EP2109664B1 - Compositions for treating hard surfaces - Google Patents

Abstract

The invention relates to compositions for treating a hard surface, in particular for cleaning and/or dirt-repellent treatment of a hard surface, containing a) at least one multi-armed silyl polyalkoxylate of the formula (I) (H-A)n-Z-[A-B—Si(OR1)r(R2)3−r]m (I), where Z is a (m+n)=valent radical having at least three carbon atoms, A is a divalent polyoxyalkylene radical, wherein the m+n polyoxyalkylene radicals bound to Z can be different from one another, and wherein one radical A is in each case bound to Z via an oxygen atom belonging to Z, and one oxygen atom belonging to A is bound to B or hydrogen, B is a chemical bond or a divalent organic radical having 1 to 50 carbon atoms, OR1 is a hydrolysable group, R1 and R2 independently of one another are a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer from 1 to 3, and m is an integer ≧1 and n is 0 or an integer ≧1, and m+n has a value from 3 to 100, b) at least one surfactant, c) water and/or at least one nonaqueous solvent, d) if appropriate further conventional components of surface treatment and/or cleaning compositions which are compatible with the remaining components of the composition.

Description

The present invention relates to the technical 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 addition of organic acids such as citric acid or sulfamic acid, so that they have a good Have efficacy 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 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, 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 (e.g., bacteria, algae, fungi, protozoa) are embedded. This can be not only a hygienic but also an aesthetic problem. As an antidote biocidal 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 to provide a hard surface with soil repellency and / or to facilitate the release of soil and / or reduce the formation or adhesion of biofilms, where these effects can be achieved optionally in a stand-alone surface treatment process, or in the course of a cleaning process, in which a surface is cleaned and at the same time provided with the aforementioned properties.

Furthermore, it is necessary for the production of such agents that the ingredients used can be easily incorporated into the recipe, and the means have a good shelf life.

The US 6423661 B1 describes silyl-terminated prepolymers for the preparation of which the OH groups of a polyether polyol, which may have up to eight arms, are reacted with an isocyanate silane. The resulting compounds called prepolymers are for use in adhesives. A use of the prepolymers in surface treatment or cleaning agents is not disclosed.

From the US 2003/0153712 A1 For example, a polyurethane prepolymer having terminal alkoxysilane and hydroxy groups is known. For the preparation, a polyether-diol is first reacted with stoichiometric diisocyanate, and the resulting isocyanate-hydroxy compound is then further treated with an aminosilane to introduce the silyl groups. The described, two-armed polyalkoxylates representing prepolymers are used for the production of sealants and adhesives.

The US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a completely silyl-terminated derivative which can be prepared starting from sorbitol as a central unit. The polyethylene glycol derivatives described in the document are said to be useful for the preparation of biodegradable polymeric hydrogels and for medical pharmaceutical use, for example, for implants.

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 provide means for improving the removability of 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 silyl-polyalkoxylate-containing agents are particularly suitable to protect a surface treated therewith from contamination and / or to facilitate the removal of contaminants from the surface.

1. a) mindestens ein mehrarmiges Silyl-Polyalkoxylat der Formel (I)
   
           (H-A)_n-Z-[A-B-Si(OR¹)_r(R²)_3-r]_m     (I)
   
   worin
   Z für einen (m+n)-wertigen Rest mit mindestens drei Kohlenstoffatomen steht,
   A einen zweiwertigen Polyoxyalkylenrest bedeutet, wobei die an Z gebundenen m+n Polyoxyalkylenreste voneinander unterschiedlich sein können, und wobei ein Rest A jeweils über ein zu Z gehöriges Sauerstoffatom mit Z und ein zu A gehöriges Sauerstoffatom mit B beziehungsweise Wasserstoff verbunden ist,
   B für eine chemische Bindung oder einen zweiwertigen organischen Rest mit 1 bis 50 Kohlenstoffatomen steht,
   OR¹ eine hydrolysierbare Gruppe bedeutet, R¹ und R² unabhängig voneinander eine lineare oder verzweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen bedeuten und r für eine ganze Zahl von 1 bis 3 steht, und
   m eine ganze Zahl ≥ 1 ist und n für 0 oder eine ganze Zahl ≥ 1 steht, und m+n einen Wert von 3 bis 100 aufweist,
2. b) mindestens ein Tensid,
3. c) Wasser und/oder mindestens ein nichtwässriges Lösungsmittel
4. d) gegebenenfalls weitere, mit den übrigen Bestandteilen des Mittels verträgliche übliche Inhaltsstoffe von Oberflächenbehandlungs- und/oder Reinigungsmitteln.

The subject of the present invention is therefore a means for the treatment of a hard surface, in particular for the cleaning and / or the dirt-repellent treatment of a hard surface, containing

1. a) at least one multi-arm silyl polyalkoxylate of the formula (I)
   
   (HA) _n -Z- [AB-Si (OR ¹ ) _r (R ² ) _3-r ] _m (I)
   
   wherein
   Z is an (m + n) -valent radical having at least three carbon atoms,
   A denotes a divalent polyoxyalkylene radical, where the m + n polyoxyalkylene radicals bonded to Z can differ from one another, and where one radical A is in each case linked to Z via an oxygen atom belonging to Z and one to A belongs to oxygen atom with B or hydrogen,
   B is a chemical bond or a bivalent organic radical having 1 to 50 carbon atoms,
   OR ^{1 is} a hydrolyzable group, R ¹ and R ^{2 are} independently a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer of 1 to 3, and
   m is an integer ≥ 1 and n is 0 or an integer ≥ 1, and m + n has a value of 3 to 100,
2. b) at least one surfactant,
3. c) water and / or at least one non-aqueous solvent
4. d) optionally further customary ingredients of surface treatment and / or cleaning agents which are compatible with the other constituents of the composition.

For the purposes of the present invention, hard surfaces are in particular 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 treatment of a surface, all conventional methods are suitable, with which the agent can be applied to the surface. For the most preferred case, that the agent is liquid at room temperature, the treatment of the surface is preferably carried out so that the agent is transferred to the surface by means of an absorbent fabric or that the agent is sprayed onto the surface. However, the treatment can also be done, for example, by immersing the surface in the agent.

For the purposes of the invention, dirt or soiling are in particular fecal dirt and / or biofilms.

By treating a hard surface with the agent according to the invention, it is protected against contamination and / or facilitates the detachment of dirt from the surface. In particular, the agent prevents the formation of biofilms without having a biocidal effect. It is believed that the effectiveness of the biofilm formation agents of the present invention is due to a bacteriostatic effect of the silyl polyalkoxylates used, thereby inhibiting the colonization of surfaces with microorganisms and hindering their attachment and propagation to the surfaces. On the other hand, since no biocidal effects were observed for the agents, they are not subject to the disadvantages mentioned in the introduction of biocides.

The agents of the present invention provide for easier soil removability and reduced tendency to re-soak and, in particular, improve the cleaning performance of hard surface cleaners. As a result, appropriately treated or cleaned surfaces are perceived longer than clean.

It has further been observed that both easier and faster removal of fecal dirt and improved rinsing of the dried (possibly colored) cleaning agent itself is possible when a silyl polyalkoxylate of the formula (I) is added to the detergent formulation. If faecal dirt meets a surface treated in this way, 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.

The use of silyl polyalkoxylates of the formula (I) as additives in surfactant-containing cleaning agents makes it possible not only to clean one surface in a single work step, but at the same time provides it with protection against dirt. In this way, for example, a calcification, an adhesion of protein or fat-containing dirt and the growth of bacteria is prevented. The treated surfaces stay clean longer and, moreover, the subsequent cleaning is greatly facilitated. This means that you need to clean the surfaces less often without sacrificing cleanliness, and their subsequent cleaning is associated with less effort insofar as it can be done in a time-saving manner and / or requires milder detergents. So it is possible in favorable cases, for a certain time alone with the help of water a sufficient To achieve cleaning effect, ie without the need for the use of a conventional cleaning agent.

The silyl polyalkoxylates of the formula (I) can be easily and simply formulated in the other constituents of the composition and, in particular, can be incorporated in a very simple manner into conventional detergent formulations. In particular, the advantageous solubility properties of these substances mean that their incorporation into customary cleaning agents does not entail any restrictions, such as a reduced sprayability.

For the purposes of this invention, multi-armed silyl polyalkoxylates contain polymer arms which are essentially star-shaped or radially bonded to a central unit.

In a preferred embodiment of the invention, a silyl polyalkoxylate of the formula (I) or a mixture of several of these compounds is used, wherein the weight average molecular weight is from 500 to 50,000, preferably from 1,000 to 20,000, and more preferably from 2,000 to 10,000. The silyl polyalkoxylate preferably contains 0.3 to 10 wt .-%, particularly preferably 0.5 to 5 wt .-% silicon, based on the total weight of the silyl polyalkoxylate.

Z preferably represents an at least trihydric, in particular tri-to octahedral, acyclic or cyclic hydrocarbon radical having 3 to 12 carbon atoms, where the radical may be saturated or unsaturated and in particular also aromatic. Z is particularly preferably the trivalent radical of glycerol or the trihydric to hexahydric radical of a sugar, for example the hexavalent radical of sorbitol or the octahedral radical of sucrose. The x-valent radical of one of the abovementioned polyols is to be understood as meaning that molecule fragment which remains from the polyol after removal of the hydrogen atoms from x alcoholic or phenolic hydroxyl groups. In principle, Z can stand for any central unit which is known from the literature for the preparation of star-shaped (pre) polymers.

Furthermore, it is particularly preferred if in formula (I) n is 0, 1 or 2 and m is a number from 3 to 8.

A is preferably selected from poly-C ₂ -C ₄ -alkylene oxides, more preferably a (co) polymer of ethylene oxide and / or propylene oxide, in particular a copolymer having a propylene oxide content of up to 60% by weight, preferably up to to 30 wt .-% and particularly preferably of up to 20 wt .-%, which may be random and / or block copolymers. Accordingly, in a further preferred embodiment of the invention in formula (I) A for - (CHR ³ -CHR ⁴ -O) _p -, wherein R ³ and R ^{4 are} independently hydrogen, methyl or ethyl and p is an integer from 2 to 10,000.

B is in particular a chemical bond or a bivalent, low molecular weight organic radical having preferably 1 to 50, in particular 2 to 20 carbon atoms. Examples of divalent low molecular weight organic radicals are short-chain aliphatic and heteroaliphatic radicals such as - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, -C (O) -NH- (CH ₂ ) ₃ - and -C (O) -NH-X-NH-C (O) -NH- (CH ₂ ) ₃ -, wherein X is a bivalent aromatic radical such as the phenylene radical or an alkylidene radical. Most preferably, B is a bond or the radical -C (O) NH- (CH ₂ ) ₃ -.

Preferably, R ¹ and R ² independently of one another are methyl or ethyl, and r is 2 or 3. Examples of radicals -Si (OR ¹ ) _r (R ² ) _3-r are dimethylethoxysilyl, dimethylmethoxysilyl, diisopropylethoxysilyl, methyldimethoxysilyl However, trimethoxysilyl and triethoxysilyl radicals are most preferred.

It is most preferred when R ¹ and R ^{2 are the} same and are methyl or ethyl.

Furthermore, it is particularly preferred if r stands for the number 3.

The sum m + n is preferably 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8, and coincides with the number of arms which is bound in the compound (I) to the central unit Z. The central unit therefore preferably has 3 to 50, in particular 3 to 10 and particularly preferably 3 to 8, oxygen atoms which serve as attachment points for the arms.

In a particular embodiment, n is 0. In the case where n> 0, the ratio n / m is between 99/1 and 1/99, preferably 49/1 and 1/49, and especially 9/1 and 1 /. 9

In a further preferred embodiment of the invention, the agent contains a mixture of at least two, in particular two to four, different multi-armed silyl polyalkoxylates of the formula (I).

It is particularly preferred if the at least two different multi-armed silyl polyalkoxylates differ in the number of their arms. Advantageously, a first silyl polyalkoxylate having 3 to 6 arms is combined with a second silyl polyalkoxylate having 6 to 10 arms.

Particular preference is given to mixtures comprising at least two different multi-arm silyl polyalkoxylates of the formula (I) where n = 0, which are selected from the group of the multi-armed silyl polyalkoxylates of the formula (I) where m = 3, m = 6 and m = 8 ,

When two different multi-arm silyl polyalkoxylates are used, they are generally present in a quantitative ratio of from 99: 1 to 1:99, preferably from 49: 1 to 1:49, and more preferably from 9: 1 to 1: 9.

In a further particularly preferred embodiment of the invention, the agent according to the invention further contains at least one hydrolyzable silicic acid derivative.

Hydrolyzable silicic acid derivatives are to be understood as meaning in particular the esters of orthosilicic acid, in particular the tetraalkoxysilanes and very particularly preferably tetraethoxysilane. For the purposes of the present invention, however, hydrolyzable silicic acid derivatives are also compounds which also carry a carbon residue on the silicon atom in addition to three alkoxy groups, for example N- (triethoxysilylpropyl) -O-polyethylene oxide-urethane, dimethyl-octadecyl- (3- (trimethoxysilylpropyl) ammonium chloride, diethylphosphatoethyltriethoxysilane and the trisodium salt of N- (trimethoxysilylpropyl) ethylenediaminetriacetic acid.

In this embodiment, it is particularly advantageous if the quantitative ratio of silyl polyalkoxylate or silyl polyalkoxylate mixture to the at least one hydrolyzable silicic acid derivative 90:10 to 10:90, preferably 50:50 to 10:90, and especially 40:60 to 20:80.

The at least one silyl polyalkoxylate of the formula (I) is usually present in the composition according to the invention in an amount of 0.001 to 20% by weight, in particular 0.01 to 10% by weight, preferably 0.05 to 5% by weight and more particularly preferably used from 0.1 to 1 wt .-%, in each case based on the total weight of the composition.

Insofar as the multi-arm silyl polyalkoxylates of the general formula (I) used according to the invention are not known from the literature, their preparation can be carried out by functionalization of suitable polyhydric polyalkoxylate precursors in analogy to known functionalization processes of the prior art.

That in the US 2003/0153712 A1 described two-arm polyurethane prepolymer having terminal alkoxysilane and hydroxy groups is prepared by first reacting a polyether diol with stoichiometric diisocyanate, and the resulting isocyanate-hydroxy compound then further with an aminosilane to introduce the silyl groups is treated. The synthesis principles used there can be basically transferred to the preparation of multi-armed polyalkoxylates according to the teachings of the present invention.

In the US 6423661 B1 silyl-terminated prepolymers are described, for their preparation, the OH groups of a polyether polyol, which may have up to eight arms, are reacted with an isocyanate silane. The teaching of this document includes prepolymers which fall under the general formula (I) of the present invention.

The US 2004/0096507 A1 is concerned with six-armed polyethylene glycol derivatives and discloses a fully silyl-terminated derivative which can be prepared starting from sorbitol as a central unit and which falls under the general formula (I) of the present invention.

Suitable polyalkoxylate precursors for the preparation of the silyl polyalkoxylates used according to the invention are in turn polyaromatic polyalkoxylates which already have the above-described multi-arm structure and which each have a hydroxyl group at the ends of the polymer arms which is partially or completely group (n) -B -Si (OR ¹ ) _r (R ² ) _3-r can be converted. The polyalkoxylate precursors of the silyl polyalkoxylates used according to the invention can be represented by the general formula (II)

Z- (A-OH) _{m + n} (II)

represent, wherein Z, A, m and n have the same meaning as previously described for the compounds of formula (I).

For example, suitable polyalkoxylate precursors are known from the literature under the name star-shaped or multi-arm polyether polyols. These polyalkoxylate precursors are prepared by polymerization of the appropriate monomers, especially ethylene oxide and / or propylene oxide, using polyfunctional small molecules such as glycerol or sorbitol as initiator. Examples of polyhydric polyether polyols ethoxylates or propoxylates of glycerol, sucrose and sorbitol, as described in the patent US 6423661 are described. Because of the statistical nature of the polymerization reaction, the abovementioned statements on the polymer arms of the silyl polyalkoxylates used according to the invention, in particular with regard to the arm length and arm number (m + n), are each understood to be a statistical average.

Suitable polyalkoxylate precursors are also commercially available in part. An example of this is Voranol 4053, a polyether polyol (poly (ethylene oxide-co-propylene oxide)) from DOW Chemicals. It is a mixture of two different polyether polyols, consisting of a 3-arm polyether polyol with glycerol as the central unit and an 8-arm polyether polyol with cane sugar as the central unit. The arms represent random copolymers of about 75% EO and about 25% PO, the OH functionality (hydroxy end groups) is an average of 6.9 at a weight average molecular weight of about 12000. This results in a Ratio of about 78% 8-arm polyether polyol and about 22% 3-arm polyether polyol. Another example is Wanol R420 from WANHUA, China, which is a mixture of a linear poly (propylene / ethylene) diethylene glycol and an 8-arm polyether polyol (poly (propyleneoxy / ethyleneoxy) sucrose) in a ratio of about 15 -25: 85-75 represents. Also commercially available is the polyether polyol Voranol CP 1421 from DOW Chemicals, which is a 3-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of about 75/25 and a weight average (Weight average molecular weight) of about 5000 is.

As starting materials for the conversion of the hydroxy end groups of the polyhydric polyalkoxylate precursor in the groups -B-Si (OR ¹ ) _r (R ² ) _3-r are in principle all functional silanes in question, which have a functional group which is opposite to the hydroxy End groups of the polyalkoxylate precursor is reactive. Examples are tetraalkoxy silanes such as tetramethyl silicate and tetraethyl silicate, (meth) acrylate silanes such as (3-methacryloxypropyl) trimethoxysilane, (methacryloxymethyl) triethoxysilane, (meth-acryloxymethyl) methyldimethoxysilane and (3-acryloxypropyl) trimethoxysilane, isocyanato-silanes such as Isocyanatopropyl) trimethoxysilane, (3-isocyanato-propyl) triethoxysilane, (isocyanatomethyl) methyldimethoxysilane and (isocyanatomethyl) trimethoxysilane, aldehyde-silanes such as triethoxysilylundecanal and triethoxysilylbutyraldehydes, epoxy-silanes such as (3-glycidoxypropyl) -trimethoxysilane, anhydride-silanes such as 3 (Triethoxysilyl) propylsuccinic anhydride, halogenated silanes such as chloromethyltrimethoxysilane and 3-chloropropyl-methyldimethoxysilane, hydroxy-silanes such as hydroxymethyltriethoxysilane, and tetraethylsilicate (TEOS), which are commercially available, for example, from Wacker Chemie GmbH (Burghausen), Gelest, Inc. (US Pat. Morrisville, USA) or ABCR GmbH & Co. KG (Karlsruhe) or herge by known methods can be made. Tetraalkoxy-silanes, isocyanato-silanes or anhydride-silanes, but in particular isocyanato-silanes or anhydride-silanes, are particularly preferably reacted with polyhydric polyalkoxylate precursors of the general formula (II). In a complete reaction of all hydroxy endings with the functional silanes obtained according to the invention used multi-arm silyl polyalkoxylates which carry at the ends of the arms exclusively radicals -B-Si (OR ¹ ) _r (R ² ) _3-r , ie where n = 0 is. The group B is in such a case, for example, exclusively in a bond, or it comprises, when an isocyanatosilane was used as a functional silane, together with the terminal oxygen atom of group A, for example, a urethane group and the atomic group, in the starting isocyanatosilane between the isocyanato group and the silyl group stands. In a complete reaction of all hydroxy ends with anhydride silanes, for example, 3- (triethoxysilyl) propylsuccinic obtained one multi-arm silyl polyalkoxylates, which also carry only radicals -B-Si (OR ¹ ) _r (R ² ) _3-r . Group B in such a case, together with the terminal oxygen atom of group A, comprises an ester group and the atomic group which in the starting anhydride silane is between the anhydride group and the silyl group.

If multi-arm silyl polyalkoxylates of the general formula (I) used according to the invention are used which carry both hydroxy and -B-Si (OR ¹ ) _r (R ² ) _3-r groups at the ends of their arms, preference is given to this proceeded that a polyalkoxylate precursor of the general formula (II) is reacted with a relation to the total of the terminal hydroxy groups substoichiometric amount of a functional silane, ie there are described above, first -B-Si (OR ¹ ) _r (R ² ) Introduced _3-r groups, but not all terminal hydroxyl groups in the polyhydric polyalkoxylate precursor reacted. In this way one obtains multi-armed polyalkoxylates which carry both hydroxy and -Si (OR ¹ ) _r (R ² ) _3-r groups. Thus, for example, in a partial reaction of the hydroxy ends of a polyhydric polyether polyol with isocyanato-silanes multi-armed polyalkoxylates which carry both terminal silyl groups and OH groups (R ¹ = OH). In a further step, the remaining or a part of the remaining hydroxyl groups can be modified as described to give radicals B-Si (OR ¹ ) _r (R ² ) _3-r .

The other components present in the aqueous composition according to the invention in addition to the at least one silyl polyalkoxylate are to be selected according to their type and the amount used in such a way that no undesired interactions with the silyl polyalkoxylate occur.

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 -alkylpolyglycol ether sulfates having 2 to 6 ethylene oxide units (EO) in the ether part as well as 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 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 to be 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. Particular preference is given to using 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.

In a preferred embodiment of the invention, the nonionic surfactant is selected from the group comprising polyalkylene oxides, in particular alkoxylated primary alcohols, where the polyalkylene oxides may also be end-capped, alkoxylated fatty acid alkyl esters, amine oxides and alkyl polyglycosides and mixtures thereof.

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.

In a particularly preferred embodiment of the invention, the compositions according to the invention contain at least one nonionic surfactant which is (s) selected in particular from the ethoxylated and / or propoxylated alcohols having 8 to 18 carbon atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and or propylene oxide units (PO) and the alkyl polyglycosides having 8 to 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units.

The compositions according to the invention preferably contain surfactants in amounts of from 0.01 to 20% by weight, in particular from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight and more preferably from 0.2 to 1% by weight. %, in each case based on the total weight of the agent.

The compositions of the invention contain water and / or at least one non-aqueous solvent. Suitable non-aqueous solvents are preferably those solvents which are miscible in any ratio with water. The nonaqueous solvents include, for example, monohydric or polyhydric alcohols, alkanolamines, glycol ethers and mixtures thereof. 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. However, in a preferred embodiment, ethanol is used as the nonaqueous solvent.

Non-aqueous solvents may be present in the composition according to the invention in amounts of from 0.01 to 99.9% by weight, in particular from 0.1 to 50% by weight, and particularly preferably from 2 to 20% by weight, based in each case on Total weight of the agent.

Water is contained in the composition according to the invention generally in amounts of 1 to 98 wt .-%, in particular 50 to 95 wt .-%, and particularly preferably 80 to 93 wt .-%, each based on the total weight of the composition.

In a further preferred embodiment, the agent according to the invention contains a thickening agent. Suitable for this purpose are in principle all viscosity regulators used in detergents and cleaners in the prior art, for example organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins , Gelatin, casein), organic modified natural products (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 like Montmorillonite, zeolites, silicas). Examples of polyacrylic and polymethacrylic compounds include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry, and Fragrance Association (US Pat. CTFA): 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 ^® polymers are available, for example the anionic non-associative polymers Aculyno ^® 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 ^8, and for example, by Fa. Kelco under the trade names Keltrol ^® and Kelzan ^® or from Rhodia is available under the trade name Rhodopol ^®. As thickeners, it is also possible to use phyllosilicates. These include, for example, available under the trade name Laponite ^® magnesium or sodium-magnesium phyllosilicates from Solvay Alkali, in particular the Laponite ^® RD or Laponite ^® RDS, and the magnesium silicates Süd-Chemie, especially the Optigel ^® SH. In a preferred embodiment, the agent according to the invention contains xanthan gum and succinoglycan gum.

If the agent according to the invention contains a thickener, it is generally present in amounts of from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.

The viscosity of the compositions according to the invention can be adjusted within a wide range depending on the intended use. Thus, for general-purpose and bathroom cleaners, generally low, almost water-thin formulations may be preferred, while for other uses, for example, toilet bowl cleaners, higher-viscosity, thickened formulations may be preferred. In general, the viscosity of the inventive compositions in the range of 1 to 3000 mPas, preferably from 200 to 1500 mPas and particularly preferably from 400 to 900 mPas (Brookfield viscometer Rotovisco LV-DV II plus, spindle 31, 20 ° C, 20 U / min).

In a preferred embodiment, the agent according to the invention has a pH of less than 9, in particular a pH of 0 to 6, preferably 1 to 5 and particularly preferably 2 to 4.

In a further, particularly preferred embodiment, the agent according to the invention contains at least one acid. 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. However, it may be preferred if acetic acid is not used as the 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 .-%, each based on the total weight of the composition.

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 are, for example, film formers, antimicrobial agents, builders, corrosion inhibitors, complexing agents, alkalis, preservatives, bleach, Enzymes and fragrances and dyes into consideration. Overall, the compositions should preferably contain not more than 30% by weight of further ingredients, preferably from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight.

The compositions according to the invention may contain film formers which may 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 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-butylcarbamate, 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. In this case, water-soluble builders are preferred because they usually less so tend 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.

Furthermore, in enzyme-containing agents, enzyme stabilizers may be present to prevent 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 To protect division. 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 agent according to the invention is preferably a cleaning agent, in particular a cleaning agent for ceramics, more preferably sanitary ceramics.

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.

The present invention likewise provides a process for preparing a composition according to the invention, in which the individual components are mixed with one another.

Another object of the present invention is a method for treating a hard surface, wherein the surface is brought into contact with an agent according to the invention, as described in the preceding text.

This process can be carried out as a stand-alone treatment process for the surface, for example with dirt-repellent properties or one or more to provide the other properties which cause the agents according to the invention according to the teaching of the present invention. The surface is brought into contact with a composition according to the invention.

Preferably, the inventive method is carried out so that the agent is distributed over the surface area and advantageously then either after a contact time of 1 second to 20 minutes, preferably 1 to 10 minutes, rinsed 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 particular, the inventive method is used to treat a surface of ceramic, glass, stainless steel or plastic.

A further embodiment of the invention relates to the use of a composition according to the invention for protecting a hard surface against stains and / or for easier removal of new stains from the surface, wherein the stain (s) are in particular faecal dirt and / or biofilms and / or or protein deposits.

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 advantageously distributed over the surface area and either rinsed after a contact 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.

A further embodiment of the invention relates to the use of an agent according to the invention for water-repellent finishing of a hard surface and / or for shortening the drying time of a hard surface after exposure to water.

For cleaning reasons, it is on the one hand more favorable if surfaces have hydrophilic properties, since such surfaces easily with conventional cleaning fluids wetted on a watery basis and thus facilitate Abwaschprozesse. On the other hand, it is also desirable that the surfaces are cleaned as quickly as possible after cleaning with water or with water-based cleaning agents again from the water film, so the water runs as quickly and completely again, and thus no water film on the surface remains, such as in a Teflon coated pan. Otherwise, when the water film dries, a residual soiling may remain on the surface, such as, for example, limescale, which looks unattractive and can promote renewed soiling, for example by proteins and microorganisms. For this reason, it is very advantageous that the treatment of a surface with the agents according to the invention makes this surface hydrophilic. This facilitates wetting and the removal of dirt and at the same time causes the surface to be easily "dewaxed" by a film of water, thereby avoiding the formation of water droplets and thus the retention of residual soiling. This feature is particularly useful where surfaces are particularly prone to lime and dirt and biofilm deposits, such as, typically, toilet bowls, sinks, baths and shower stalls. Another benefit of this feature is that water drains from treated surfaces faster, allowing them to dry faster. In a cleaning process, a rinse with pure water is usually required after treating the surface with detergent. It is desirable that the surfaces after this rinse quickly dry again, for example, because a fast-drying surface in a consumer enhances the impression of cleanliness.

Likewise provided by the present invention is the use of an agent according to the invention for the bacteriostatic finishing of a hard surface.

A particular advantage of the silyl polyalkoxylates of the formula (I) used in accordance with the invention lies in the fact that colonization by and growth of microorganisms is suppressed on surfaces treated with them without the need for biocides. This achieves a surface finish on which bacteria can not multiply or only in a much slower way. This is a clear advantage over the prior art, especially in view of the fact that the use of biocides is becoming increasingly critical with regard to environmental and consumer protection.

A further embodiment of the invention therefore relates to the use of a multi-arm silyl polyalkoxylate of the formula (I)

(HA) _n -Z- [AB-Si (OR ¹ ) _r (R ² ) _3-r ] _m (I)

wherein
Z is an (m + n) -valent radical having at least three carbon atoms,
A denotes a divalent polyoxyalkylene radical, where the m + n polyoxyalkylene radicals bonded to Z can differ from one another, and where one radical A is in each case linked to Z via an oxygen atom belonging to Z and one to A belongs to oxygen atom with B or hydrogen,
B is a chemical bond or a bivalent organic radical having 1 to 50 carbon atoms,
OR ^{1 is} a hydrolyzable group, R ¹ and R ^{2 are} independently a linear or branched alkyl group having 1 to 6 carbon atoms and r is an integer of 1 to 3, and
m is an integer ≥ 1 and n is 0 or an integer ≥ 1, and m + n has a value of 3 to 100,
for the bacteriostatic treatment of a hard surface.

embodiments A. Synthesis Examples: 1. Preparation of a six-armed triethoxysilyl-terminated polyalkoxylate

The starting material used was a polyether polyol which is a 6-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of 80/20 and a molecular weight of 12,000 g / mol, obtained by anionic ring-opening polymerization of ethylene oxide and propylene oxide using sorbitol as initiator. Before further reaction, the polyether polyol was heated in vacuo with stirring for 1 h at 80 ° C. A solution of polyether polyol (3 g, 0.25 mmol), triethylenediamine (9 mg, 0.081 mmol) and dibutyltin dilaureate (9 mg, 0.014 mmol) in 25 mL of anhydrous toluene was added, to which was added a solution of (3-isocyanatopropyl ) triethoxysilane (0.6 ml, 2.30 mmol) in 10 ml of anhydrous toluene was added dropwise. The solution was further stirred at 50 ° C overnight. After removing the toluene under vacuum, the crude product was repeatedly washed with anhydrous ether. After vacuum drying, the product, each having a triethoxylsilyl group at the free ends of the polymer arms of the star-shaped prepolymer, was obtained as a colorless viscous liquid. IR (film, cm ^-1 ): 3349 (m, -CO-NH-), 2868 (s, -CH ₂ -, -CH ₃ ), 1719 (s, -C = O), 1456 (m, -CH ₂ -, -CH ₃ ), 1107 (s, -COC-), 954 (m, -Si-O-). ¹ H-NMR (benzene-d ₆ , ppm): 1.13 (d, -CH ₃ of polymer arms), 1.21 (t, -CH ₃ of silane end groups), 3.47 (s, -CH ₂ of polymer arms), 3.74 (q, -CH ₂ of silane end groups). The triethoxysilyl-terminated polyalkoxylate obtained has a molecular weight of 13,500.

2. Preparation of a three-armed triethoxysilyl-terminated polyalkoxylate

Voranol CP 1421 from DOW Chemicals was dried in vacuo with stirring for 1 h at 80 ° C. To 2.04 g (0.41 mmol) of the dried polyether polyol was slowly added 317 mg (1.0 equivalents) of (3-isocyanatopropyl) triethoxysilane. The reaction mixture was further stirred under inert gas at 100 ° C for 2 days until the vibration band of the NCO group disappeared upon IR measurement. The product, each having a triethoxylsilyl group at the free ends of the polymer arms of the polyether polyol, was obtained as a colorless viscous liquid.

3. Preparation of a mixture containing a three-armed and an eight-armed triethoxysilyl-terminated polyalkoxylate

Voranol 4053 from DOW Chemicals was dried in vacuo with stirring for 1 h at 80 ° C. To 209 g (16.9 mmol) of the dried polyether polyol, 20.9 mg (0.01%) of dibutyltin dilaurate and 30.3 g (1.0 equivalent) of (3-isocyanatopropyl) triethoxysilane became slow added. The reaction mixture was further stirred under inert gas at room temperature for 2 days until the NCO band disappeared on IR measurement. The product was obtained, which in each case has a triethoxylsilyl group at the free ends of the polymer arms of the polyether polyol and represents a mixture of a 3-armed and an 8-armed polyalkoxylate in a ratio of about 20/80, as a colorless viscous liquid.

B. Test Methods and Results: 1.2. Easy-to-clean test with IKW ballast dirt:

IKW ballast dirt was after the literature SOFW Journal, 1998, 124, 1029 , produced. The test surfaces were overcoated with ballast soil and dried overnight at room temperature. After drying, the surfaces were rinsed with running water. The amount and distribution of residual debris remaining on the surfaces (white fat layer) was used as a criterion for the easy-to-clean effect.

1.3. Easy-to-clean test with shoe cream dirt:

Shoe polish dirt was made as follows: A mixture of black shoe polish (6.5% by weight), Mazola oil (3.5% by weight), gravy (26% by weight) and tap water (64% by weight) became 100 ° C cooked for 2 min. Subsequent stirring for 20 minutes and cooling to room temperature gave the shoe cream stain. The test surfaces were dipped in the shoe cream soil for 2 minutes. After removal, the test surfaces were dried at room temperature for 1 min and then rinsed with running water. The amount and distribution of residual debris left on the surfaces (white fat layer) were used as criteria for the easy-to-clean effect.

1.4. Easy-to-clean test with synthetic fecal contamination:

It was a synthetic Fäkalanschmutzung according to the patent DE 103 57 232 B3 produced. Similar to the test procedure described there, the fecal soiling was applied punctiform (diameter 10 mm) to the test surfaces using a metal template and dried at room temperature for 15 min. After drying, the surfaces were rinsed in a laboratory rinse, which simulates the flushing of a toilet flush toilet, with evenly flowing water. The time (in seconds) that elapses from the start of the rinse to the time when the yellowish brown fecal stain was completely removed from the surfaces and the amount and distribution of residual debris (white fat layer) were used as criteria for the Easy -to-clean effect used. In addition, it was also taken into account whether the surfaces become dry again quickly after rinsing off.

1.5. Anti-scale test:

To carry out the test, a calcium-magnesium-rich mineral water brand Contrex was used. The test surfaces were immersed in this water at room temperature for 24 hours. After removal, the test surfaces were dried in air for 2 hours and then in dist. Water immersed for 20 min. After removal, the test surfaces were air dried for an additional 2 hours. It was only followed by a qualitative visual assessment of whether and with what amount of lime the surfaces are covered. Thereafter, a quantitative determination of the amount of lime deposited on the surfaces was carried out. For this purpose, the accumulated lime was dissolved with dilute hydrochloric acid and the amount of calcium and magnesium ions in the resulting aqueous solution was determined by titration (standard method from Metrohm). The normalized amount of lime (mg / cm ² ) was used as a criterion for the anti-lime effect.

1.6. Microbiological investigations: 1.6.1 Biorepulsive Performance in the Adhesion Test:

The biorepulsive performance of a test substance was determined in an adhesion test for microorganisms with the organisms Staphylococcus aureus DSM799 and Pseudomonas aeruginosa DSM939. For this purpose, the substances to be tested were applied to hard surfaces, which have relevance in the household, such. As ceramic, plastic, stainless steel and glass. Specimens of 18x18 mm format were first washed with sterile and distilled water and dried. The thus prepared specimens were overlaid with a germ suspension and incubated for one hour. Subsequently, the seed suspensions were filtered off with suction and the test pieces were washed twice. After transfer to sterile test plates, the test specimens for S. aureus were overlaid with nutrient agar and then incubated for 48 hours at 30 ° C. For P. aeruginosa, the test specimens were shaken in buffer, then overlaid with nutrient agar plus 10% TZC and then incubated for 24 hours at 30 ° C. The shaking fluid was filtered through a membrane and the filters were incubated on Caso agar for 24 hours at 30 ° C. The extent of seed growth indicative of colonization of the specimens with nuclei is reported relative to an untreated surface, thereby setting the microbial load of the control specimen as 100%.

1.6.2. Anti-bioburden properties in the biofilm test:

In order to obtain longer-term, application-oriented statements on the surface efficiency of coatings on ceramics, coated surfaces (2 × 2 cm) were exposed to biofilm growth for 24 hours. The test specimens were placed in a microtiter plate consisting of 6 chambers. For this purpose, a germ mixture consisting of Dermacoccus nishinomiyaensis DSMZ 20448, Bradyrhizobium japonicum DSMZ 1982 and Xanthomonas campestris DSMZ 1526, which forms a stable biofilm in aqueous environments, was added at a bacterial count of 106 cfu / ml. For the biofilm experiment, the germs in the above-mentioned concentration together with a diluted complete medium (50 times DGHM-water-diluted TBY) were added to the microtiter plate, which is used in the form as a miniaturized biofilm test system. Double determinations were made by each approach, i. Two specimens per batch were examined. The 6-well plates were shaken for 24 h at 30 ° C and 60 rpm. After the given incubation times, 1 ml each per batch was taken for germ count determination, diluted in tryptone-NaCl solution and plated out on caso-agar. The resulting plates were incubated at 37 ° C for 24 h and then counted. The test specimens were removed from the microtiter chambers for drying at room temperature and then stained with 6 ml of 0.01% safranine solution for 15 minutes. Thereafter, the dyeing solution was sucked off, and the test pieces were rinsed to remove the unbonded dye from the test pieces. After drying, the dyed test specimens were evaluated.

1.6.3. Practical laboratory test in the toilet reactor:

Parallel to 1.6.2. The test specimens were examined in an almost automatically running, application-oriented WC reactor, which simulates the function of a toilet from its construction. This system makes it possible to examine adhesion and biofilm formation in a test system on several different surfaces over a short and long period of time (in this case: total running time of two days). In addition, in contrast to the microtiter plate system, it is a dynamic system because fresh medium (TBY / DGHM water 1:50) is constantly passed over the test specimens. Furthermore, the surfaces fall dry in phases and are then covered with liquid again. This change is very similar to the processes in a toilet, where the ceramic surfaces can also be alternately wetted or dried. The biofilms produced in the reactor correspond to those of microtiter plates in terms of strength and homogeneity. The reactor was first filled with 680 ml of medium, inoculated with the germ mixture described in 1.6.2 and incubated overnight, so that the bacterial flora could establish in the system. As in the real toilet, water flushing was done from a storage vessel by opening a solenoid valve, which in turn was controlled by a timer. The curvature of the toilet bowl was adjusted by clamping the specimens by means of an adapter in the reactor interior. Per Rinse was usually used about 600 mL of water. The first and second day post-incubation were each rinsed 15 times, with the single rinse lasting 20 minutes. The first specimen was taken in the morning on the first day, after there were no or few rinses. The second withdrawal took place in the afternoon after the rinses, overnight the reactor was filled with medium without rinsing. The specimens were dried after removal from the reactor at room temperature and then stained with 6 ml of 0.01% safranine solution for 15 minutes. Thereafter, the dyeing solution was sucked off, then the dyeing solution was sucked off, and the test pieces rinsed to remove the unbound dye from the test specimens. After drying, the dyed test specimens were scanned and evaluated with Corel Draw Paint 9. In order to be able to deduct the background value caused by the surfaces of the substrates used from the measured value, untreated surfaces were additionally scanned.

2. Preparation of formulations with silyl polyalkoxylates: 2.1. Formulation A:

A mixture of the silyl polyalkoxylate from Synthesis Example 1 (4.8% by weight), water (2.4% by weight) and acetic acid (2.4% by weight) in ethanol (ad 100% by weight) was stirred at room temperature for 1 day. Subsequently, 1 part by weight of this mixture was mixed with 20 parts by weight of an agent of the following composition: C _8-10 alkyl polyglycoside 2.5 g lactic acid 2.0 g water ad 100 g

2.2. Formulation B:

By mixing the components, a formulation having the following composition was prepared: Silyl polyalkoxylate from Synthesis Example 1 0.25 g C _8-10 alkyl polyglycoside 2.5 g lactic acid 2.0 g water ad 100 g

2.3. Formulation C:

By mixing the components, a formulation having the following composition was prepared: Silyl polyalkoxylate from Synthesis Example 1 0.25 g C _8-10 alkyl polyglycoside 1.0 g Fatty alcohol ethoxylate 1.0 g formic acid 5.0 g water ad 100 g

2.4. Formulation D1:

A mixture of the silyl polyalkoxylate of Synthesis Example 1 (2.50 wt.%), Tetraethoxysilane (5.00 wt.%), Water (3.75 wt.%), And acetic acid (3.75 wt.%). ) in ethanol (ad 100% by weight) was stirred at room temperature for 1 day. Subsequently, 1 part by weight of this mixture was mixed with 5 parts by weight of an agent of the following composition: C _8-10 alkyl polyglycoside 1.0 g Fatty alcohol ethoxylate 1.0 g formic acid 5.0 g water ad 100 g

2.5. Formulation D2:

A mixture of the silyl polyalkoxylate of Synthesis Example 1 (2.50 wt%), tetraethoxysilane (15.00 wt%), water (3.75 wt%), and acetic acid (3.75 wt%). ) in ethanol (ad 100% by weight) was stirred at room temperature for 1 day. Subsequently, 1 part by weight of this mixture was mixed with 5 parts by weight of an agent of the following composition: C _8-10 alkyl polyglycoside 1.0 g Fatty alcohol ethoxylate 1.0 g formic acid 5.0 g water ad 100 g

2.6. Formulation D3:

A mixture of the silyl polyalkoxylate of Synthesis Example 1 (2.50 wt.%), Tetraethoxysilane (5.00 wt.%), Water (3.75 wt.%), And acetic acid (3.75 wt.%). ) in ethanol (ad 100% by weight) was stirred at room temperature for 1 day. Subsequently, 1 part by weight of this mixture was mixed with 5 parts by weight of an agent of the following composition: C _8-10 alkyl polyglycoside 2.5 g lactic acid 2.0 g water ad 100 g

2.7. Formulation E:

A mixture of the silyl polyalkoxylate from Synthesis Example 1 (2.0 wt%), N- (triethoxysilylpropyl) -O-polyethylene oxide-urethane (4.0 wt%), water (1.0 wt%) and acetic acid (1.0 wt%) in ethanol (ad 100 wt%) was stirred at room temperature for 1 day. Subsequently, 1 part by weight of this mixture was mixed with 10 parts by weight of an agent of the following composition: C _8-10 alkyl polyglycoside 1.0 g Fatty alcohol ethoxylate 1.0 g formic acid 5.0 g water ad 100 g

3. Surface treatment and examination of the surfaces: 3.1. Quick drying effects:

the formulation A prepared in 2.1 was sprayed onto a cleaned tile or glass surface. After brief exposure, the surface was rinsed with running water. This gave a coating which is hydrophilic (water contact angle about 40 °) and at the same time water-wicking (low hysteresis). Because of this water-wicking property, the surface becomes instantly dry when rinsed with water.

3.2. Easy-to-clean test with IKW ballast dirt:

the formulation A prepared in 2.1 was sprayed onto a cleaned black tile or glass surface. After brief exposure, the surface was rinsed with running water. The Easy-to-Clean test on the manufactured surfaces was carried out according to the procedure 1.2, with reference to an untreated tile or glass surface. Under identical conditions, it was found that the IKW ballast dirt on the prepared coating was completely removed, while a white greasy layer remained on the uncoated tile or glass surface.

3.3. Easy-to-clean test with shoe cream dirt:

the formulation A prepared in 2.1 was sprayed onto a cleaned white tile or glass surface. After brief exposure, the surface was rinsed with running water. The Easy-to-Clean test on the manufactured surfaces was carried out according to the procedure 1.3, with reference to an untreated tile or glass surface. Under identical conditions, it was found that the shoe polish stain on the prepared coating was completely removed while leaving a white greasy layer on uncoated tile or glass surfaces.

3.4. Easy-to-clean test with synthetic fecal soiling:

the formulations D1, D2 or E prepared in 2.4, 2.5 and 2.7, respectively, were applied uniformly on cleaned tile surfaces (test flakes from Villeroy & Boch). After ten minutes of exposure, the surface was rinsed with running water. The Easy-to-Clean test on the manufactured surfaces was carried out according to procedure 1.4, with reference to an untreated tile. Under identical conditions it was found that the Fäkalanschmutzungen were removed from the surfaces treated according to the invention in comparison with the reference faster and leaving behind less residues (white fat layers). The results are summarized in the table below. formulation Speed of removal arrears drying time D1 + + + D2 ++ + + e ++ + + ++ much better than reference,
+ better for reference,
- no difference to the reference,

3.5. Anti-scale test:

A cleaned slide (26 cm x 76 cm) was immersed in formulation D3 prepared in 2.6. After brief exposure, the surface was rinsed with running water. This gave a coating on both sides of the slide. The anti-lime test on the prepared surfaces was performed according to protocol 1.5, using as reference an untreated slide. Under identical conditions, it was found that hardly any calcification could be observed on the produced coating, whereas on uncoated surfaces a clear white layer of lime remained. Further quantitative determination by titration revealed a reduction of calcification by using the formulation according to the invention by about 90%.

3.6. Microbiological investigations:

3.6.1. Biorepulsive Performance in the Adhesion Experiment: It was first tested whether the silyl polyalkoxylates used according to the invention and their formulations show a biocidal activity. For this purpose, a mixture of the silyl polyalkoxylate from Synthesis Example 1 (5.0% by weight), water (2.5% by weight), acetic acid (2.5% by weight) and ethanol (ad 100% by weight) was used as sample used for the microbiological investigations described in 1.6.1. The reference was an identical mixture without silyl polyalkoxylate. The results showed that the growth of bacteria was identical for the two samples, ie that the silyl polyalkoxylates in the concentration range of about 0.1 to about 5% have no effects on the growth of S. aureus and P. aeruginosa.

Furthermore, according to the procedure 1.6.1, an adhesion test of bacteria was carried out on surfaces which had been treated with the agents according to the invention. For this purpose, first a mixture of the silyl polyalkoxylate from Synthesis Example 1 (4.8 wt .-%), water (2.4 wt .-%), acetic acid (2.4 wt .-%) in ethanol (ad 100 wt. -%) stirred at room temperature for 1 day. It was then diluted with a surfactant-containing agent (consisting of: C _8-10 -Alkylpolyglykosid 2.5 g, lactic acid 2.0 g, water ad 100 g) until a final concentration of the silyl polyalkoxylate of 0.3 wt. -% was reached (formulation F1). Another formulation (Formulation F2) was prepared in an analogous manner but additionally containing tetraethoxysilane (on a weight basis double the amount of silyl polyalkoxylate). Coverslips (20mm x 20mm) were dipped in the respective formulation for 1 min, followed by rinsing with running water. The reference was an untreated cover glass. The results showed that both inventive formulations against both test organisms used (Staphylococcus aureus and Pseudomonas aeruginosa) compared to the uncoated control a comparably strong and compared to the reference a significant adhesion reduction on glass caused. This is a purely biorepulsive effect, because a biocidal effect could not be detected. The formulations exhibited the best germ repellent action compared with the water germ P. aeruginosa, which was practically used for toilet and bath hygiene, where over 50% of germ reduction could be detected in comparison with the control.

3.6.2. Anti-bioburden properties in the biofilm test:

The tests were carried out according to the procedure 1.6.2. The formulation F1 already described under 3.6.1 was used. The ceramic tiles (25 mm x 25 mm) were cleaned with ethanol, then dried. From about 15 cm distance, the formulation F1 was sprayed onto the cleaned tile, left for 15 minutes and then rinsed with water. After 15 minutes, the procedure was repeated to produce 4x, 5x and 7x sprayed tiles as a result. Tiles were used in each case, which were sprayed only with the surfactant-containing agent (consisting of: C _8-10 -Alkylpolyglykosid 2.5 g, lactic acid 2.0 g, water to 100 g). The tiles were then dried for two hours at 60 ° C and then used for the tests. Tiles treated with Formulation F1 showed a marked visible biofilm reduction compared to control, with 7 fold sprayed tiles the effect was most pronounced. These effects were not based on biocidal effects, according to cultural analyzes.

3.6.3. Practical laboratory test in the toilet reactor:

The tests were carried out according to the procedure 1.6.3. For this, the tiles (25 mm x 25 mm) as in 3.6.2. sprayed with the formulation F1 used there, wherein each tile 6 sprays were used. Tiles were used as controls, which were only used with the also under 3.6.2. described surfactant-containing agents were sprayed. It was found after increasing rinsing steps that a significant reduction of the adhesion of microorganisms to the ceramic could be achieved by the treatment according to the invention. Even after two days of intensive rinsing, the tiles equipped according to the invention had a more than 50% reduction in biofilm formation over the control.

3.7. Comparison of surfaces treated according to the invention and prior art in terms of easy-to-clean properties:

In cleaning areas, hydrophobic, especially superhydrophobic surfaces are often used to achieve easy-to-clean properties. A typical example is hydrophobic, rainwater repellent formulations for car windshields. In this example, a hydrophobic surface with a water contact angle of about 100 °, made of perfluorosilane, was compared with a surface treated according to the invention with regard to its easy-to-clean effects. To this end, two formulations were first prepared: a mixture of the silyl polyalkoxylate of Synthesis Example 1 (0.50 wt%), water (0.25 wt%), acetic acid (0.25 wt%), and ethanol ( ad 100% by weight) was stirred at room temperature for 2 days (formulation G). Another mixture consisting of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (10% by weight), water (7.0% by weight), acetic acid (7.0% by weight) and ethanol (ad 100% by weight). %) was stirred at room temperature for 1 day (Formulation V). The hydrophilic surface coated according to the invention was prepared by immersing a slide in Formulation G and then rinsing with running water. The perfluorosilane coatings were prepared by DipCoating (pull rate 50 mm / min) on wipers from Formulation V followed by rinsing with ethanol and running water. The untreated slide served as reference. The comparisons were made as described in 1.3 (shoe cream test) or by comparing the running behavior of ink (ink test). For this purpose, the respective surface was dipped in black ink and then slowly pulled out. The wettability and the liquid repellency of the surfaces were evaluated. While the ink was well drained from the surfaces treated with formulations G and V, respectively, the surface treated according to the invention had become completely free of traces of ink while treated with formulation V Surface of several scattered small ink droplets stuck, the reference surface was almost completely covered with ink. In the shoe polish test, residual debris on the reference surface as well as on the surface treated with Formulation V was found while the surface treated according to the invention was free of debris. This example shows that the treatment according to the invention not only makes surfaces water-repellent, but at the same time can also effectively prevent the deposition of greasy soil on surfaces.

3.8. Stability study of the prepared formulation:

The formulation prepared in 2.1 was tested in terms of appearance (cloudiness, precipitation, etc.) and its ability to produce the hydrophilic and water repellent surfaces of the present invention under real conditions (room temperature and normal humidity). The test was conducted one month apart. For this purpose, the formulation was applied to tile and glass surfaces as described above, and the resulting surfaces were evaluated for their wetting and dewetting with water. The results showed that the formulation did not change from appearance to effect within the test period (about 1 year), suggesting that it is stable under the conditions indicated.

3.9. Stability studies:

The formulation A prepared in 2.1 was sprayed onto a cleaned tile or glass surface. After brief exposure, the surface was rinsed with running water. This gave a coating which is hydrophilic (water contact angle about 40 °) and at the same time water-wicking (low hysteresis). The treated tile or glass surface was stored under normal conditions (room temperature and normal humidity) and evaluated for watering and dewetting one month apart. The results showed that no change in water wettability and water drainage behavior on the surface could be detected within the test period (about 8 months), indicating that the coating is stable under the conditions indicated.

10.3. Results for different silyl polyalkoxylates:

With the silyl polyalkoxylates from Synthesis Examples 2 and 3, similar results were achieved both in the test with IKW ballast soil (see 1.2.) And in the test with shoe cream soil (see 1.3.) As with the silyl polyalkoxylate from Synthesis Example 1. All these substances were clearly superior to the reference in these tests to very clearly superior.

Claims (15)

1. An agent for the treatment of a hard surface, in particular for the cleaning and/or for the stain-resistant treatment of a hard surface, containing

   a) at least one multi-armed silyl polyalkoxylate of the formula (I)
   
           (H-A)_n-Z-[A-B-Si(OR¹)_r(R²)_3-r]_m     (I)
   
   wherein
   Z represents an (m+n)-valent radical having at least three carbon atoms,
   A is a bivalent polyoxyalkylene radical, wherein the m+n polyoxyalkylene radicals bound to Z can be different from each other, and a radical A is in each case bound to Z via an oxygen atom belonging to Z and to B via an oxygen atom belonging to A or to hydrogen, respectively,
   B represents a chemical bond or a bivalent organic radical having 1 to 50 carbon atoms,
   OR¹ is a hydrolysable group, R¹ and R² are independently of one another a linear or branched alkyl group having 1 to 6 carbon atoms, and r represents an integer of 1 to 3, and
   m is an integer ≥ 1, and n represents 0 or an integer ≥ 1, and m+n has a value of 3 to 100,

   b) at least one surfactant,

   c) water and/or at least one non-aqueous solvent,

   d) optionally further customary ingredients of surface treatment and/or cleaning agents, the ingredients being compatible with the other components of the agent.
2. The agent according to claim 1, characterized in that in formula (I), Z represents an at least trivalent, in particular trivalent to octavalent, acyclic or cyclic hydrocarbon radical having 3 to 12 carbon atoms.
3. The agent according to claim 1 or 2, characterized in that in formula (I), n represents 0, 1 or 2, and m is a number from 3 to 8.
4. The agent according to one of claims 1 to 3, characterized in that in formula (I), A represents -(CHR³-CHR⁴-O)_p-, wherein R³ and R⁴ are independently of one another hydrogen, methyl or ethyl, and p is an integer from 2 to 10,000.
5. The agent according to one of claims 1 to 4, characterized in that in formula (I), B represents a bond or the radical -C(O)-NH-(CH₂)₃-.
6. The agent according to one of claims 1 to 5, characterized in that it contains at least one hydrolysable silicic acid derivative, preferably at least one ester of orthosilicic acid, particularly at least one tetraalkoxysilane and particularly preferably tetraethoxysilane.
7. The agent according to one of claims 1 to 6, characterized in that the surfactant is selected from the group of non-ionic surfactants.
8. The agent according to one of claims 1 to 7, characterized in that the non-aqueous solvent is selected from the group comprising monovalent or multivalent alcohols, alkanolamines, glycol ethers and mixtures thereof.
9. A method for producing an agent according to one of claims 1 to 8, characterized in that the individual components are mixed with each other.
10. A method for treating a hard surface in which the surface is contacted with an agent according to one of claims 1 to 8.
11. The method according to claim 10, characterized in that the hard surface is the surface of ceramics, glass, stainless steel or plastic.
12. Use of an agent according to one of claims 1 to 8 for the protection of a hard surface from soiling and/or for an easier removal of new soiling from the surface.
13. Use of an agent according to one of claims 1 to 8 for rendering a hard surface water-repellent and/or for shortening the drying time of a hard surface after exposure to water.
14. Use of an agent according to one of claims 1 to 8 for rendering a hard surface bacteriostatic.
15. Use of a multi-armed silyl polyalkoxylate of the formula (I)
    
            (H-A)_n-Z-[A-B-Si(OR¹)_r(R²)_3-r]_m     (I)
    
    wherein
    Z represents an (m+n)-valent radical having at least three carbon atoms,
    A is a bivalent polyoxyalkylene radical, wherein the m+n polyoxyalkylene radicals bound to Z can be different from each other, and a radical A is in each case bound to Z via an oxygen atom belonging to Z and to B via an oxygen atom belonging to A or to hydrogen, respectively,
    B represents a chemical bond or a bivalent organic radical having 1 to 50 carbon atoms,
    OR¹ is a hydrolysable group, R¹ and R² are independently of one another a linear or branched alkyl group having 1 to 6 carbon atoms, and r represents an integer of 1 to 3, and
    m is an integer ≥ 1, and n represents 0 or an integer ≥ 1, and m+n has a value of 3 to 100,
    for rendering a hard surface bacteriostatic.