EP2473592A1

EP2473592A1 - Agent for treating hard surfaces

Info

Publication number: EP2473592A1
Application number: EP10743172A
Authority: EP
Inventors: Birgit Veith; Mirko Weide; Nadine Warkotsch; Brigitte Giesen; Stefan Stumpe; Roland Breves
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2009-09-01
Filing date: 2010-08-19
Publication date: 2012-07-11
Anticipated expiration: 2030-08-19
Also published as: US20120156377A1; PL2473592T3; DE102009029060A1; HUE031859T2; WO2011026735A1; EP2473592B1; ES2618862T3

Abstract

The invention relates to agents for treating a hard surface, particularly for cleaning and/or for giving a hard surface a dirt-repellent finish, containing at least two components selected from the group consisting of a multi-armed star-shaped polyalkoxylate, a polyesteramide, and a copolymer made of quaternary ammonium acrylamide and acrylic acid.

Description

"Agents for the treatment of hard surfaces"

The invention relates to agents for treating a hard surface, in particular for cleaning and / or stain-resistant finishing of a hard surface, comprising at least two components selected from the group consisting of a multi-armed star-shaped polyalkoxylate, a polyesteramide and a copolymer of quaternary ammonium acrylamide and acrylic acid.

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, there has been a search for a means to improve not only the cleanliness of detergents, but to prevent or at least aggravate the contamination of surfaces at the outset.

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, there have also been found means by which surfaces can be subsequently and in a manner feasible also in a household equipped so that they less easily pollute or easier to clean at least for a certain period of use (also called "semi-permanent equipment" designated).

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 in an acidic state, for example by adding organic acids such as citric acid or sulfamic acid, so that they have a good activity against lime and urine stone. In general, the cleaning performance is also Good against fecal soiling, although mechanically, ie with the aid of a toilet brush, the toilet surface must be acted upon. This mechanical complexity increases even with older, already dried stains, even moist fecal soiling can stubbornly adhere to ceramic materials.

From the patent application WO 2006/005358 copolymers are known which consist of at least one each of an anionic vinyl monomer, a vinyl monomer having a quaternary ammonium group or a tertiary amino group, and a nonionic hydrophilic vinyl monomer or a polyfunctional vinyl monomer. These copolymers are 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 compositions for providing a hard surface with soil-repelling and / or facilitating the removal of soil and / or reducing 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 object of the invention was therefore to remedy the above-described disadvantages of the prior art, at least partially. In particular, the object was the provision of means for the improvement of the removability of dirt and biofilms of hard surfaces, in particular toilet ceramics, as well as the prevention of new formation of such soiling on such surfaces.

In the published patent applications WO2008 / 068236 and WO2008 / 068235 the use of multi-armed silyl polyalkoxylates is described in this sense, which are suitable for finishing surfaces.

Furthermore, it is known from published patent application WO2009 / 071452 that polyester amides can be used to finish surfaces.

Surprisingly, it has now been found that mixtures of at least two components selected from the group consisting of

a) a multi-armed star-shaped polyalkoxylate,

b) a polyesteramide and

c) a copolymer of quaternary ammonium acrylamide and acrylic acid

have significantly improved properties over the individual components.

The present invention therefore provides a means for treating a hard surface, in particular for cleaning and / or stain-proofing a hard surface and / or for reducing the adhesion of microorganisms to a hard surface, comprising at least two components selected from the group from a) a multi-armed star-shaped polyalkoxylate,

b) a polyesteramide and

c) a copolymer of quaternary ammonium acrylamide and acrylic acid.

In a preferred embodiment, a mixture of a multi-armed silyl polyalkoxylate and a polyesteramide is used here. In a further preferred embodiment, a mixture of a multi-armed silyl polyalkoxylate and a copolymer of qaternärem ammonium acrylamide and acrylic acid is used.

In a further preferred embodiment, a mixture of a polyesteramide and a copolymer of quaternary ammonium acrylamide and acrylic acid is used.

In a further preferred embodiment, a mixture of a multi-arm silyl polyalkoxylate, a polyesteramide and a copolymer of quaternary ammonium acrylamide and acrylic acid is used.

Multi-arm star-shaped polyalkoxylates

Multi-armed star-shaped polyalkoxylates in the context of this invention contain polymer arms which are essentially star-shaped or radially bonded to a central unit and each comprise polyoxyalkylene units, preferably polyoxyethylene units and / or polyoxypropylene units. The number of polymer arms is preferably 3 to 20, in particular 3 to 8. The weight average molecular weight is preferably 500 to 100,000, in particular 1000 to 50,000, and particularly preferably 2,000 to 30,000. Peripherals on the polymer arms may optionally also contain functional groups, such as positively or negatively charged groups or reactive groups. Multi-arm star-shaped polyalkoxylates which can be used according to the invention are described, for example, in the patent specifications WO2003 / 063926, WO2007 / 096056 and DE102008063070.

In a preferred embodiment according to the invention is used as a multi-armed star-shaped polyalkoxylate a SilyI polyalkoxylate or a mixture of several of these compounds, wherein the silyl group is preferably located peripherally on the polymer arms. The SilyI polyalkoxylate contains preferably 0.3 to 10 wt .-%, particularly preferably 0.5 to 5 wt .-% silicon, based on the total weight of the silyl polyalkoxylate. The peripheral silyl groups themselves are preferably bonded to alkoxy and alkyl groups; instead, or in addition, further functional groups may in turn be attached to the SilyI groups.

The multi-arm Silyl polyalkoxylate is preferably a compound of the formula (I)

(HD) _p -Z- [DE-Si (OR) _r (R ² ) ₃ - _r ] o (I) wherein

Z is an (o + p) -valent radical having at least three carbon atoms, D denotes a divalent polyoxyalkylene radical, where the o + p polyoxyalkylene radicals bonded to Z may differ from one another, and wherein one radical D is in each case bonded via an oxygen atom to Z and an oxygen atom belonging to D to E or hydrogen is

E is a chemical compound or a bivalent organic radical having from 1 to 50 carbon atoms,

OR is a hydrolyzable group, R and R ² 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

o is 0 or an integer> 1 and p is 0 or an integer> 1, and o + p has a value of 3 to 100.

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) p is 0, 1 or 2 and o is a number from 3 to 8.

D is preferably selected from poly-C ₂ -C ₄ -alkylene oxides, particularly 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 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) D is - (CHR ³ -CHR ⁴ -O) _q -, where R ³ and R ^{4 are} independently hydrogen, methyl or ethyl and q is an integer of 2 to 10,000 means.

E stands in particular for 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 (0) -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, E is a bond or the radical -C (O) -NH- (CH ₂ ) ₃ -. Preferably, R and R ^{2 are} independently methyl or ethyl, and r is 2 or 3. Examples of -Si (OR) _r (R ² ) 3- _r are dimethylethoxysilyl, dimethylmethoxysilyl, diisopropylethoxysilyl, methyldimethoxysilyl, methyldiethoxysilyl -, Trimethoxysilyl-, triethoxysilyl or tri-t-butoxysilyl radicals, but most preferred are trimethoxysilyl and triethoxysilyl radicals.

It is most preferred when R 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 o + p 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, more preferably 3 to 10, and particularly preferably 3 to 8 oxygen atoms which serve as attachment points for the arms.

In a particular embodiment, o is 0. In the case where o> 0, the ratio o / p 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 composition comprises a mixture of at least two, in particular two to four, different multi-branched 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.

Particularly preferred are mixtures comprising at least two different multi-armed silyl polyalkoxylates of the formula (I) with p = 0, which are selected from the group of the multi-armed silyl polyalkoxylates of the formula (I) with o = 3, o = 6 and o = 8th.

If 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 in particular from 9: 1 to 1: 9.

With regard to the preparation of silyl polyalkoxylates which can be used according to the invention, reference is also made in particular to the published patent applications WO2008 / 068236 and WO2008 / 068235. Suitable polyalkoxylate precursors for preparing silyl polyalkoxylates useful in this invention are For example, under the trade names Voranol 4053, Wanol R420 or Voranol CP 1421 available. Voranol 4053 is 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-armed 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) with an EO / PO ratio of approx. 75/25 and a weight average molecular weight of about 5,000.

The silyl polyalkoxylates which can be used according to the invention are obtainable starting from these polyalkoxylate precursors by reacting the hydroxy end groups of these polyhydric polyalkoxylate precursors with functional silanes which have a functional group which is reactive with the hydroxy end groups of the polyalkoxylate precursor. Examples are tetraalkoxy silanes such as tetramethyl silicate and tetraethyl silicate, (meth) acrylate silanes such as (3-methacryloxypropyl) trimethoxysilane, (methacryloxymethyl) triethoxysilane, (methacryloxymethyl) methyldimethoxysilane and (3-acryloxypropyl) trimethoxysilane, isocyanato-silanes such as isocyanatopropyl) trimethoxysilane, (3-isocyanato-propyl) triethoxysilane, (isocyanatomethyl) methyldimethoxysilane and (isocyanato-methyl) trimethoxysilane, aldehyde-silanes such as triethoxysilylundecanal and triethoxysilylbutyraldehydes, epoxy-silanes such as (3-glycidoxypropyl) -trimethoxysilane, anhydride-silanes such as 3- (triethoxysilyl) propylsuccinic anhydride, halo-silanes such as chloromethyltrimethoxysilane and 3-chloropropyl-methyldimethoxysilane, hydroxy-silanes such as hydroxymethyltriethoxysilane, and tetraethylsilicate (TEOS), which are commercially available from, for example, Wacker Chemie GmbH (Burghausen), Gelest, Inc (Morrisville, USA) or ABCR GmbH & Co. KG (Karlsruhe) or by known methods can be produced. Particular preference is given to using tetraalkoxy-silanes, isocyanato-silanes or anhydride-silanes, but in particular isocyanato-silanes or anhydride-silanes for the preparation of silyl-polyalkoxylates which can be used according to the invention.

The multi-armed, star-shaped polyalkoxylate, and in particular the silyl polyalkoxylate, in the composition according to the invention preferably in an amount of 0.001 to 5 wt .-%, in particular 0.005 to 2 wt .-%, particularly preferably 0.02 to 0.5 wt .-% and especially 0.05 to 0.3 wt .-% used, each based on the total weight of the composition. polyester

The polyesteramides to be used according to the invention preferably contain at least groups of the formula (II)

and / or at least two groups according to formula (III)

in which

Y is H, Ci-20-alkyl, C ₆ -io-aryl,

stands,

B is C ₂ -24 alkylene or C ₆ -24-arylene;

R 1, R 2, R 3, R 4, R _{5 and} R ₆ independently of one another are H, C _1-8 -alkyl or C ₆ -aryl-aryl,

R7 and R8 are independently of one another optionally substituted by heteroatoms Ci_ ₂ 8-

Alkyl or C ₆ -io-aryl,

and m and n independently assume a value of 1 to 4, wherein the value of m and n is preferably 1.

In this case, the polyesteramide is particularly preferably a polymer of the formula (IV)

in which

W for H, C alkyl, C ₆ . ₁₀ -aryl or

stands,

A for OH or

stands,

B is C ₂ -24 alkylene or C ₆ -24-arylene;

X ₂ for H, X

stands,

R _1, R _2, R ₃ , R ₄ , R _{5 and} R ₆ independently of one another are H, C _1-8 -alkyl, C 6-10 -aryl or -CH ₂ -OX ₂ , R 7 and R 8 independently of one another represent optionally substituted by hetero atoms and / or heteroatom-containing groups substituted Ci_ ₂ 8-alkyl or C ₆ -io-aryl.

In a very particularly preferred embodiment, the polyesteramide is a polymer of the formula (V)

in which

A for OH or

stands,

B for C ₂ -24-alkylene or C ₆ -24-arylene is λ for

stands,

X _{2 is} hydrogen, X ·,

stands, R 3 and R ₆ independently of one another are H, C _1-8 -alkyl or C ₆ -aryl-aryl,

R 7 and R 8 independently of one another represent optionally substituted by hetero atoms and / or heteroatom-containing groups substituted Ci_ ₂ 8-alkyl or C ₆ -io-aryl.

In all of the abovementioned embodiments, R _{3 and} R 6 are preferably C 1-4 -alkyl, particularly preferably methyl or ethyl. Furthermore, in all are above embodiments R7 and R8 preferably represents optionally substituted by hetero atoms and / or by heteroatom-containing groups substituted CI_ ₂ -alkyl, more preferably substituted by hetero atoms and / or by heteroatom-containing groups C ₂ -, C ₃ - or C ₆ alkyl.

R 7 and R 8 may in particular be mono- or polysubstituted by groups selected from alcohols, ethers, polyethers, esters, cyanide, carbonate, urethane, urea, amide, imide, amine, imine, imidazole, oxime, sulfide, thiol, thiourea, sulfone , Sulfone oxide, sulfate, phosphate, phosphine, phosphine oxide, silane, silicone, silicate, fluorine, chlorine, bromine or iodine and from groups containing at least one of the aforementioned functional groups.

Examples of radicals R7 and R8 according to the invention are di (m) ethylaminoethyl, di (m) ethylaminopropyl and di (m) ethylaminohexyl and quaternized forms of these radicals; Tri (m) ethylsilylpropyl, tri (m) ethoxysilylpropyl, perfluorooctyl, perfluorooctyl (m) ethyl, (M) ethoxyethyl, (M) ethoxy-2-propyl, maleimidopropyl, maleimidohexyl, octenylsuccinimidohexyl, hexahydrophthalimidohexyl, 2- (benz) imidazolethyl, diphenylphosphinoethyl , Furfuryl, cyanoethyl, cyanopropyl and optionally substituted morpholine, thiomorpholine, piperidine, pyrrolidine, oxazolidine, thiazolidine or piperazine.

In one particularly preferred embodiment of the invention, the radicals R7 and R8 contain independently quaternized amino groups or polyether groups, in particular polyoxyethylene groups, or any mixtures thereof, wherein in the same molecule some radicals R7 and R8 only quaternized amino groups and other radicals R7 and R8 only polyether groups, especially polyoxyethylene , may contain. The polyoxyethylene groups here preferably contain 3 to 20, particularly preferably 5 to 15, in particular 6 to 10 oxyethylene units, where the hydroxy end group of the oxyethylene units can be etherified with a short-chain alcohol, in particular methanol.

In a very particularly preferred embodiment, at least 10%, preferably at least 20% or 30%, of the radicals R 7 and R 8 are tri (m) ethylammoniumalkyl radicals, in particular selected from tri (m) ethylammoniumethyl, tri (m ) ethylammoniumpropyl and tri (m) ethylammoniumhexyl. In a further very particularly preferred embodiment, at least 10%, preferably at least 20% or 30%, of the radicals R7 and R8 are polyoxyethylene groups having 6 to 10, preferably 7, 8 or 9, oxyethylene units which are optionally terminal may be etherified with methyl or ethyl.

In all of the abovementioned embodiments, B may be optionally substituted, preferably by a radical Ci_ ₂ 6-alkyl, more preferably by methyl, octenyl, nonenyl, decenyl, undecenyl or dodecenyl. In this case, B may in particular be a radical optionally substituted by one of the abovementioned radicals selected from among ethylene, ethenylene, 1,3-propylene, 1,2-cyclohexyl, 1,2-phenylene, 1,3-phenylene, 1, 4-phenylene, 2,3-norbornyl, 2,3-norbornen-5-yl and 1,2-cyclohex-4-enyl.

The molecular weight of the polyesteramides according to the invention is preferably from 600 g / mol to 50,000 g / mol, more preferably from 1000 g / mol to 40,000 g / mol, especially from 5000 g / mol to 35,000 g / mol. The polyesteramide according to the invention may be both linear and branched, but it is preferably a branched polymer, more preferably a highly branched polymer.

With regard to polyesteramides which can be used according to the invention and in particular with regard to their preparation, particular reference is also made to the disclosure content of WO 99/16810 and WO 00/58388. Polyesteramides which can be used according to the invention are obtainable, for example, under the trade names Hybrane DAEO 5000 28037 or Hybrane Quat 48 from DSM.

The polyesteramides are preferably present in the compositions according to the invention in an amount of 0.02 to 5.0% by weight, more preferably in an amount of 0.05 to 2.0% by weight, in particular in an amount of 0.1 to 1, 0 wt .-%, especially in an amount of 0, 1 to 0.8 wt .-%, included.

Copolymers of quaternary ammonium acrylamide and acrylic acid

The copolymers of quaternary ammonium acrylamide and acrylic acid are preferably copolymers of diallyldimethylammonium acrylamide and acrylic acid. Such copolymers are available, for example, under the trade name Mirapol Surf from Rhodia. Especially Mirapol Surf-S100, Mirapol Surf-S1 10, Mirapol Surf-S210 or Mirapol Surf-S500 and mixtures thereof can be used according to the invention.

The copolymer inks of the ammonium acrylate and acrylic acid are preferably present in the compositions of the invention in an amount of from 0.1 to 5.0% by weight, more preferably in an amount from 0.2 to 2.0 wt .-%, in particular in an amount of 0.3 to 1, 0 wt .-%, especially in an amount of 0.4 to 0.8 wt .-%, included. For the purposes of the present invention, hard surfaces are in particular surfaces of stone or ceramic materials, hard plastics, glass or metal. It may be hard surfaces such as walls, work surfaces, Fu floors or sanitary items. In particular, the invention relates to surfaces of ceramics, preferably sanitary ceramics, and more particularly of toilet bowls.

Embodiments of the present invention include all of the prior art and / or all suitable administration forms of the agents according to the invention. These include, for example, solid, pulverulent, liquid, gelled or pasty agents, if appropriate also of several phases, compressed or uncompressed; further include, for example: extrudates, granules, tablets or pouches, packed both in large containers and in portions.

The agent according to the invention is preferably a toilet cleaner, a bath cleaner or an all-purpose cleaner. When used as a WC cleaner, an agent according to the invention preferably has a pH of from 1 to 5, in particular from 1 to 3; when used as a bath cleaner preferably has a pH of 1 to 6, in particular from 3 to 5; and when used as a general-purpose cleaner preferably has a pH of 8 to 12, in particular from 9 to 1 1.

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 from contamination and / or facilitates the detachment of contaminants from the surface and / or reduces the adhesion of microorganisms. By "reducing the adhesion" is here preferably to be understood that at least 20, 40 or 60%, more preferably at least 80, 90 or 95% less microorganisms adhere to the hard surface than when using a treatment agent without addition according to the invention polymers to be used Percentages here refer to the difference in the total mass of the adhered material. The microorganisms whose adhesion is reduced are preferably selected from bacteria, fungi, especially molds, viruses, especially bacteriophages, and algae.

The bacteria whose adhesion is reduced are preferably selected from the group consisting of Gram-negative and Gram-positive bacteria, especially pathogenic bacteria selected from Propionibacterium acnes, Staphylococcus aureus, Streptococcus spp., Corynebacterium spp., Micrococcus spp. (especially M. sedentarius), Bacillus anthracis, Neisseria spp., Pseudomonas aeruginosa, P. pseudomallei, Borrelia burgdorferi, Treponema pallidum, Mycobacterium spp., Escherichia coli and Actinomyces spec., Salmonella spec., Actinobacteria (especially Brachybacterium spec), alpha proteobacteria (especially Agrobacterium spec), beta-Proteobacteria (especially Nitrosomonas spec), Aquabacterium spec, Hydrogenophaga, gamma-Proteobacteria, Stenotrophomonas sp., Xanthomonas spec., Haemophilus spec. and all microorganisms described by Paster et al. (J. Bac. 183 (2001) 12, 3770-3783).

Microorganisms that are particularly relevant to biofilm formation, and whose adhesion is particularly preferably reduced, are for example Aeromonads, Agrobacterium, Aquabacterium, Bradyrhizobium japonicum, Burkholderia cepacia, Chromobacterium violaceum, Dermacoccen, Enterobacter agglomerans, Erwinia carotovora, Erwinia chrysanthemi, Escherichia coli, Nitrosomona europaea, Obesumbacterium proteus, Pantoea stewartii, Pseudomonas, Ralstonia solanacearum, Rhizobium, Rhodobacter sphaeroides, Salmonella enterica, Serratia, Vibrio anguillarum, Vibrio fischeri, Xanthomonas, Xenorhabdus nematophilus, Yersinia, Zooshikella gangwhensis, Cythophaga sp. KT0803, Psychrobacter glacinola, Pseudoalteromonas carragenovora, Shewanella baltica and Bacillus subtilis. Some of these biofilm-forming agents are also relevant in the marine field, as they can contribute to the so-called fouling on submerged surfaces.

In particular, the agent preferably prevents the formation of biofilms without having a biocidal activity. It is believed that the effectiveness of the anti-biofilm formation agents of the present invention is due to a bacteriostatic effect of the polymers used, which inhibits the colonization of the surfaces with microorganisms and hampers their adhesion and proliferation 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 compositions of the present invention provide for easier soil removability and reduced tendency to re-soak, and more particularly improve the cleaning performance of hard surface cleaners. As a result, appropriately treated or cleaned surfaces are perceived longer than clean. It has also 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 the polymer formulation 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 colored cleaning formulations are allowed to act on the surface for a longer time, and as a result the drying of the formulation occurs to some extent, the colored film formed is nevertheless easily and completely removed during the next rinsing process.

The use of polymer mixtures according to the invention as additives in surfactant-containing cleaning agents makes it possible not only to clean a 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 to achieve a sufficient cleaning effect, ie. without requiring the use of a conventional cleaning agent.

The polymers of the polymer mixtures according to the invention can be easily and simply formulated with the other constituents of the composition and, in particular, can be incorporated very easily 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.

In a further preferred embodiment of the invention, the agent according to the invention also 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 also include compounds which, in addition to three alkoxy groups, also carry a carbon radical on the silicon atom, for example N- (triethoxysilylpropyl) -O-polyethylene oxide-urethane, Dimethyl-octadecyl (3- (trimethoxysilylpropyl) ammonium chloride, diethylphosphatoethyltriethoxysilane and the trisodium salt of N- (trimethoxysilylpropyl) ethylenediaminetriacetic acid.

The other components contained in the agent according to the invention are to be selected according to their nature and the amount used so that there are no undesired interactions with the polymers to be used according to the invention.

The compositions according to the invention preferably comprise at least one surfactant which is selected from the anionic, nonionic, amphoteric and cationic surfactants and mixtures thereof. With regard to surfactants which can be used according to the invention, reference is made in particular to published patent application WO2008 / 101909.

Suitable anionic surfactants are preferably C ₈ -C ₈ -alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C ₈ -C ₂ 0-alkanesulfonates, C ₈ -C ₈ -monoalkyl sulfates, C ₈ -C ₈ -alkyl polyglycol ether sulfates with 2 to 6 ethylene oxide units (EO) in the ether part and sulfosuccinic acid mono- and di-C ₈ -C ₈ -alkyl esters. Further, also C ₈ -C ₈ a-olefin sulfonates, sulfonated C ₈ -C ₈ fatty acids, especially dodecyl benzene sulfonate, C ₈ -C ₂ 2-carboxylic acid amide ether sulfates, C ₈ -C ₈ -Alkylpolyglykolethercarboxylate, C ₈ -C ₈ - N-acyl taurides, C ₈ -C ₈ -N sarcosinates and C ₈ -C ₈ -alkyl isethionates or mixtures thereof. The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, eg dodecylbenzenesulfonic acid. Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkanesulfonate having about 15 carbon atoms and sodium dioctylsulfosuccinate. Sodium fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates having 12 to 14 C atoms have proven to be particularly suitable.

Suitable nonionic surfactants are particularly C ₈ -C ₈ alcohol polyglycol ethers, ie ethoxylated and / or propoxylated alcohols having 8 to 18 carbon atoms in the alkyl moiety and 2 to 15 ethylene oxide (EO) and / or propylene oxide units (PO), C ₈ - C ₈ -carboxylic acid polyglycol esters having 2 to 15 EO, for example tallow fatty acid + 6-EO esters, ethoxylated fatty acid amides having 12 to 18 C atoms in the fatty acid part and 2 to 8 EO, long-chain amine oxides having 14 to 20 C atoms and long-chain alkylpolyglycosides with 8 to mention 14 carbon atoms in the alkyl moiety and 1 to 3 glycoside units. Examples of such surfactants are oleyl-cetyl-alcohol with 5 EO, nonylphenol with 10 EO, lauric acid diethanolamide, Kokosalkyldimethylaminoxid and Kokosalkylpolyglucosid with an average of 1, 4 glucose units. Particularly preferred are C ₈ _i ₈ fatty alcohol polyglycol ethers with insbesond e re 2 to 8 EO, for example C ₂ fatty alcohol + 7 EO ether, and C ₈ _i ₀ alkyl polyglucosides used with 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 '") (R ^IV ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ¹ " 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 Ci ₀ -C ₈ alkyl dimethylcarboxymethylbetain and Cn-Ci ₇ -Alkylamidopropyl-dimethylcarboxymethylbetain.

Geeig Nete Kationtens id e are ua. The two-part amino acids are of the formula el (R ^VI ) (R ^V ") (R ^VI ") (R ^IX ) N ⁺ X ^" , in which R ^VI to R ^{IX are} four or the same various, 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 agent contains only one or more anionic surfactants as surface-active components, preferably C ₈ -C ₈ -alkyl sulfates and / or C ₈ -C- ₈ - Alkyl ether sulfates, and / or one or more nonionic surfactants, preferably C ₈ _i ₈ - Fettalkoholpolyglykolether having 2 to 8 EO and / or C ₈ _i ₀ -Alkylpolyglucoside 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 to 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 according to 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 ethers, 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. For this purpose, all viscosity regulators used in detergents and cleaners in the state of the art, such as organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch , Dextrins, gelatin, casein), organic modified natural products (carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and the like, core flour ethers), organic fully synthetic thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides) and inorganic thickeners (polysilicic acids, clay minerals such as 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. Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci_ ₄ -alkanols formed ester (INCI acrylates copolymer), which include about the copolymers of methacrylic acid Butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or butyl acrylate and methyl methacrylate (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-io-30-alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci_ ₄ - Alkanols formed, esters (INCI Acrylates / CI O-30 alkyl acrylate crosspolymer) include. 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, eg propoxylated guar, as well as 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, hydroxypropylmethyl or hydroxyethyl methyl cellulose or cellulose acetate. As thickeners, it is also possible to use phyllosilicates. 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, in general, low-boiling, almost water-based moldings may be preferred, while for other purposes, for example, cleaners for toilet bowls, 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. As acids, particularly 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 else sulfamic acid are used. However, it may be preferred if acid is not used as the acid. In addition, however, the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or mixtures thereof can be used. 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, for example, other acids, salts, film formers, antimicrobial agents, builders, corrosion inhibitors, complexing agents, sequestering agents, electrolytes, foam inhibitors, Disintegrationshilfsstoffe, soil release agents or soil repellents, UV absorbents, alkalis, preservatives, bleach , Bleach activators, bleach catalysts, enzymes, enzyme stabilizers, abrasives, polymers 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 contain one or more antimicrobial active ingredients, preferably in an amount of 0.01 to 1 wt.%, In particular of 0.05 to 0.5 wt.%, Particularly preferably of 0.1 to 0.3 wt .-%. Geeig net, for example, antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their Derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides. Furthermore, antimicrobially effective essential oils can be used, which at the same time provide for a scenting of the cleaning agent.

Water-soluble and / or water-insoluble builders can be used in the compositions according to the invention. Water-soluble builders are preferred because they tend to be less likely to leave insoluble residues on hard surfaces. Typical builders which may be present in the context of the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, 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. With regard to further builders and / or cobuilders which can be used according to the invention and their preferred amounts used, reference is made to the publication WO2008 / 101909. 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. With regard to further corrosion inhibitors which can be used according to the invention, in particular also glass corrosion inhibitors, reference is made to the published patent application WO2008 / 101909.

Chelating agents, also known as sequesterants, are agents that can complex and inactivate metal ions to prevent their detrimental effects on the stability or appearance of the agents, such as clouding. On the one hand, it is important to 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 with acidic detergents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents. In some circumstances, a bleach activator may be included in addition to the bleaching agent. With regard to further bleaches which can be used according to the invention and with regard to bleach activators and bleach catalysts which can be used according to the invention and with regard to their preferred amounts used, reference is made to published patent application WO2008 / 101909.

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 their mixtures, 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.

With regard to further enzymes and enzyme stabilizers which can be used according to the invention and their preferred amounts used, reference is made to the published patent application WO2008 / 101909.

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

With regard to inventively preferred sequestering agents, electrolytes, foam inhibitors, Disintegrationshilfsstoffe, "soil release" agents or "soil repellents" and UV absorbents and with respect to their preferred amounts used reference is made to the publication WO2008 / 101909.

A hard surface cleaner according to the invention may also contain one or more propellants (INCI propellants), usually in an amount of from 1 to 80% by weight, preferably from 1 to 5% by weight, in particular from 2 to 10% by weight, more preferably 2.5 to 8% by weight, most preferably 3 to 6% by weight.

With regard to blowing agents which can preferably be used according to the invention, reference is made to published patent application WO2008 / 101909.

A further subject of the present invention is also a product comprising a hard surface cleaner according to the invention and a spray dispenser. In the case of the product, this can be both a single-chamber and a multi-chamber container, in particular a two-chamber container. Preferably, the spray dispenser is a here manually activated spray dispenser, in particular selected from the group comprising aerosol spray dispensers (pressurized gas containers, also known as spray can), even pressure-building spray dispenser, pump spray dispenser and trigger spray dispenser, in particular pump spray dispenser and trigger spray dispenser with a container made of transparent polyethylene or polyethylene terephthalate. Spray dispensers are described in more detail in WO 96/04940 (Procter & Gamble) and the US patents cited therein about spray dispensers, to which reference is made in this regard and the contents of which are hereby incorporated by reference. Trigger spray dispensers and pump sprayers have the advantage over compressed gas tanks that no propellant must be used. By means of suitable particles-passing attachments, nozzles, etc. (so-called "nozzle valves") on the spray dispenser, optionally contained enzyme in this embodiment can optionally also be added to the composition in a form immobilized on particles and thus metered in as a cleaning foam.

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.

A further subject of the present invention is a method for treating a hard surface, in which the surface is brought into contact with a medium according to the invention as described in the preceding text.

This process may be carried out as a stand-alone treatment process for the surface, for example, to provide it with antisoiling properties or one or more of the other properties which effect the agents of the invention in accordance with the teachings of the present invention. The surface is brought into contact with a composition according to the invention.

Preferably, the method according to the invention is carried out so that the agent is distributed over the surface area and advantageously subsequently either after a contact time of 1 second to 20 minutes, preferably 1 to 10 minutes, rinsed or allowed 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 an agent according to the invention for protecting a hard surface against soiling and / or for easier detachment of the surface, wherein it is possible to the soiling (s) is in particular faecal dirt and / or biofilms and / or protein deposits.

In a preferred embodiment of the invention, means according to the invention are provided for the improved removal of faecal dirt and / or biofilms from the surfaces of irrigation toilets and / or for reducing the soiling of such surfaces with faecal 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, on the one hand, it is more favorable if surfaces have hydrophilic properties, since such surfaces can easily be wetted with conventional aqueous-based cleaning liquids and thus facilitate washing-off processes. 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, a calabagging process, which may well look good and may 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, while at the same time "softening" the surface of a film of water, thus avoiding the formation of water droplets and thus the retention of residual soils. and dirt and biofilm deposits, such as, typically, toilet bowls, sinks, bathtubs, and shower cubicles. 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 polymer mixtures used according to the invention is that the colonization by and growth of microorganisms is suppressed on surfaces treated therewith 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 polymer mixtures according to the invention for the bacteriostatic finishing of a hard surface.

According to the invention, particularly preferred bath cleaners comprise

0.5 to 12 wt .-%, preferably 1 to 10 wt .-% and in particular 2 to 8 wt .-% of organic acid and / or a salt of organic acids, preferably selected from formic acid, citric acid, lactic acid and mixtures thereof and Salts of these organic acids;

0, 1 to 5 wt .-%, preferably 0.2 to 4 wt .-% and in particular 0.5 to 3 wt .-% of surfactant (s), preferably nonionic (s) and / or anionic (s) surfactant ( e), particularly preferably nonionic surfactant (s), in particular alkylpolyglycoside (s);

0, 1 to 5 wt .-%, preferably 0.2 to 4 wt .-% and in particular 0.5 to 3 wt .-% thickener; such as

0.01 to 5 wt.%, Preferably 0.02 to 4 wt.% And in particular 0.05 to 3 wt.% Of at least two polymers selected from the group consisting of a multi-arm polyalkoxylate, in particular silyl polyalkoxylate, a polyesteramide and a copolymer of quaternary ammonium acrylamide and acrylic acid;

at a pH of 1 to 6, preferably 3 to 5. Particularly preferred WC cleaners according to the invention

at a pH of 1 to 5, preferably 1 to 3.

All-purpose cleaners particularly preferred according to the invention comprise:

0.05 to 5 wt .-%, preferably 0, 1 to 2 wt .-% and in particular 0.2 to 1 wt .-% of organic acid and / or a salt of organic acids, preferably selected from formic acid, citric acid, lactic acid and mixtures thereof and salts of these organic acids;

0, 1 to 8 wt .-%, preferably 0.2 to 6 wt .-% and in particular 0.5 to 5 wt .-% of surfactant (s), preferably nonionic (s) and / or anionic (s) surfactant ( e), more preferably sulfate (s), sulfonate (s), fatty alcohol ethoxylate (s), alkyl polyglycoside (s) or mixtures thereof;

0, 1 to 8 wt .-%, preferably 0.5 to 6 wt .-% and in particular 1 to 5 wt .-% of fatty acid (s), in particular to Ci2-18 fatty acid (s), and / or a Salt thereof;

0, 1 to 6 wt .-%, preferably 0.2 to 5 wt .-% and in particular 0.5 to 4 wt .-% of an organic solvent, in particular ethanol; such as

at a pH of 8 to 12, preferably 9 to 11. embodiments

Example 1: Synthesis of multi-armed silyl polyalkoxylates a) 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, which is characterized 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 = 0), 1456 (m, -CH ₂ -, -CH ₃ ), 1 107 (s, -COC-), 954 (m, -Si-O-). 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 obtained -terminated polyalkoxylate has a molecular weight of 13500. b) 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. c) 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 was slowly added 20.9 mg (0.01%) of dibutyltindilaurate and 30.3 g (1.0 equivalents) of (3-isocyanatopropyl) triethoxysilane. As an alternative to the dibutyltin dilaureate, it is also possible to use DABCO (1,4-diazabicyclo [2.2.2] octane) as the catalyst. The reaction mixture was further stirred under blanketing gas at room temperature for 2 days until the NCO band in the IR measurement had disappeared. The product, 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, was obtained as a colorless viscous liquid (Hydrostellan S100).

Example 2: WC reactor test with individual polymers and polymer mixtures

The preventive effect with regard to the biofilm reduction of different polymers as a function of their concentration in a commercially available WC cleaner was investigated in an application-oriented dynamic test system. The preventive effect of the individual polymers was also compared with the effect of mixtures of these polymers.

The so-called toilet reactor replaces the flushing cycles of a toilet and thus the periodic wetting and drying of ceramic surfaces.

This system makes it possible to examine adhesion and biofilm formation in a test system on several different surfaces over a defined period of 48 h. Instead of using water in a real toilet, fresh medium (TBY 1:50) is passed over the tiles in this model.

The reactor is first filled with 680 ml of medium and inoculated with a germ mixture consisting of Dermacoccus nishinomiyaensis DSMZ 20448, Bradyrhizobium japonicum DSMZ 1 982 and Xanthomonas campestris DSMZ 1526, which forms a stable biofilm in aqueous environments. The incubation takes place overnight, so that the germ flora can establish itself in the system.

The "water scavenging" takes place semi-automatically controlled by a pump and the time-delayed opening of a solenoid valve. Per wash, 680 ml of medium are used. The first and second days after incubation are rinsed 15 times each, with a single rinse lasting 20 minutes.

The tiles are removed after a total of 30 rinses at the end of the reactor run.

The horizontally placed tiles were submerged in 15-20 ml of the polymer solutions with defined concentrations for three minutes before being clamped in the reactor, then rinsed briefly with water and dried at 60 ° C. for two hours. The solvent used was a detergent formulation.

The ceramic tiles are 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 is filtered off, with H ₂ O _b idest unbound dye removed from the glasses and the colored tiles are dried. The stained surfaces are scanned and evaluated with Corel Draw Paint 9. The background value (caused by the ceramic) is measured from untreated surfaces and from the color intensity of the stained Tiles removed. As a reference, the intensity of the biofilm on tiles, which were previously treated only with the cleaner without polymer addition, set to 100% biofilm formation and 0% biofilm reduction.

Table 1: Biofilm reducing effect of individual polymers and combinations of polymers formulated in a WC cleaner

The data in% by weight relate in each case to the amount of active substance contained.

DSM Hybrane DAEO 5000 is a branched polyester amide quaternized

Contains ammonium groups and long-chain polyoxyethylene groups.

Surprisingly, it turned out that combinations of the polymers show a significantly higher preventive effect on biofilm formation than the individual polymers in the same amount used. It can therefore be assumed that there is a synergistic effect. When using polymer mixtures thus the same overall effect can be achieved with a relatively small total amount of polymers. Example 3: Verification of the biocidal properties of the polymers

The biocidal properties of the individual polymers were investigated in accordance with DIN standard EN 1276 on Staphylococcus aureus, Enterococcus hirae, Pseudomonas aeruginosa and Escherichia coli.

The biocidal properties were then compared with the biorepulsive properties of the polymers, which were determined as described in Example 2.

As a reference for this experiment tiles were used, which were treated in advance with water to determine a biofilm reduction by the toilet cleaner itself.

With regard to the biorepulsive activity of the WC-Reinger showed with the addition of the polymers HydroStellan, DSM Hybrane Quat and DSM Hybrane 5000 each by about 70% increased biofilm reduction. The biocidal effect of the various detergent formulations, however, remained largely intact. Both the 80% cleaner / polymer formulations under 'clean' and 'dirty' conditions, and the 10% formulations under 'clean' conditions showed the same biocidal effect as the toilet cleaner without polymer.

Table 2: Comparison of biocidal (EN1276) and biorepulsive activity (biofilm reduction) of various polymers formulated in WC-Jumbo

EN 1276 biofilm

Concentration 80% reduction

Experimental condition clean dirty [%]

WC cleaner + S. aureus 2,97E + 05 2,97E + 05 71 ± 5

0.25% by weight E. hirae 1.32E + 05 1.32E + 05

Hydrostellan P. aeruginosa 2.73E + 05 2.73E + 05

E. coli 1 .73E + 05 1.73E + 05

WC cleaner + S. aureus 2,97E + 05 2,97E + 05 66 ± 7

1% by weight AS DSM E. hirae 1.32E + 05 1.32E + 05

Hybrane DAEO Quat P. aeruginosa 2.73E + 05 2.73E + 05

E. coli 1.73E + 05 1.73E + 05

WC cleaner + S. aureus 2,97E + 05 2,97E + 05 68 ± 4

1% by weight AS DSM E. hirae 1.32E + 05 1.32E + 05

Hybrane DAEO P. aeruginosa 2.73E + 05 2.73E + 05

5000 E. coli 1.73E + 05 1.73E + 05

WC cleaner S. aureus 2,97E + 05 2,97E + 05 -6 ± 1

(Control) E. hirae 1.32E + 05 1.32E + 05

P. aeruginosa 2.73E + 05 2.73E + 05

E. coli 1 .73E + 05 1.73E + 05 Example 4: Formulations a) WC cleaner formulations

The data in the table are in wt .-% of active substance based on the total composition. The pH of the compositions was adjusted to 2.2. The viscosity of the compositions at 20 ° C was 550 mPaxs (Brookfield LV-DV II +, spindle 31, 20 rpm). b) bath cleaner formulations

The data in the table are in wt .-% of active substance based on the total composition. The pH of the compositions was adjusted to 3.9. The Viscosity of the compositions was less than 10 mPaxs at 20 ° C (Brookfield LV-DV II +, spindle 31, 20 rpm). c) All-purpose cleaner

The data in the table are in wt .-% of active substance based on total composition. The pH of the compositions was adjusted to 10.0.

Claims

claims:

Claims 1. A hard surface treatment agent, in particular for cleaning and / or stain-proofing a hard surface, and / or for reducing adhesion of microorganisms to a hard surface, comprising at least two components selected from the group consisting of

a) a multi-armed star-shaped polyalkoxylate,

b) a polyesteramide and

c) a copolymer of quaternary ammonium acrylamide and acrylic acid.

2. Composition according to claim 1, characterized in that it is the multi-arm star-shaped polyalkoxylate is a silyl polyalkoxylate, in particular a compound of formula (I)

(HD) _{p is} -Z- [DE-Si (OR) _r (R ² ) ₃ - _r ] o (I) wherein

Z is an (o + p) -valent radical having at least three carbon atoms, preferably an at least trihydric, in particular tri-to octahydric, acyclic or cyclic hydrocarbon radical having 3 to 12 carbon atoms,

D denotes a divalent polyoxyalkylene radical, where the o + p polyoxyalkylene radicals bonded to Z can differ from one another, and where one D radical is in each case linked to Z via an oxygen atom belonging to Z and one to D belongs to E or hydrogen, and wherein D preferably represents - (CHR ³ -CHR ⁴ -O) q-, where R ³ and R ^4, independently of one another, denote hydrogen, methyl or ethyl and q denotes an integer from 2 to 10 000,

E is a chemical bond or a divalent organic radical having 1 to 50 carbon atoms, preferably a covalent bond or the radical -C (O) -NH- (CH ₂ ) ₃ -,

o is 0 or an integer> 1 and p is 0 or an integer> 1, and o + p has a value of 3 to 100, where o is preferably 0, 1 or 2 and p is a number from 3 to 8 means.

3. Composition according to one of claims 1 to 2, characterized in that the silyl polyalkoxylate has a weight average molecular weight (weight average) of 500 to 100,000.

4. Composition according to one of claims 1 to 3, characterized in that the polyesteramide at least two groups of the formula (II)

contains, where

Y is H, C 1 cycloalkyl, C,

stands,

B is C ₂ -24 alkylene or C ₆ -24-arylene;

R1, R2, R3, R4, R5 and R6 are independently H, CI_ ₈ - (cyclo) alkyl or C _6- stand io aryl,

R 7 and R 8 are each independently of one another optionally substituted by hetero atoms Ci-28-alkyl or C ₆ -io-aryl,

and m and n independently assume a value of 1 to 4.

Agent according to one of claims 1 to 4, characterized in that the polyesteramide at least two groups of formula (III)

contains, where

Y is H, C 1 cycloalkyl, C,

stands,

B is C ₂ -24 alkylene or C ₆ -24-arylene;

R7 represents optionally substituted by hetero atoms Ci_ ₂ 8-alkyl or C ₆ -io-aryl, and m and n independently of one another assume a value of 1 to 4.

Agent according to one of Claims 1 to 5, characterized in that the polyesteramide is a polymer of the formula (IV) OO R1 R2 R3 H

V (IV)

is, where

W is H, d-20 alkyl, C ₆ aryl, or -i ₀

stands,

A for OH or

stands,

B is C ₂ -24 alkylene or C ₆ -24-arylene;

stands, or

_stands

R1, R2, R3, R4, R5 and R6 are independently H, Ci _-8 alkyl, C ₆ -io-aryl, or - CH ₂ -OX ₂ are provided,

R7 and R8 independently of one another are optionally substituted by hetero atoms Ci-28 alkyl or C ₆ -io-aryl.

7. Composition according to one of claims 1 to 6, characterized in that it is in the polyester amide to a polymer according to formula (V)

is, where

A for OH or

stands,

B is C ₂ -24 alkylene or C ₆ -24-arylene;

stands,

X _{2 is} hydrogen, X ·,

R7

R8

O O stands,

R 3 and R ₆ independently of one another are H, C _1-8 -alkyl or C ₆ -aryl-aryl,

8. Composition according to one of claims 4 to 7, characterized in that R7 and R8 are independently mono- or polysubstituted by groups selected from alcohols, ethers, polyethers, esters, cyanide, carbonate, urethane, urea, amide, imide, Amine, imine, imidazole, oxime, sulfide, thiol, thiourea, sulfone, sulfone oxide, sulfate, phosphate, phosphine, phosphine oxide, silane, silicone, silicate, fluorine, chlorine, bromine or iodine and from groups the at least one of the aforementioned functional groups contain.

9. Composition according to one of claims 4 to 8, characterized in that R7 and R8 independently of one another quaternized amino groups or polyether groups, in particular polyoxyethylene groups, or any mixtures thereof and in particular selected from tri (m) ethylammoniumalkyl radicals and optionally etherified polyoxyethylene groups 6 to 10 oxyethylene units.

10. Composition according to one of claims 1 to 9, characterized in that the polyester has a molecular weight of 600 g / mol to 50,000 g / mol.

1 1. A composition according to any one of claims 1 to 10, characterized in that it is the quaternary ammonium acrylamide of the copolymer of quaternary ammonium acrylamide and acrylic acid is a Diallyldimethylammoniumacrylamid.

12. Composition according to one of claims 1 to 1 1, characterized in that it contains at least one surfactant.

13. Composition according to one of claims 1 to 12, characterized in that it has a pH of less than 9, in particular from 0 to 6, preferably from 1 to 5 and particularly preferably from 2 to 4.

14. Composition according to one of claims 1 to 13, characterized in that it is a cleaning agent, preferably a cleaning agent for ceramics, especially for sanitary ware.

15. A method for treating a hard surface, wherein the surface is brought into contact with a composition according to any one of claims 1 to 22, wherein the agent is distributed over the surface area and either after a contact time of 1 second to 20 minutes, preferably 1 to 10 minutes, rinsed or allowed to dry.

16. The method according to claim 15, characterized in that it is the surface of ceramic, glass, stainless steel or plastic in the hard surface.

17. Use of a composition according to any one of claims 1 to 14 for protecting a hard surface against stains and / or for easier removal of Neuanschmutzungen from the surface and / or to reduce the adhesion of microorganisms to the hard surface, wherein the soiling (s) is in particular faecal dirt and / or biofilms and / or protein deposits.

18. Use of a composition according to any one of claims 1 to 14 for the water-repellent finish of a hard surface and / or for shortening the drying time of a hard surface after exposure to water and / or for bacteriostatic finishing a hard surface.