the original Area covered with a visible blue film of cleaner formulation, while no visible film was present when using the formulations according to the invention E1, E2 and E3.

Furthermore, three coating solutions E4 to E6 were prepared as examples of non-thickened formulations, which also contained an active ingredient used in the invention, and a comparative solution V2. Composition [% by weight] E4 E5 E6 V2 active substance 2 5 5 0 Lauryl ether sulfate + 2 EO 3 3 - 3 C _8-10 alkyl polyglycoside - - 3 - PEG 40,000 MW 1 - - - citric acid 0.5 0.5 0.5 0.5 ethanol 8th 8th 8th Perfume 0.05 0.05 0.05 0.05 water ad 100 ad 100 ad 100 ad 100

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 comparison 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 ), allowed to dry for 30 minutes and rinsed off. 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 (13)

1. Use of one or more polycarbonate-, polyurethane- and/or polyureapolyorganosiloxane compound(s) containing at least one structural element of the formula (I):
   
           -Y-A-(C=O)-A-     (I),
   
   each A being independently selected from S, O and NR¹,

   Y being selected from di- to polyvalent, in particular tetravalent, straightchain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon residues with up to 1000 carbon atoms (the carbon atoms of an optionally present polyorganosiloxane unit not being included in said number), which may contain one or more groups selected from -O-, -(CO)-, -NH-, -NR²-, -(N⁺R²R³)- and a polyorganosiloxane unit with 2 to 1000 silicon atoms,

   R¹ being hydrogen or a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 40 carbon atoms, which may contain one or more groups selected from -O-, -(CO)-, -NH- and -NR²-,

   R² being a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 40 carbon atoms, which may contain one or more groups selected from -O-, -(CO)- and -NH,

   R³ being a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 100 carbon atoms, which may contain one or more groups selected from -O-, -(CO)- and -NH-, or being a divalent residue which forms cyclic structures within the residue Y,

   or one or both of the residues A adjacent to Y may form a nitrogenous heterocyclic residue with the residue Y located between them,
   and in the entire compound all the residues A or Y or R¹ or R² or R³ stated in formula (I) not necessarily being identical, providing that, in the entire compound, at least one of the residues Y comprises a polyorganosiloxane unit with 2 to 1000 silicon atoms,
   or the acid addition compounds and/or salts thereof,
   for treating a hard surface, the treated surface being protected from soiling and/or the detachment of soiling from the surface being facilitated, and/or for improving the cleaning performance of a cleaning agent for a hard surface.
2. Use according to claim 1, characterised in that the polyorganosiloxane structural element present in the polycarbonate- and/or polyurethanepolyorganosiloxane compounds is the structure -(R⁴ ₂SiO)_p-(SiR⁴ ₂)- , in which R⁴ is a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 20 carbon atoms, and p is 1 to 999.
3. Use according to claim 2, characterised in that the polycarbonate- and/or polyurethane-polyorganosiloxane compounds contain on average at least two, in particular at least three, of the stated polyorganosiloxane structural elements.
4. Use according to one of claims 1 to 3, characterised in that, in the polycarbonate- and/or polyurethane-polyorganosiloxane compound, at least one of the Y units according to the structural element of the formula (I) comprises a grouping -NR²- and/or at least one of the Y units according to the structural element of the formula (I) comprises a grouping -(N⁺R²R³)-.
5. Use according to one of claims 1 to 4, characterised in that oligoethoxy and/or oligopropoxy groups are present in at least one of the units Y, R¹, R² and/or R³ according to the structural element of the formula (I), the degrees of oligomerisation of which groups in particular being in the range from 2 to 60.
6. Use according to one of claims 1 to 5, characterised in that oligoethyleneimine groups are present in at least one the units Y, R¹, R² and/or R³ according to the structural element of the formula (I), the degrees of oligomerisation of which groups are in particular in the range from 10 to 150000.
7. Use according to one of claims 1 to 6, characterised in that the compound of the formula (I) is a polycarbonate- and/or polyurethanepolyorganosiloxane compound which contains at least one structural element of the formula (II) or formula (III):
   
           -A-Y-A-(CO)-O-Z-(CHOH)-Z-O-(CO)-     (II),
   
           -A-Y-A-(CO)-O-(CHCH₂OH)-Z-O-(CO)-     (III),
   
   in which A and Y have the meanings stated for formula (I) and
   Z is selected from divalent, straight-chain, cyclic or branched, saturated or unsaturated, optionally substituted hydrocarbon residues with 1 to 12 carbon atoms.
8. Use according to one of claims 1 to 7, characterised in that the surface is of ceramics, in particular of ceramic sanitary ware.
9. Use according to one of claims 1 to 8, characterised in that the soiling comprises faecal soiling and/or biofilms.
10. A method for treating a hard surface, in which the surface is brought into contact with an active ingredient selected from polycarbonate, polyurethane and/or polyurea compounds containing at least one structural element of the formula (I):
    
            -Y-A-(C=O)-A-     (I),
    
    

    each A being independently selected from S, O and NR¹,

    Y being selected from di- to polyvalent, in particular tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon residues with up to 1000 carbon atoms (the carbon atoms of an optionally present polyorganosiloxane unit not being included in said number), which may contain one or more groups selected from -O-, -(CO)-, -NH-, -NR²-, -(N⁺R²R³)- and a polyorganosiloxane unit with 2 to 1000 silicon atoms,

    R¹ being hydrogen or a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 40 carbon atoms, which may contain one or more groups selected from -O-, -(CO)-, -NH- and -NR²-,

    R² being a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 40 carbon atoms, which may contain one or more groups selected from -O-, -(CO)- and -NH-,

    R³ being a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 100 carbon atoms, which may contain one or more groups selected from -O-, -(CO)- and -NH-, or being a divalent residue which forms cyclic structures within the residue Y,

    or one or both of the residues A adjacent to Y may form a nitrogenous heterocyclic residue with the residue Y located between them,
    and in the entire compound all the residues A or Y or R¹ or R² or R³ stated in formula (I) not necessarily being identical, providing that, in the entire compound, at least one of the residues Y comprises a polyorganosiloxane unit with 2 to 1000 silicon atoms, or the acid addition compounds and/or salts thereof,
    and with a surfactant.
11. A method according to claim 10, characterised in that the active ingredient and the surfactant are spread extensively over the surface and either rinsed off after a period of action of 1 to 10 minutes or alternatively left to dry, and/or in that contacting proceeds at a temperature of 5 to 50°C, in particular of 15 to 35°C.
12. A method according to claim 10 or 11, characterised in that it is a cleaning method.
13. An agent for treating a hard surface containing a polycarbonate- and/or polyurea-polyorganosiloxane compound containing at least one structural element of the formula (I):
    
            -Y-A-(C=O)-A-     (I),
    
    each A being independently selected from S, O and NR¹,

    Y being selected from di- to polyvalent, in particular tetravalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic, substituted or unsubstituted hydrocarbon residues with up to 1000 carbon atoms (the carbon atoms of an optionally present polyorganosiloxane unit not being included in said number), which may contain one or more groups selected from -O-, -(CO)-, -NH-, -NR²-, -(N⁺R²R³)- and a polyorganosiloxane unit with 2 to 1000 silicon atoms,

    R¹ being hydrogen or a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 40 carbon atoms, which may contain one or more groups selected from -O-, -(CO)-, -NH- and -NR²-,

    R² being a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 40 carbon atoms, which may contain one or more groups selected from -O-, -(CO)- and -NH-,

    R³ being a straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon residue with up to 100 carbon atoms, which may contain one or more groups selected from -O-, -(CO)- and -NH-, or being a divalent residue which forms cyclic structures within the residue Y,

    or one or both of the residues A adjacent to Y may form a nitrogenous heterocyclic residue with the residue Y located between them,
    and in the entire compound all the residues A or Y or R¹ or R² or R³ stated in formula (I) not necessarily being identical, providing that, in the entire compound, at least one of the residues Y comprises a polyorganosiloxane unit with 2 to 1000 silicon atoms, or the acid addition compound and/or salt thereof,
    in particular in quantities of 0.01 to 50 wt.%, preferably of 0.2 to 15 wt.%, and particularly preferably of 0.5 to 5 wt.%, relative to the total weight of the agent,
    at least one surfactant and
    optionally water and/or further conventional constituents, compatible with the other ingredients, of surface treatment or cleaning agents.