EP4025109B1 - Cleaning robot comprising a cleaning cloth and cleaning means - Google Patents

Description

The present invention relates to a cleaning robot comprising a cleaning cloth and a cleaning agent and the use of a concentrated cleaning agent in such a cleaning robot.

Cleaning robots for damp wiping are known from the prior art, comprising a cleaning cloth and a cleaning agent, the cleaning robot being designed to guide the cleaning cloth over a hard surface. This makes it easy to clean hard surfaces without the consumer having to hold the tablecloth himself, as is the case with conventional manual surface cleaning. Such cleaning robots allow for convenient and thorough cleaning of hard surfaces.

In order to enable thorough cleaning of hard surfaces, the use of a cleaning agent is required. By using at least one surfactant, dirt can be effectively removed from the hard surfaces.

A cleaning robot will be in the EP 3482669 A1 described. Also the DE 1 020131 08905 A1 , EP 3 400009 A2 and DE 20 2017 107847 U1 describe methods of cleaning hard surfaces.

However, it was found that the cleaning performance of cleaning agents known from the prior art is not satisfactory when used in a cleaning robot.

The object of the present invention was therefore to provide a cleaning robot comprising a cleaning agent which enables improved cleaning performance.

This object is achieved by a cleaning robot comprising a cleaning cloth and a cleaning agent, wherein the cleaning robot is designed to guide the cleaning cloth over a hard surface, characterized in that the cleaning agent in dynamic measurement at 23°C with a surface age of 0.3 Seconds has a surface tension of at most 40 mN/cm, preferably at most 38 mN/cm and particularly preferably at most 35 mN/cm.

Without being bound to any theory, the following statements were made in the present case:
Surfactants lower the surface tension of aqueous compositions and thus enable effective surface cleaning. The lowering of the surface tension is achieved by the addition of surfactants to the surface. This is a dynamic process, so that the equilibrium value of the surface tension is not reached immediately after film formation, but only after a certain time. It is observed here that the surface tension approaches the surface tension equilibrium value from an initially relatively high value as time progresses. In other words, sufficiently low surface tension values for good cleaning only occur after a certain time.

In manual surface cleaning, the cleaning agent is applied to the hard surface. For this purpose, the cleaning agent is either applied directly to the surface or a cleaning cloth is saturated with the cleaning agent. In any case, with such a manual cleaning, a certain amount of time elapses before the actual cleaning process takes place. The surfactants have enough time to accumulate on the surface of the detergent film that is formed and thus reduce the surface tension. In other words, during the manual cleaning process, the cleaning agent usually has the equilibrium value of the surface tension.

In the case of automatic surface cleaning by means of a cleaning robot, the cleaning agent is applied to the hard surface, with the wiping process taking place essentially at the same time as the cleaning agent is applied. In contrast to manual cleaning, the surfactants have little time to accumulate on the surface of the cleaning agent film that has formed and thus reduce the surface tension. In other words, in the automatic cleaning process, the cleaning agent usually does not have the equilibrium value of the surface tension. In order to enable good cleaning, a cleaning agent must be used in which a sufficiently strong reduction in surface tension has taken place shortly after film formation.

According to the invention, the dynamic surface tension is determined by bubble pressure tensiometry. These methods are known to those skilled in the art. An air bubble is created in the liquid to be examined for a certain period of time. The measured value that occurs during this period corresponds to the surface tension at a specific surface age. If you now change the lifetime of the air bubble, i.e. the surface age, the surface tension of the cleaning liquid can be determined as a function of the surface age. The measurements take place under standard conditions, specifically at a temperature of 23°C.

According to a particularly preferred embodiment, the cleaning robot is designed to guide the cleaning cloth over the hard surface at a speed of at least 5 cm/s, preferably at least 10 cm/s, more preferably at least 20 cm/s. In the case of such fast-moving cleaning robots in particular, it was found that an improvement in the cleaning performance can be achieved if a cleaning agent is used which, when measured dynamically at 23°C and with a surface age of 0.3 seconds, has a surface tension of at most 40 mN/cm, preferably at most 38 mN/cm and particularly preferably at most 35 mN/cm. As already described above, the cleaning agent usually does not have its equilibrium value during the automatic cleaning process with fast cleaning robots. A cleaning agent must therefore be used in which a sufficiently strong reduction in surface tension has taken place shortly after film formation.

According to a preferred embodiment, the cleaning robot is described, wherein the cleaning robot is designed to guide the cleaning cloth over the hard surface at a speed of at least 5 cm/s, preferably at least 10 cm/s, more preferably at least 20 cm/s.

According to a preferred embodiment of the cleaning robot, the decrease in the surface tension of the cleaning agent during dynamic measurement at 23° C. is at least 2 mN/cm, preferably 5 mN/cm, within a surface service life of 0.3 seconds.

According to a preferred embodiment, the cleaning robot is described, wherein the cleaning robot is designed to convey the cleaning agent out of a cleaning agent tank and to apply it to the cleaning cloth.

According to a further aspect of the invention, the use of a concentrated cleaning agent in a cleaning robot is described, characterized in that the cleaning agent is diluted with water in the robot and after at least tenfold dilution, preferably about 14-fold dilution in the cleaning robot with dynamic measurement at 23° C has a surface tension of at most 40 mN/cm, preferably at most 38 mN/cm and particularly preferably at most 35 mN/cm at a surface age of 0.3 seconds. A tenfold dilution means that for one part concentrated detergent there are 10 parts water.

According to a preferred embodiment, the use of the concentrated cleaning agent is described, with the cleaning robot being designed as the cleaning cloth at a speed of at least 5 cm/s, preferably at least 10 cm/s, more preferably at least 20 cm/s over the hard surface.

The concentrated cleaning agent formulations according to the invention are described below by way of example, without the invention being restricted to these exemplary embodiments. If ranges, general formulas or compound classes are specified below, these should not only include the corresponding ranges or groups of compounds that are explicitly mentioned, but also all sub-ranges and sub-groups of compounds that are obtained by removing individual values (ranges) or compounds can become. In the context of the present invention, compounds such. B. polyethers described, which can have different units several times, these can occur statistically distributed (random oligomer) or ordered (block oligomer) in these compounds. Details of the number of units in such compounds are to be understood as the average, averaged over all corresponding compounds.

In the context of the present invention, fatty acids or fatty alcohols or their derivatives—unless otherwise stated—are representative of branched or unbranched carboxylic acids or alcohols or their derivatives preferably having 6 to 22 carbon atoms. The former are preferred in particular because of their vegetable basis as based on renewable raw materials for ecological reasons, but without restricting the teaching according to the invention to them. In particular, the oxo-alcohols or derivatives thereof obtainable, for example, by _Roelen 's oxo-synthesis can also be used accordingly.

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

Substances that are also used as ingredients in cosmetic products are referred to below, where appropriate, in accordance with the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds have an INCI name in English, herbal ingredients are listed exclusively in Latin according to Linnaeus, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI designations are dem International Cosmetic Ingredient Dictionary and Handbook-Seventh Edition (1997) published by The Cosmetic, Toiletry, and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA , is published and contains more than 9,000 INCI designations and references to more than 37,000 trade names and technical designations including their associated distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns ingredients to one or more chemical classes, such as polymeric ethers, and one or more functions (Functions), for example Surfactants - Cleansing Agents, which it in turn explains in more detail and to which reference may also be made below.

The indication CAS means that the following sequence of numbers is a designation of the Chemical Abstracts Service.

Unless explicitly stated otherwise, the amounts given in percent by weight (% by weight) relate to the entire composition. These percentage amounts relate to active contents.

nonionic surfactants

Nonionic surfactants within the scope of the invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also useful are ethylene oxide/propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers. Another important class of nonionic surfactants which can be used according to the invention are the polyol surfactants and here in particular the glycosurfactants such as alkyl polyglycosides and fatty acid glucamides. The alkyl polyglycosides are particularly preferred, in particular the alkyl polyglucosides, the alcohol being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched C ₈ - to C ₁₈ -alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, especially 1.1 to 3, most preferably 1.1 to 1.7, for example C _8-10 -alkyl-1.5-glucoside (DP of 1.5). In addition, fatty alcohol alkoxylates (fatty alcohol polyglycol ethers) are also preferred, in particular unbranched or branched, saturated or unsaturated C _8-22 alcohols alkoxylated with ethylene oxide (EO) and/or propylene oxide (PO) with a degree of alkoxylation of up to 30, preferably ethoxylated C _{12- C 22} fatty alcohols with a degree of ethoxylation of less than 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example C _16-18 fatty alcohol ethoxylates with 25 EO.

In addition to or independently of the nonionic surfactant, the cleaning agent according to the invention can contain at least one anionic surfactant. Preferred anionic surfactants here are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkyl benzene sulfonates, olefin sulfonates, alkane sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-C ₈ -C ₁₈ -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, Ether carboxylic acids and alkyl (ether) phosphates and α-sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

In the context of the present invention, preference is given to the linear alkylbenzene sulfonates, fatty alcohol sulfates and/or fatty alcohol ether sulfates, in particular the fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, while fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably with relatively long-chain alcohols for the purposes of the present invention. As a rule, a complex mixture of addition products with different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment of the alkoxylation consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Preferred fatty alcohol ether sulfates are the sulfates of lower ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO. In the case of the alkylbenzene sulfonates, preference is given in particular to those having about 12 carbon atoms in the alkyl moiety, for example linear sodium C _10-18 -alkylbenzene sulfonate. Preferred olefin sulfonates have a carbon chain length of 14-16.

The anionic surfactants are preferably used as sodium salts, but can 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, and in the case of sulfonates also in the form its corresponding acid, e.g. dodecylbenzenesulfonic acid.

In addition to the types of surfactants mentioned so far, the agent according to the invention can also contain cationic surfactants and/or amphoteric surfactants.

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

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi )(R ^vii )(R ^viii )(R ^ix )N ⁺ X ^- , where R ^vi to R ^ix are four of the same or different types, in particular two long and two short-chain alkyl radicals and X ^- stand for an anion, in particular a halide ion, for example didecyl dimethyl ammonium chloride, alkyl benzyl didecyl ammonium chloride and mixtures thereof. Other suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which is possibly already present due to other ingredients, can be improved.

The total surfactant content of such a preferably aqueous detergent formulation is preferably 0.1 to 40% by weight and particularly preferably 0.1 to 12.0% by weight, based on the formulation as a whole.

Other ingredients commonly found in hard surface cleaners may also be included in the cleaner. This group of other possible ingredients includes, but is not limited to, acids, bases, organic solvents, salts, chelating agents, fillers, builders, bleaching agents and mixtures thereof.

water soluble salts

The cleaning agent according to the invention can also contain one or more water-soluble salts in a total amount of 0.1 to 75% by weight. These can be inorganic and/or organic salts.

Inorganic salts that can be used according to the invention are preferably selected from the group consisting of colorless, water-soluble halides, sulfates, sulfites, carbonates, hydrogen carbonates, nitrates, nitrites, phosphates and/or oxides of alkali metals, alkaline earth metals, aluminum and/or transition metals; ammonium salts can also be used. Halides and sulfates of the alkali metals are particularly preferred; the at least one inorganic salt is therefore preferably selected from the group consisting of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof. In a preferred embodiment, sodium chloride and/or sodium sulfate is used.

The organic salts that can be used according to the invention are, in particular, colorless, water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and/or transition metal salts of carboxylic acids. The salts are preferably selected from the group consisting of formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.

solvent

In one embodiment, the cleaning composition of the present invention is an aqueous hard surface cleaning composition. In a preferred embodiment, it can contain one or more other water-soluble organic solvents in addition to water, usually in an amount of 0 to 15% by weight, preferably 1 to 12% by weight, in particular 3 to 8% by weight.

Within the scope of the teaching according to the invention, the solvents are used as required, in particular as hydrotropes and viscosity regulators. They have a solubilizing effect, in particular for surfactants and electrolytes as well as perfume and dye, and thus contribute to their incorporation, prevent the formation of liquid-crystalline phases and contribute to the formation of clear products. The viscosity of the agent according to the invention decreases as the amount of solvent increases. Finally, as the amount of solvent increases, the cold cloud point and clear point of the agent according to the invention decrease.

Suitable solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C1-20 hydrocarbons, preferably C2-15 hydrocarbons, with at least one hydroxyl group and optionally one or more ether functions C-O-C, d. H. oxygen atoms interrupting the carbon chain.

Preferred solvents are the - optionally unilaterally etherified with a C1-6 alkanol - C2-6 alkylene glycols and poly-C2-3-alkylene glycol ethers with an average of 1 to 9 identical or different, preferably identical, alkylene glycol groups per molecule as well as the C1-6 -Alcohols, preferably ethanol, n-propanol or iso-propanol.

Exemplary solvents are the following compounds named according to INCI: Buteth-3, butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyloctanol, diethylene glycol, dimethoxydiglycol, dimethyl ether, dipropylene glycol, ethoxydiglycol, Ethoxyethanol, Ethyl Hexanediol, Glycol, Hexanediol, 1,2,6-Hexanetriol, Hexyl Alcohol, Hexylene Glycol, Isobutoxypropanol, Isopentyldiol, Isopropyl Alcohol (iso-Propanol), 3-Methoxybutanol, Methoxydiglycol, Methoxyethanol, Methoxyisopropanol, Methoxymethylbutanol, Methoxy PEG- 10, Methylal, Methyl Alcohol, Methyl Hexyl Ether, Methylpropanediol, Neopentyl Glycol, PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-6 Methyl Ether, Pentylene Glycol, Phenoxyethanol, PPG-7 , PPG-2-Buteth-3, PPG-2 Butyl Ether, PPG-3 Butyl Ether, PPG-2 Methyl Ether, PPG-3 Methyl Ether, PPG-2 Propyl Ether, Propanediol, Propyl Alcohol (n-Propanol), Propylene Glycol, Propylene Glycol Butyl Ether, Propylene Glycol Propyl Ether, Tetrahydrofurfuryl Alcohol, Trimethylhexanol.

Longer-chain polyalkylene glycols, in particular polypropylene glycols, are also preferred. PPG-400 or PPG-450 are particularly preferred, but polypropylene glycols with longer chain lengths can also be used for the purposes of this invention.

The solvent is preferably selected from the group consisting of ethanol, propanol, isopropanol, ethylene glycol, butyl glycol, propylene glycol, polypropylene glycol and also alcohol amines, in particular monoethanolamine and mixtures thereof Extremely preferred solvents are the C2 and C3 alcohols, ethanol, n-propanol and/or isopropanol and the polyalkylene glycols, especially polypropylene glycols, especially PPG-400, and also alcohol amines, especially monoethanolamine and mixtures thereof.

A mixture of isopropanol and monoethanolamine is very particularly preferably used as the organic solvent.

In addition to the solvents described above, alkanolamines, for example, can also be used as solubilizers, in particular for perfumes and dyes.

Builders

Furthermore, the cleaning agent according to the invention can contain all builders customarily used in detergents and cleaning agents, in particular silicates, carbonates, organic cobuilders and also the phosphates.

The silicates include crystalline, layered sodium silicates of the general formula NaMSi _x O _2x+1 yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. In addition, amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6 can be used. which also includes water glass. In the context of this invention, the term "amorphous" also means "X-ray amorphous". This means that in X-ray diffraction experiments the silicates do not produce any sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation which have a width of several degree units of the diffraction angle. Furthermore, zeolites can be used as builder substances, preferably zeolite A and/or P. However, zeolite X and mixtures of A, X and/or P are also suitable.

Both the monoalkali metal salts and the dialkali metal salts of carbonic acid and sesquicarbonates can be contained in the agents as carbonates. Preferred alkali metal ions are sodium and/or potassium ions, soda (sodium carbonate) and potash (potassium carbonate) being particularly preferred.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use is not to be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) being particularly preferred, are the most important in the detergent and cleaning agent industry.

"Alkali metal phosphates" is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ can be distinguished in addition to higher molecular weight representatives. Suitable phosphates are sodium dihydrogen phosphate, NaH ₂ PO ₄ , disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , and the Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher molecular weight sodium and potassium phosphates, in which one can distinguish between cyclic representatives, the sodium or potassium metaphosphates, and chain-type types, the sodium or potassium polyphosphates. A large number of terms are used for the latter in particular: melted or calcined phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

In particular, polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates can be present as organic cobuilders.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycine diacetic acid, saccharic acids and mixtures of these. In addition to the salts, the acids per se can also be used.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g/mol. The molar masses given for polymeric polycarboxylates are weight-average molar masses M _w of the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid standard which, due to its structural relationship with the polymers examined, provides realistic molecular weight values.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. as particularly suitable Copolymers of acrylic acid with maleic acid have been found which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids, is generally 2000 to 100,000 g/mol.

To improve water solubility, the polymers can also contain allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid, as a monomer.

Particular preference is also given to biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives as monomers or salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers .

Further preferred copolymers preferably have acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers.

Other suitable builder substances are polymeric aminodicarboxylic acids, their salts or their precursors, in particular polyaspartic acids or their salts and derivatives, as well as polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. and dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. These are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g/mol.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine-N,N'-disuccinate (EDDS), are further suitable cobuilders, preferably in the form of their sodium or magnesium salts, furthermore iminodisuccinates (IDS) and their derivatives, for example hydroxyiminodisuccinates (HDIS), and acetylated hydroxycarboxylic acids or their salts, which can optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups.

The phosphonates represent another class of substances with cobuilder properties. These are in particular hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, with the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of the neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP. HEDP from the class of the phosphonates is preferably used as the builder. The amino alkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable, particularly if the agents also contain bleach, to use aminoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth metal ions can be contained in the particulate agents as cobuilders.

acids

One or more acids and/or their salts can be present to improve the cleaning performance against limescale. The acids are preferably produced from renewable raw materials. 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 and mixtures thereof are therefore particularly suitable as acids. In addition, however, the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or amidosulfonic acid or mixtures thereof can also be used. The acids and/or their salts are particularly preferably selected from the group consisting of citric acid, lactic acid, formic acid, their salts and mixtures thereof. They are preferably used in amounts of 0.01 to 10% by weight, particularly preferably 0.2 to 5% by weight.

bases

Alkalis can also be present in detergent blocks according to the invention. The bases used 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 carbon atoms in the molecule, preferably the ethanolamines, in particular monoethanolamine.

complexing agent

Complexing agents ( INCI chelating agents), also known as sequestering agents, are ingredients that are capable of complexing and inactivating metal ions in order to prevent their adverse effects on the stability or the appearance of the cleaning agents according to the invention, for example turbidity. On the one hand, it is important to complex the calcium and magnesium ions of the water hardness, which are incompatible with numerous ingredients. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished product. In addition, the complexing agents support the cleaning effect.

For example, the following complexing agents designated according to INCI are suitable: aminotrimethylene phosphonic acid, beta-alanine diacetic acid, calcium disodium EDTA, citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric 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 Oxide, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA Polyphosphates, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

bleach

According to the invention, bleaching agents can be added to the cleaning product. Suitable bleaching agents include peroxides, peracids and/or perborates, sodium percarbonate or phthalimidoperoxyhexanoic acid being particularly preferred. Bleaching agents containing chlorine, such as trichloroisocyanuric acid or sodium dichloroisocyanurate, on the other hand, are less suitable for acidic cleaning agents due to the release of toxic chlorine gas vapours, but they can be used in alkaline cleaning agents. In some cases, a bleach activator may be needed in addition to the bleach.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Of all the bleach activators known to the person skilled in the art from the prior art, polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), are acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used. Combinations of conventional bleach activators can also be used. These bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 up to 6% by weight, based in each case on the total weight of the bleach activator-containing agents.

auxiliaries and additives

In addition to the components mentioned above, the agent according to the invention can contain one or more other auxiliaries and additives that are customary, especially in cleaning agents for hard surfaces. These include, for example, organic fillers (in particular sugar, sugar alcohols, glycerol, glycols and polymers thereof), hydrophobicity mediators (such as paraffin, for example), UV stabilizers, perfume oils, antimicrobial agents, pearlescent agents (INCI Opacifying Agents; for example glycol distearate, for example ^Cutina® AGS from BASF, or mixtures containing it, e.g. Euperlane ^® from BASF), other opacifying agents, dyes, corrosion inhibitors, bitter substances, preservatives (e.g. the technical 2-bromo-2-nitropropane-1, also known as Bronopol, 3-diol (CAS 52-51-7), which is commercially available, for example, as Myacide ^® BT or as Boots Bronopol BT from Boots, or mixtures containing bronopol such as Preventol ^® (ex Lanxess) or Parmetol ^® (ex Schülke & Mayr )), disinfectants, enzymes, pH adjusters, fragrances and additives that improve skin feel or care for the skin (e.g. dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial Hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes, glycerin, urea, quaternized hydroxyethyl cellulose), additives to improve sagging and drying behavior or for stabilization. These auxiliaries and additives are usually present in amounts of not more than 5% by weight.

fragrances

The product according to the invention can contain one or more fragrances, preferably in an amount of 0.01 to 10% by weight, in particular 0.05 to 8% by weight, particularly preferably 0.1 to 5% by weight. D-limonene can be present as a perfume component. In another embodiment, the cleaning agent block according to the invention contains a perfume made from essential oils (also referred to as essential oils). As such, for example, pine, citrus, jasmine, patchouli, rose or ylang-ylang oil can be used for the purposes of this invention. Also suitable are clary sage oil, chamomile oil, lavender oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. Other fragrances commonly used in detergents and cleaning agents are also suitable for use in the cleaning agent block according to the invention, for example other essential oils, esters, alcohols, aldehydes or terpenes.

Antimicrobial agents

Disinfection and sanitation represent a special form of cleaning. In a corresponding special embodiment of the invention, the cleaning agent therefore contains one or more antimicrobial active ingredients, preferably in an amount of 0.01 to 1% by weight, preferably 0.02 to 0.8% by weight, in particular 0.05 to 0.5% by weight, particularly preferably 0.1 to 0.3% by weight, extremely preferably 0.2% by weight.

Within the scope of the teaching according to the invention, the terms disinfection, sanitation, antimicrobial effect and antimicrobial active ingredient have the customary meaning. While disinfection in the narrower sense of medical practice means killing - theoretically all - infectious germs, sanitation means the elimination of all germs as far as possible - including the saprophytic germs that are normally harmless to humans. The extent of the disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with a decreasing content of antimicrobial active ingredient or increasing dilution of the agent for use.

Suitable according to the invention are, for example, antimicrobial active ingredients from the groups of alcohols, aldehydes, antimicrobial acids and their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and 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, iodophors, active chlorine-releasing compounds and peroxides. Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylene-bis(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-( 3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)bis(1-octanamine)dihydrochloride, N,N'-bis(4- chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines and sodium dichloroisocyanurate (DCI, 1,3-dichloro-5H-1,3,5-triazine-2, 4,6-trione sodium salt). Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, essential oils with an antimicrobial effect can also be used, which at the same time ensure that the cleaning product is scented. However, particularly preferred antimicrobial agents are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride, peroxo compounds, in particular hydrogen peroxide, alkali metal hypochlorite, sodium dichloroisocyanurate and mixtures thereof.

preservatives

Preservatives can also be contained in detergent products according to the invention. As such, essentially the substances mentioned for the antimicrobial agents can be used.

dyes

The detergent product according to the invention can contain one or more colorants ( INCI colorants) as further ingredients. Both water-soluble and oil-soluble dyes can be used as dyes, whereby on the one hand the compatibility with other ingredients, for example bleaches, must be taken into account and on the other hand the dye used should not have a substantive effect on the metal and ceramics even after prolonged exposure. The dyes are preferably present in an amount of 0.0001 to 0.1% by weight, in particular 0.0005 to 0.05% by weight, particularly preferably 0.001 to 0.01% by weight.

corrosion inhibitors

Suitable corrosion inhibitors ( INCI Corrosion Inhibitors) are, for example, the following substances named according to INCI : cyclohexylamine, diammonium phosphate, dilithium oxalate, dimethylaminomethylpropanol, dipotassium oxalate, dipotassium phosphate, disodium phosphate, disodium pyrophosphate, disodium tetrapropenyl succinate, hexoxyethyl diethylammonium, phosphate, nitromethane, potassium Silicates, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.

rinse regulators

The substances referred to as rinsing regulators primarily serve to control the consumption of the agents during use in such a way that the intended service life is adhered to. Suitable regulators are preferably solid, long-chain fatty acids, such as stearic acid, but also salts of such fatty acids, fatty acid ethanolamides, such as coconut fatty acid monoethanolamide, or solid polyethylene glycols, such as those with molecular weights between 10,000 and 50,000.

enzymes

The cleaning product can also contain enzymes, preferably proteases, lipases, amylases, hydrolases and/or cellulases. They can be added to the agent according to the invention in any form established according to the prior art. These include solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed 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 enclosed as in a set gel or in those of core-shell Type in which an enzyme-containing core with covered with a protective layer impermeable to water, air and/or chemicals. Additional active substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. 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 due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.

Furthermore, enzyme stabilizers can be present in cleaning products containing enzymes in order to protect an enzyme contained from damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage. Depending on the enzyme used, particularly suitable enzyme stabilizers are: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, such as substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with a reduced C terminus), amino alcohols such as mono-, di-, triethanolamine and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ such as succinic acid, other dicarboxylic acids or salts of the acids mentioned; 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 from the prior art. Combinations of stabilizers are preferably used, 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.

PH value

The pH of the agents according to the invention can be adjusted using customary pH regulators, for example citric acid or NaOH. It is preferred here that the agent has a pH in a range from 5 to 11.5, preferably 7 to 11.3.

To adjust and/or stabilize the pH, the agent according to the invention can also contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5% by weight, preferably 0.005 to 3% by weight, in particular 0.01 to 2% by weight, particularly preferably 0.05 to 1% by weight, extremely preferably 0.1 to 0.5% by weight, for example 0.2% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate·2H ₂ O and tripotassium citrate·H ₂ O.

The invention is described in more detail using the following drawings and examples:
figure 1 shows a cleaning robot 1 comprising a cleaning cloth 10 in a view from below. The cleaning robot 1 guides the cleaning cloth 10 over a hard surface. The cleaning robot 1 is moved over the hard surface by means of wheels 20 . The cleaning robot 1 moves at a certain speed along the direction indicated by the dashed arrow.

figure 2 shows the cleaning robot 1 including the cleaning cloth 10 in a side view. The cleaning agent is conveyed out of the cleaning agent tank 30 and first applied to the cleaning cloth 10 and then directly to the surface 5 to be cleaned by means of the cleaning cloth 10 . In the case of automatic surface cleaning by means of the cleaning robot 1, the cleaning agent is applied to the hard surface 5 when the robot moves, with the wiping process taking place essentially at the same time as the application of the cleaning agent. In contrast to manual cleaning, the surfactants have little time to accumulate on the surface of the cleaning agent film that has formed and thus reduce the surface tension. In other words, in the automatic cleaning process, the cleaning agent usually does not have its equilibrium value. In order to enable good cleaning, a cleaning agent must be used in which a sufficiently strong reduction in surface tension has taken place shortly after film formation.

Table 1 below shows the concentrated composition used: Table 1: component Amount AS [% by weight] Water 93.8 sodium hydroxide 0.1 alkyl benzene sulfonate 0.4 fatty acid 0.1 Fatty alcohol ethoxylate C6.5 EO 0.3 Fatty alcohol ethoxylate C12-18.7 EO 0.1 isopropanol 1.5 Phenoxyethanol, pure 1.0 perfume, dyes >3 monoethanolamines 1.5 preservatives >3

The amounts given are to be understood as the active substance in the concentrated composition.

Table 2 below shows the surface tension which was determined for the composition according to Table 1 after diluting 18 ml of concentrated cleaning agent with 250 ml of water (temperature 23° C.). The pH in the used (diluted) composition was pH = 10.6. Table 2: surface age [seconds] Surface tension [mN/cm] 0.08 40.0 0.22 35.5 0.31 34.2 0.44 33:1 0.87 31:3 1.2 30.3

The cleaning agent listed here as an example thus shows a surface tension of about 34 mN/cm in a dynamic measurement at 23° C. with a surface age of 0.3 seconds and is therefore below the particularly preferred limit value of 35 mN/cm.

The cleaning agent shown is therefore particularly well suited for use with the cleaning robot according to the invention. A sufficiently strong reduction in surface tension thus takes place soon after film formation and thus a preferred cleaning performance. However, the composition given is only to be understood as an example and not as a restriction. The person skilled in the art will be able to adjust the surface tension (lowering of the surface tension) according to the invention by changing individual components and dilution parameters of other compositions.

Claims (7)

1. Cleaning robot (1) comprising a cleaning cloth (10) and a cleaning agent, the cleaning robot (1) being designed to guide the cleaning cloth (10) over a hard surface (5) and the cleaning agent comprising at least one surfactant, characterized in that the cleaning agent has a surface tension of at most 40 mN/cm, preferably at most 38 mN/cm and particularly preferably at most 35 mN/cm, when measured dynamically at 23°C at a surface age of 0.3 seconds.
2. Cleaning robot (1) according to claim 1, wherein the cleaning robot (1) is designed to guide the cleaning cloth (10) over the hard surface (5) at a speed of at least 5 cm/s, preferably at least 10 cm/s more preferably at least 20 cm/s.
3. Cleaning robot (1) according to claim 1 or 2, wherein the change in surface tension of the cleaning agent when measured dynamically at 23°C is at least 2 mN/cm, preferably at least 5 mN/cm, within a surface lifetime of 0.3 seconds.
4. Cleaning robot (1) according to any one of the preceding claims, wherein the reduction of the surface tension of the cleaning agent when measured dynamically at 23°C is at least 3 mN/cm, further preferably at least 5 mN/cm within a surface lifetime of 0.3 seconds.
5. Cleaning robot (1) according to any one of the preceding claims, wherein the cleaning robot (1) is configured to convey the cleaning agent out of a cleaning agent tank (30) and apply it to the cleaning cloth (10).
6. Use of a concentrated cleaning agent in a cleaning robot (1), characterized in that the cleaning agent, after at least tenfold dilution in the cleaning robot, has a surface tension of at most 40 mN/cm, preferably at most 38 mN/cm and particularly preferably at most 35 mN/cm, when measured dynamically at 23°C at a surface age of 0.3 seconds.
7. A method of cleaning a surface using a cleaning robot according to any one of the preceding claims, wherein the cleaning cloth (10) is passed over the hard surface (5) at a speed of at least 5 cm/s, preferably at least 10 cm/s more preferably at least 20 cm/s.

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