EP3237592A1

EP3237592A1 - Polymers for cleaners with surface-modifying effect

Info

Publication number: EP3237592A1
Application number: EP15816459.0A
Authority: EP
Inventors: Stefan Karsten; Marion Erbe; Martina Seiler; Doris Dahlmann; Michael Wolpers; Thomas Möller
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2014-12-23
Filing date: 2015-12-18
Publication date: 2017-11-01
Also published as: DE102014226909A1; WO2016102389A1

Abstract

The present invention relates to a cleaning material for hard surfaces, especially ceramic surfaces in bathroom and kitchen, comprising - based on the total weight of the material - 0.2 to 10 wt% of an acidic aqueous composition comprising: at least one oxoacid of phosphorus and at least 0.2 wt%, calculated on the basis of elemental silicon and based on the total weight of the acidic aqueous composition, of at least one organosilane compound having at least one hydrolysable substituent and 1 - 3 non-hydrolysable substituents, at least one of the non-hydrolysable substituents having at least one amino group, and the absolute number of substituents on each silicon atom of an organosilane compound being 4, and also to the use of this cleaning material for the cleaning and/or surface modification of hard surfaces.

Description

Polymers for surface-modifying cleaners

The present invention relates to a hard surface cleaner, especially bathroom and kitchen ceramics containing surface modifying polymers based on organosilanes, and to the use of this hard surface cleaning detergent.

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 ceramics are mentioned here. Surfactant-containing agents are usually used for cleaning such surfaces, the cleaning action of which is based primarily on the ability of surfactants to solubilize dirt particles and thus render them removable or rinsable from the surface. Depending on the nature of the surface and the nature of the dirt, the dirt on the surface, however, can adhere strongly. This is especially true when the soiling remains on the surface for a long time and the adhesion is further enhanced by aging processes. As a result, the dirt can be very difficult to remove and thus cause a great deal of cleaning. Limescale, which forms after drying detergent application due to lack of wetting agent from dried water droplets on the surfaces, make already cleaned surfaces look dirty and gray again. Such staining and streaking is in principle observable on hard surfaces of all kinds, but especially on glass and ceramic surfaces, and is brought into contact by the consumer with a reduced cleaning performance of the cleaning agent used.

For this reason, an intensive search is being made for agents which not only improve the cleaning power of cleaning agents, but also prevent or at least hinder limescale deposition and redeposition of surfaces as they are approached.

The object of the present invention was therefore to provide liquid detergents which, with consistently good or even improved cleaning performance, bring about an improvement in the dirt-repellent properties and in the water drainage on the surfaces cleaned with them.

It has now been found that the use of organosilane-based polymeric compounds leads to a performance improvement of cleaning agents in the treatment of hard surfaces.

A first subject of the present invention is therefore a hard surface cleaner, in particular ceramic surfaces, containing, based on the total weight of the Cleaning agent, 0.2 to 10 wt .-%, preferably 0.2 to 5 wt .-%, of an acidic aqueous composition comprising:

(i) at least one oxo acid of the phosphorus and

(ii) at least 0.2% by weight, calculated based on the element silicon and based on the total weight of the acidic aqueous composition, of at least one organosilane compound having at least one hydrolyzable substituent and 1-3 non-hydrolyzable substituents, at least one of non-hydrolyzable substituent at least one amino group, and wherein the absolute number of substituents on each silicon atom of an organosilane compound is 4.

Likewise provided by the present invention is the use of a surface cleaning agent according to the invention for cleaning and / or surface modification of hard surfaces, in particular of ceramic surfaces, for reducing limescale and improving the dirt-repellent properties of the surface.

Another aspect of the present invention is a method of cleaning hard surfaces using the detergents of the present invention.

Finally, a last aspect of the present invention relates to the use of an acidic aqueous composition comprising:

(i) at least one oxo acid of the phosphorus; and

(ii) at least 0.2% by weight, calculated on the silicon element and the acidic aqueous composition, of at least one organosilane compound having at least one hydrolyzable substituent and 1-3 non-hydrolyzable substituents, at least one of the nonhydrolyzable substituents has at least one amino group, and wherein the absolute number of substituents on each silicon atom of an organosilane compound 4,

to improve the dirt-repellent effect of a hard surface.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. Numerical ranges indicated in the format "from x to y" include the above values. If several preferred numerical ranges are in this Format, it is self-evident that all areas that result from the combination of the various endpoints are also captured.

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. In particular, the oxo alcohols or their derivatives, which are obtainable, for example, by the RoELEN's oxo synthesis, can also be used correspondingly.

"At least one" as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With respect to an ingredient, the indication refers to the kind of the ingredient and not to the absolute number of molecules. "At least one acid" thus means, for example, at least one type of acid, ie that one type of acid or a mixture of several different acids can be used. The term, together with weights, refers to all compounds of the type indicated which are included in the composition / mixture, i. that the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.

All percentages given in connection with the compositions described herein, unless explicitly stated otherwise, relate to% by weight, in each case based on the mixture in question.

Whenever alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.

Substances which also serve as ingredients of cosmetic products are referred to below, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed only after Linne in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names can be found in the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), published by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1 101 17th Street, NW, Suite 300, Washington, DC 20036, USA, and contains more than 9,000 INCI names, as well as references to more than 37,000 trade names and technical names, including its distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, such as polymer ethers, and one or more functions, such as surfactants-cleansing agents, which are further explained and discussed below possibly also referred to. The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.

For the purposes of the invention, cleaning compositions or cleaning agents include, but are not limited to:

Means for cleaning and / or disinfecting hard surfaces, such as all-purpose cleaners, floor cleaners, glass cleaners, kitchen cleaners, bath and sanitary cleaners, toilet cleaners, disinfectant cleaners.

Formulation types of cleansers include, but are not limited to: cleansing and disinfectant concentrates, liquid cleaners or disinfectants, sprays for cleansing or disinfecting, emulsions and gels. A concentrate is usually an aqueous preparation with an increased active substance content, which is adjusted by dilution (usually with water) to the concentration corresponding to the respective application. Concentrates may preferably contain additional antioxidants or stabilizers.

The surfaces to be treated include, but are not limited to, glass, plastics, metals, steel, wood, stone materials, ceramics, cement, coatings, and composites, particularly ceramics.

In various embodiments of the present invention, the aqueous acidic composition is used in an amount of from 0.2 to 10% by weight, preferably from 0.2 to 5% by weight, based on the total weight of the cleaning agent.

If concentrates of the cleaning composition according to the invention are present, they are diluted prior to use such that when applied to the surface the composition according to the invention is present in the abovementioned final concentration.

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, in particular liquid, gel or pasty agents, packed both in large containers and in portions.

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. 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.

The use of the compositions according to the invention as additives for hard surface cleaners makes it possible, in a single work step, not only to clean a surface, but at the same time provide it with dirt-repellent properties. In this way, for example, a calcification is prevented. The treated surfaces remain 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 time-saving and / or milder detergents are needed.

For the purposes of the present invention, an "organosilane" comprises a tetravalent silicon atom having four polar, covalently bonded substituents, at least one of these bonds being a covalent Si-C bond Such a covalent Si-C bond always carries a nonhydrolyzable substituent In the context of the present invention, therefore, a hydrolyzable substituent is by definition not linked via such a covalent Si-C bond to the silicon atom of the organosilane compound.

The person skilled in the art knows that organosilanes dissolved in water can undergo multiple hydrolysis and self-condensation reactions and are thus in an equilibrium between hydrolyzed and condensed form.

The acidic compositions used in hard surface cleaning compositions according to the invention comprise at least one oxoacid of phosphorus (i) and at least 0.2% by weight, calculated on the silicon element and the aqueous composition, of at least one organosilane compound (ii) having at least a hydrolyzable substituent and 1-3 non-hydrolyzable substituents, wherein at least one of the nonhydrolyzable substituents has at least one amino group, and wherein the absolute number of substituents on each silicon atom of an organosilane compound is 4.

The aqueous acidic composition according to the present invention may further contain other organosilane compounds which do not correspond to the organosilanes (ii). However, it is preferred that the absolute amount of organosilanes, calculated on the silicon element, in the acidic aqueous compositions of the invention is not more than 15% by weight, based on the total weight of the composition. The proportion of organosilanes (ii) in the total amount of organosilanes in the aqueous acid Composition calculated in each case based on the element silicon, is at least 30 mol%, preferably at least 40 mol%.

A hard surface cleaning agent in the sense of the present invention preferably contains organosilanes (ii) selected from the group consisting of compounds of the formula (1):

(H2N - [(CH 2) m NH] n (CH 2) p) y -Si-X (4-y) (1) wherein each X is a hydrolyzable substituent independently selected from the group consisting of alkoxy groups with not more than 4, preferably not more than 2 carbon atoms;

wherein m and p are each independently an integer in the range of 1-4;

wherein n is an integer in the range of 0-8, preferably in the range of 0-3; and

where y is an integer in the range of 1 to 3, preferably 1.

Particularly preferred in this context are compounds of the formula (1) selected from the group consisting of monoaminoalkylalkoxysilanes, such as, for example, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethyltrimethoxysilane,

Aminoethyltriethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane,

Aminopropylmethyldimethoxysilane and aminopropylmethyldiethoxysilane; Diaminoalkylalkoxysilanes such as aminoethylaminopropyltrimethoxysilane, aminoethylaminopropyltriethoxysilane; and so-called triaminoalkylalkoxysilanes, such as

Aminoethylaminoethylaminopropyltrimethoxysilane (trimethoxysilylpropyldiethylenetriamine) or aminoethylaminoethylaminopropyltriethoxysilane (triethoxysilylpropyldiethylenetriamine).

Furthermore, in preferred embodiments of the cleaning agents according to the invention in addition to the organosilanes (ii) in the aqueous composition contain other, other organosilane compounds which are preferably selected from organosilane compounds having at least one hydrolyzable substituent and 1 to 3 non-hydrolyzable substituents, wherein at least one of non-hydrolyzable substituent carries a hydroxyl or oxirane (epoxy) group. Particularly preferred are those other organosilane compounds which are selected from the group consisting of (3-glycidyloxypropyl) trimethoxysilane and / or (3-glycidyloxypropyl) triethoxysilane. The proportion of such organosilanes having at least one hydroxyl or oxirane group, each calculated based on the element silicon, based on the total amount of organosilanes in the composition is at least 10 mol%, preferably at least 20 mol%.

In preferred embodiments, the molar ratio of the amount of organosilanes, calculated based on the element silicon, to the amount of oxo acids of the phosphor, calculated based on the element phosphorus, in the range of 1-5, preferably in the range of 2-4.

Oxo acids of phosphorus (i) can be selected, for example, from the group consisting of: organophosphoric acids, phosphonic acids and / or phosphoric acids, the proportion of organophosphoric acids, based on the total amount of oxo acids of the phosphorus, being at least 10 mol%, preferably at least 40 mol%, particularly preferably at least 80 mol%, calculated based on the element phosphorus

The organophosphoric acids contained in the detergents according to the invention may, in various embodiments of the invention, have at least two phosphonic acid groups which are linked to one another via an alkylene, oxyalkylene or aminoalkylene group, where the alkylene, oxyalkylene or aminoalkylene groups may be substituted by amino, hydroxyl, , Aminoalkyl and / or hydroxyalkyl groups each having not more than 4 carbon atoms. The shortest alkylene bridge linking two phosphonic acid groups preferably has not more than 4 carbon atoms. Examples of such organophosphoric acids are etidronic acid (1-hydroxyethylidenediphosphonic acid) and alendronic acid (4-amino-1-hydroxypropylsidene).

The organophosphorus acids selected from the group of α-aminophosphonic acids of the formula (2) are particularly preferred:

wherein n is an integer of at least 1 but not more than 5, preferably not more than 3; wherein m is an integer of at least 1 but not more than 5;

wherein the substituent Y is selected from the group consisting of -P (= O) (OX) 2, -OH, -NH 2, preferably selected from the group consisting of -P (= O) (OX) 2 and -OH;

wherein the radicals X are independently selected from the group consisting of

Hydrogen, aliphatic groups of not more than 4 carbon atoms, alkali metal cations,

Ammonium or quaternary ammonium cations;

and wherein at least one of the radicals X is hydrogen.

In a particularly preferred embodiment, the organophosphoric acids are selected from the group of α-aminophosphonic acids according to formula (3):

wherein n is an integer of at least 1 but not more than 5, preferably not more than 3; wherein the radicals X are independently selected from the group consisting of hydrogen, aliphatic groups having not more than 4 carbon atoms, alkali metal cations, ammonium or quaternary ammonium cations;

and wherein at least one of the radicals X is hydrogen.

In particularly preferred embodiments of the present invention, the preferred α-aminophosphonic acids are nitrilotris (methylenephosphonic acid),

Ethylenediaminetetrakis (methylenephosphonic acid) and / or diethylenetriaminepentakis (methylenephosphonic acid) and their alkali metal, ammonium or quaternary ammonium salts.

It is preferable that the acidic character of the aqueous composition is caused by the oxo acids of the phosphor. The amount of acids having a pKA value for the first deprotonation step of more than 3.5 is therefore preferably less than 0.05% by weight, based on the total weight of the aqueous composition. In particularly preferred embodiments, the acidic aqueous composition contains less than 0.05% by weight, in particular less than 0.01% by weight, of other acids.

Furthermore, in a preferred embodiment, formic acids and / or other, related carboxylic acids, for example acetic acid, may additionally be used.

The pH of the aqueous acidic composition used according to the invention is in the range from 1 to 6, preferably in the range from 2.0 to 5.5.

The aqueous, acidic composition may be sol-gel systems. The acidic, aqueous solutions of the above-described organosilanes are the starting materials, which then form sol particles by the hydrolysis and polycondensation of the organosilanes and then gel. The resulting in the hydrolysis alcohols can be removed, for example, by vacuum distillation from the system.

In addition, the compositions according to the invention may contain customary other constituents of cleaning agents, in particular cleaning agents for the treatment of hard surfaces, as far as they do not interact in an undesired manner with the substances used according to the invention. As such other ingredients are, for example, surfactants, solvents, thickeners, 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 absorbers , Alkalis, preservatives, bleaches, bleach activators, bleach catalysts, enzymes, enzyme stabilizers, abrasives, polymers and fragrances and dyes. Overall, the compositions should preferably contain not more than 30% by weight of other ingredients, preferably from 0.01 to 30% by weight, in particular from 0.2 to 15% by weight, based on the total weight of the respective composition.

The other components contained in the cleaning agent according to the invention are to be selected according to their type and the amount used so that there are no undesired interactions with the organosilane compounds 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 International Publication WO2008 / 101909.

Suitable anionic surfactants are preferably Cs-ds-alkylbenzenesulfonates, in particular having about 12 C atoms in the alkyl moiety, C8-C20-alkanesulfonates, Cs-ds-monoalkyl sulfates, Cs-ds-Alkylpolyglykolethersulfate with 2 to 6 ethylene oxide units (EO) in the ether part and Sulfosuccinic acid mono- and di-Cs-ds-alkyl esters. Also suitable are Cs-ds-α-olefinsulfonates, sulfonated Cs-ds-fatty acids, in particular dodecylbenzenesulfonate, C8-C22-carboxylic acid amide ether sulfates, Cs-ds-alkylpolyglycol ether carboxylates, Cs-ds-N-acyltaurides, Cs-Ci8-N-sarcosinates and Cs -ds-Alkylisethionate or mixtures thereof are used. The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, eg Dodecylbenzenesulfonic. Examples of such surfactants are sodium cocoalkyl sulfate, sodium sec-alkanesulfonate having about 15 carbon atoms and sodium dioctylsulfosuccinate. Sodium fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates having 12 to 14 C atoms have proven to be particularly suitable.

Particularly suitable nonionic surfactants are Cs-ds-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), Cs-ds-carboxylic acid polyglycol esters with 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 Cs-ds-fatty alcohol polyglycol ethers having in particular 2 to 8 EO, for example C 12 -fatty alcohol + 7-EO-ethers, and Cs-to-alkylpolyglucosides 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 "') (R ^IV ) (R ^v ) N ⁺ CH 2 COO -, in which R" 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 Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-Alkylamidopropyldimethylcarboxymethylbetain.

Suitable cationic surfactants include u. the quaternary ammonium compounds of the formula (R ^VI ) (R ^V ") (R ^VI ") (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, didecyldimethylammonium chloride, Alkylbenzyldidecylammoniumchlorid and mixtures thereof.

However, in a preferred embodiment, the surfactant component comprises only one or more anionic surfactants, preferably Cs-Os-alkyl sulfates and / or Cs-Os-alkyl ether sulfates, and / or one or more nonionic surfactants, preferably Cs-ds fatty alcohol polyglycol ethers having 2 to 8 EO and / or Cs-Oo-alkylpolyglucosides 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 3% by weight. -%, in each case based on the total weight of the agent.

The compositions according to the invention contain water or else additionally at least one nonaqueous solvent. As non-aqueous solvents are preferably those Solvents which are miscible in any proportions 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 cleaning agent according to the invention contains a thickener. In principle, all viscosity regulators used in detergents and cleaning agents 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 esters (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 from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with CW alkanols (INCI Acrylates / Oo-30 Alkyl Acrylate Crosspolymer). 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, hydroxypropylmethyl or hydroxyethylmethylcellulose 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, generally low, nearly 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, preferably a pH of from 1 to 6, particularly preferably from 2 to 5.5.

In a further, particularly preferred embodiment, the cleaning 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.

The compositions according to the invention may contain film formers which may contribute to a better wetting of the surface. For this purpose, all in the prior art in washing and cleaning agents used film-forming polymers into consideration. 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 .-%. Suitable examples are antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and derivatives thereof such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butylcarbamate, 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 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. 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.

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 deal with many Ingredients incompatible calcium and magnesium ions of the water hardness to complex. 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. With regard to further bleaches which can be used according to the invention and with regard to Reference is made to published patent application WO2008 / 101909, which relates to bleach activators and bleach catalysts which can be used according to the invention and to preferred amounts used.

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

In addition, enzyme stabilizers may be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention from damage such as, for example, inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage. Suitable enzyme stabilizers, in each case depending on the enzyme used, are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, for example substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of said acids; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known in the art. Preference is given to using combinations of stabilizers, for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

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 against light 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. The product may be both a single-chamber and a multi-chamber container, in particular a two-chamber container. The spray dispenser is preferably a manually activated spray dispenser, in particular selected from the group consisting of aerosol spray dispensers (also known as spray can), pressure-building spray dispensers, pump spray dispensers and trigger spray dispensers, in particular pump spray dispensers and trigger spray dispensers with a transparent polyethylene or polyethylene terephthalate container. 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 atomizers 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.

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.

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 method according to the invention serves to treat a surface of ceramic, glass, stainless steel or plastic, very particularly preferably ceramic.

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.

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 can be easily wetted with conventional cleaning liquids on an aqueous basis and thus facilitate washing-up 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, 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 hydrophobicizes this surface. This facilitates the removal of dirt and at the same time causes water to bead off the surface and not wet it, thereby avoiding the formation of water droplets and thus the retention of residual stains. This feature is particularly useful where surfaces are particularly prone to limescale, dirt and biofilm deposits, such as toilet bowls, sinks, bathtubs 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 dry quickly after this rinse, For example, because a fast-drying surface in a consumer enhances the impression of cleanliness.

Examples

Example 1: Formulations used

The table below shows an example of a formulation used for the cleansing compositions according to the invention.

Table 1: Formulation used

The new compound used is an acidic sol-gel product of phosphoric acid and three silanes. These are aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane and propyltrimethoxysilane. The hydrolysis product methanol is removed from the system by vacuum distillation.

Example 2: Investigation of Surface Modification

A black tile of the company Mosa (Mastricht, NL) (wall tile Royal Mosa code NEN.EN 1441 1 GL B III 15cmx15cm) is first cleaned with a commercially available scouring milk and then treated once with ethanol and cleaned.

The tile is "halved" with an adhesive strip, and a paper towel is used to apply a defined amount of the sol-gel compound of the invention as described in Example 1 (eg 0.5-1 ml) to one side of the tile distributed and then allowed to dry.

After drying, the drainage behavior is visually evaluated.

On the untreated side of the tile, water spreads completely and no single drops form on the tile. By treating the tile with the acid sol-gel compound, the tile is rendered extremely hydrophobic, so that the water does not spread, but bubbles off. In addition, a lower calcification was observed in comparison to the untreated tile.

Claims

claims

1. A hard surface cleaning agent, in particular ceramic surfaces, containing, based on the total weight of the cleaning agent, 0.02 to 10% by weight, preferably 0.02 to 1% by weight, of an acidic aqueous composition comprising:

(i) at least one oxo acid of the phosphorus; and

2. Detergent according to claim 1, characterized in that the absolute amount of organosilane compounds in the acidic aqueous composition, calculated based on the element silicon, is not more than 10% by weight, and / or wherein the proportion of organosilanes (ii), calculated in each case based on the element silicon and based on the total amount of organosilanes in the acidic aqueous composition, at least 30 mol%, preferably at least 40 mol%.

3. Cleaning agent according to one of claims 1 or 2, characterized in that the at least one organosilane compound (ii) is selected from the group consisting of compounds of formula (1):

(H2N - [(CH 2) m NH] n (CH 2) p) γ-Si-X (4-y) (1) wherein each X represents hydrolyzable substituents independently selected from the group consisting of alkoxy groups with no more as 4, preferably with not more than 2 carbon atoms;

wherein m and p are each independently an integer in the range of 1-4; wherein n is an integer in the range of 0-8, preferably in the range of 0-3;

and wherein y is an integer in the range of 1 to 3, preferably 1.

4. Cleaning agent according to one of the claims 1 to 3, characterized in that in the acidic aqueous composition in addition to the at least one organosilane compound (ii) at least one further organosilane compound is present, which is in particular selected from organosilane compounds having at least one hydrolyzable substituent and 1 - 3 non-hydrolyzable substituents, wherein at least one of the non-hydrolyzable substituents carries a hydroxyl or oxirane group.

5. Cleaning agent according to claim 4, characterized in that the proportion of organosilanes having at least one hydrolyzable substituent and 1-3 non-hydrolyzable substituents, wherein at least one of the non-hydrolyzable substituents has at least one hydroxyl or oxirane group, calculated based on the Element silicon and based on the total amount of organosilanes in the acidic aqueous composition, at least 10 mol%, preferably at least 20 mol%.

6. Cleaning agent according to one of claims 1 to 5, characterized in that the at least one oxo acid of the phosphorus (i) is selected from the group consisting of organophosphoric acids, phosphonic acids and / or phosphoric acids, wherein the proportion of organophosphoric acids based on the total amount of oxo acids of the phosphorus is preferably at least 10 mol% calculated based on the element phosphorus.

7. Cleaning agent according to claim 6, characterized in that the organophosphoric acids are selected from the group consisting of α-aminophosphonic acids according to the general structural formula (2)

wherein n is an integer of at least 1 but not more than 5, preferably not more than 3;

wherein m is an integer of at least 1 but not more than 5;

wherein the substituent Y is selected from the group consisting of -P (= O) (OX) ₂ , -OH, -NH ₂ , preferably -P (= O) (OX) ₂ and -OH;

wherein the radicals X are independently selected from the group consisting of hydrogen, aliphatic groups having not more than 4 carbon atoms, alkali metal cations, ammonium or quaternary ammonium cations;

and wherein at least one of the radicals X is hydrogen.

8. A detergent according to any one of claims 1 to 7, characterized in that the molar ratio of the amount of organosilanes, calculated based on the element silicon, to the amount of oxo acids of the phosphorus, calculated based on the element phosphorus, in the range of 1 - 5, preferably in the range of 2-4.

9. Cleaning agent according to one of claims 1 to 8, characterized in that it comprises at least one carboxylic acid, preferably formic acid.

10. Cleaning agent according to one of claims 1 to 9, characterized in that the amount of acids having a pKA value for the first deprotonation of more than 3.5 less than 0.05 wt .-% based on the total weight of the acidic aqueous composition is.

1 1. Cleaning agent according to one of claims 1 to 10, characterized in that the pH of the aqueous acidic composition in the range of 1 - 6, preferably in the range of 2.0 - 5.5.

12. Cleaning agent according to one of claims 1 to 1 1, characterized in that the cleaning agent at least one further ingredient, preferably at least two further ingredients selected from the group consisting of surfactants, solvents, thickeners, other acids, salts, film formers, antimicrobial agents , Builders, corrosion inhibitors, chelating agents, sequestering agents, electrolytes, foam inhibitors, disintegration aids, soil release agents, UV absorbers, UV alkalis, preservatives, bleaching agents, bleach activators, bleach catalysts, enzymes, enzyme stabilizers, abrasives, polymers and fragrances. and dyes and mixtures thereof.

13. Use of a cleaning agent according to one of claims 1 to 12 for cleaning and / or surface modification of hard surfaces.

14. A method for cleaning hard surfaces using a detergent according to any one of claims 1 to 12.

15. Use of an acidic aqueous composition comprising:

(i) at least one oxo acid of the phosphorus; and

(ii) at least 0.2% by weight, calculated based on the element silicon and based on the total weight of the acidic aqueous composition, of at least one organosilane compound having at least one hydrolyzable substituent and 1-3 non-hydrolyzable substituents, at least one of non-hydrolyzable substituent has at least one amino group, and wherein the absolute number of substituents on each silicon atom of an organosilane compound is 4,

to improve the dirt-repellent effect of a hard surface.