EP4025109A1

EP4025109A1 - Cleaning robot comprising a cleaning cloth and a cleaning agent

Info

Publication number: EP4025109A1
Application number: EP20767747.7A
Authority: EP
Inventors: Arnd Kessler; Slavoljub Barackov; Ingo Hardacker
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2019-09-05
Filing date: 2020-09-01
Publication date: 2022-07-13
Anticipated expiration: 2040-09-01
Also published as: KR20220057541A; DE102019213539A1; US20220183527A1; CN114340462B; EP4025109B1; WO2021043772A1; CN114340462A

Abstract

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

Description

"Cleaning robot comprising a cleaning cloth and a cleaning agent"

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 wet 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. In this way, hard surfaces can be cleaned comfortably without the consumer having to guide the tablecloth himself, as is the case with conventional manual surface cleaning. Such cleaning robots allow a comfortable and thorough cleaning of hard surfaces.

The use of a detergent is required to enable thorough cleaning of hard surfaces. The use of at least one surfactant can effectively remove dirt from the hard surfaces.

However, it has been 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, the cleaning robot being designed to guide the cleaning cloth over a hard surface, characterized in that the cleaning agent with 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 a 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 the surfactants to the surface. This is a dynamic process so that the equilibrium value of the surface tension does not change after film formation immediately, but only after a certain time. It is observed here that the surface tension, from an initially relatively high value, approaches the surface tension equilibrium value as time progresses. In other words, surface tension values that are sufficiently low for good cleaning are only established after a certain period of time.

With manual surface cleaning, the detergent is applied to the hard surface. For this purpose, the cleaning agent is either applied directly to the surface or a cleaning cloth is soaked in the cleaning agent. In any case, with such manual cleaning, a certain time passes before the actual cleaning process takes place. The surfactants have sufficient time to accumulate on the surface of the cleaning agent film that has formed and thus to reduce the surface tension. In other words, in 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, the wiping process taking place essentially at the same time as the cleaning agent is applied. In contrast to manual cleaning, the surfactants only have little time to accumulate on the surface of the cleaning agent film that has formed and thus to reduce the surface tension. In other words, during the automatic cleaning process, the cleaning agent generally 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 already taken place shortly after film formation.

According to the invention, the dynamic surface tension is determined by means of bubble pressure tensiometry. These methods are known to the person skilled in the art. An air bubble is generated 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 certain surface age. If you change the lifetime of the air bubble, i.e. the surface age, the surface tension of the cleaning liquid can be determined depending on the surface age. The measurements take place under standard conditions, in particular 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 particular in the case of such fast-moving cleaning robots, it was found that an improvement in cleaning performance can be achieved if a cleaning agent is used which, when measured dynamically at 23 ° C., has 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, in the automatic cleaning process with fast cleaning robots, the cleaning agent usually does not have its equilibrium value. A cleaning agent must therefore be used in which a sufficiently strong reduction in surface tension has already taken place shortly after film formation.

According to a preferred embodiment, the cleaning robot is described, the cleaning robot being 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.

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

According to a preferred embodiment, the cleaning robot is described, the cleaning robot being 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 ten-fold dilution, preferably about 14-fold dilution in the cleaning robot with 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. A tenfold dilution is understood to mean that there are 10 parts of water for one part of concentrated cleaning agent.

According to a preferred embodiment, the use of the concentrated cleaning agent is described, the cleaning robot being 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 .

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 areas, general formulas or compound classes are specified below, these are not only intended to represent the corresponding areas or groups of Connections include that are explicitly mentioned, but also all sub-areas and sub-groups of connections that can be obtained by removing individual values (areas) or connections. Are in the context of the present invention compounds such. B. polyethers described, which can have multiple units, so these can be statistically distributed (statistical oligomer) or ordered (block oligomer) occur in these compounds. Information on the number of units in such compounds is to be understood as an average value, averaged over all corresponding compounds.

In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms. The former are preferred for ecological reasons, in particular because of their vegetable base, rather than based on renewable raw materials, without, however, 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 in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient to balance the charge - as the anion.

Substances that also serve as ingredients of cosmetic agents are referred to below, if applicable, in accordance with the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds have an INCI name in English, herbal ingredients are listed exclusively according to Linne in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names are the 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 and more than 9,000 INCI names as well as references to more than 37,000 trade names and technical names including the associated distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns the ingredients to one or more chemical classes, for example Polymerie Ethers, and a or several functions, e.g. surfactants - Cleansing Agents, to 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 stated in percent by weight (% by weight) relate to the total composition. These percentage amounts relate to the active content.

Nonionic surfactants

Nonionic surfactants in the context 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. Ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides and fatty acid polyglycol ethers can also be used. Another important class of nonionic surfactants which can be used according to the invention are the polyol surfactants and, in this case, especially the glycoturfactants, such as alkyl polyglycosides and fatty acid glucamides. The alkyl polyglycosides are particularly preferred, in particular the alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched Cs to Cis alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, in particular 1.1 to 3, extremely preferably 1.1 to 1.7, for example Cs-io-alkyl-1.5-glucoside (DP of 1.5). In addition, the fatty alcohol alkoxylates (fatty alcohol polyglycol ethers) are preferred, in particular unbranched or branched, saturated or unsaturated Cs-22 alcohols alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO) with a degree of alkoxylation of up to 30, preferably ethoxylated Ci2-22- 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 Ci6-18 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 are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzene 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-Cs-Cis-alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides) phosphinates and ether carboxylic acids, fatty acid carboxylic acids, and ethereal carboxylic acids can also be used in the context of the present invention Sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

In the context of the present invention, the linear alkylbenzenesulfonates, fatty alcohol sulfates and / or fatty alcohol ether sulfates, in particular the fatty alcohol sulfates, are preferred. 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, for the purposes of the present invention preferably with longer-chain alcohols. 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. Another 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 with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO. In the case of the alkylbenzenesulfonates, preference is given in particular to those with about 12 carbon atoms in the alkyl part, for example linear sodium Cio-18-alkylbenzenesulfonate. 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, as well as 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, for example dodecylbenzenesulfonic acid.

In addition to the previously mentioned types of surfactants, 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 ^iN ) (R ^iv ) (R ^v ) N ⁺ CH2COO-, in which R ^{iN is} an alkyl radical optionally interrupted by heteroatoms or heteroatom groups and having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^v denote identical or different alkyl radicals with 1 to 3 carbon atoms, in particular Cio-Cis-alkyl-dimethylcarboxymethylbetaine and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetaine.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X, in which R ^vi to R ^{ix represent} four identical or different types, in particular two long-chain and two short-chain , Alkyl radicals and X- stand for an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof. Further 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. By using quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.

The total surfactant content of such a, preferably aqueous, cleaning agent 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. Further ingredients that are commonly contained in hard surface cleaning agents can also be included in the cleaning agent. This group of further possible ingredients includes, but is not limited to, acids, bases, organic solvents, salts, complexing agents, fillers, builders, bleaching agents and mixtures thereof.

Water soluble salts

The cleaning agent according to the invention can furthermore 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 which can be used according to the invention are preferably selected from the group comprising 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 comprising 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 which 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 comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.

solvent

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

In the context 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, especially for surfactants and electrolytes, as well as perfume and dyes, 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 cloudiness 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 COC, ie oxygen atoms interrupting the carbon atom chain.

Preferred solvents are the C2-6 alkylene glycols - optionally etherified on one side with a C1-6 alkanol - 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, butoxy diglycol, butoxyethanol, butoxyisopropanol, butoxy propanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyloctanol, diethylene glycol, dimethoxy diglycol, dimethyl ether, dipropylene glycol, ethoxy diglycol, Ethoxyethanol, ethyl hexanediol, glycol, hexanediol, 1, 2,6- hexanetriol, hexyl alcohol, hexylene glycol, isobutoxypropanol, isopentyldiol, isopropyl alcohol (isopropanol), 3-methoxybutanol, methoxydiglycol, methoxyethanol, methoxyisopropanol, methoxymethylbutanol, methoxymethylbutanol 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 Prop yl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.

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

The solvent is preferably selected from the group comprising ethanol, propanol, isopropanol, ethylene glycol, butyl glycol, propylene glycol, polypropylene glycols and alcohol amines, in particular monoethanolamine and mixtures thereof

Extremely preferred solvents are the C2 and C3 alcohols, ethanol, n-propanol and / or iso-propanol and the polyalkylene glycols, especially polypropylene glycols, especially PPG-400 and 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.

Builder

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

The silicates include, on the one hand, crystalline, layered sodium silicates of the general formula NaMSi _x C> 2x _{+ i} yFLO, 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 module Na2 <D: S1O2 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 also be used water glass is also to be expected. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not give 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 also sesquicarbonates can be contained in the agents as carbonates. Preferred alkali metal ions are sodium and / or potassium ions, so soda (sodium carbonate) and potash (potassium carbonate) are particularly preferred.

It goes without saying that the generally known phosphates can also be used as builder substances, provided that such use should not be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry. "Alkali metal phosphates" is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HRq3) _h and orthophosphoric acid H3PO4 in addition to higher molecular weight representatives. Suitable phosphates are sodium dihydrogen phosphate, NaH ₂ P0 ₄ , disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0 ₄ , trisodium phosphate, tertiary sodium phosphate, Na3P0 ₄ , tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 07, as well as the by condensation of NaH ₂ P0 ₄ or the KH2PO4 arise with higher molecular weight Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used for the latter in particular: fused 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, further organic cobuilders (see below) and phosphonates can be contained as organic co-builders.

Organic builder substances which can be used 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 that such use is not objectionable for ecological reasons, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures of these. In addition to the salts, the acids themselves 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 of the respective acid form, which were basically determined 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 similarity to the polymers under investigation, provides realistic molecular weight values.

Copolymers of polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid, are also suitable. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 100000 g / mol.

To improve the water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers. Biodegradable polymers composed of more than two different monomer units are also particularly preferred, 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-alkylallylsulphonic 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.

Further 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 polyol carboxylic 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 more suitable co-builders, preferably in the form of its sodium or magnesium salts, further iminodisuccinate (IDS) and derivatives thereof, for example Hydroxyiminodisuccinate (HDIS) and also 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 hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. 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, the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. They are preferably in the form of the neutrally reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. From the class of phosphonates, HEDP is preferably used as the builder. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, it can be preferred to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the phosphonates mentioned. In addition, all compounds which are able to form complexes with alkaline earth metal ions can be contained in the particulate agents as co-builders.

Acids

One or more acids and / or their salts can be included to increase the cleaning performance against lime. The acids are preferably made 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 comprising 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

The detergent blocks according to the invention can also contain alkalis. The bases used in the agents according to the invention are preferably those from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide. In addition, however, ammonia and / or alkanolamines with up to 9 carbon atoms in the molecule can also be used, preferably the ethanolamines, in particular monoethanolamine.

Complexing agents

Complexing agents (// VC / Chelating Agents), also called sequestering agents, are ingredients that are able to complex and inactivate metal ions in order to prevent their adverse effects on the stability or appearance of the cleaning agents according to the invention, for example cloudiness. On the one hand, it is important to complex the calcium and magnesium ions of 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.

The following complexing agents, designated according to INCI, are suitable, for example: Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acycloon, Dipotassium Diphosphane, Pentamethylene Phosphonic EDacycloid, Dipotassium Diphosphate , Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene, Pentasodium Phosphonate Ethylene Phosphonate, Pentasodium Ethylenediamine Triphosphate, Pentasodium Phosphonethine, Pentasodium Phosphonethate, Pentasodium Phosphonetine Tetramate 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-phosphate, Sodium Sodium metasilicates, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, sodium trimetaphosphates, TEA-EDTA, TEA-polyphosphate, tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium etidronate, Tetrasodium Pyrophosphate, tripotassium EDTA, trisodium dicarboxymethyl alaninates, Trisodium EDTA , Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

Bleach

According to the invention, bleaches can be added to the cleaning product. Suitable bleaching agents include peroxides, peracids and / or perborates, sodium percarbonate or phthalimidoperoxyhexanoic acid is particularly preferred. Chlorine-containing bleaches 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 vapors, but can be used in alkaline cleaning agents. In addition to the bleaching agent, a bleach activator may also be required under certain circumstances.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, give 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, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferred. 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, especially 2 to 8% by weight and particularly preferably 2 to 6% by weight, each based on the total weight of the bleach activator-containing agents used.

Auxiliaries and additives

In addition to the components mentioned above, the agent according to the invention can contain one or more other auxiliary substances and additives which are customary in cleaning agents for hard surfaces in particular. These include, for example, organic adjusting agents (in particular sugar, sugar alcohols, glycerine, glycols and polymers of the same), hydrophobicity mediators (such as e.g. Paraffin), UV stabilizers, perfume oils, antimicrobial agents, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ^® AGS from BASF, or mixtures comprising, for example, the Euperlane ^® from BASF), more opacifiers, colorants.. , Corrosion inhibitors, bitter substances, preservatives (for example the technical 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), also known as Bronopol, which, for example, as Myacide ^® BT or Boots Bronopol BT from the company Boots is commercially available, or mixtures containing bronopol such as Preventol ^® (ex Lanxess) or Parmetol ^® (ex Schülke & Mayr)), disinfectants, enzymes, pH adjusters, fragrances and additives that improve 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 nsate, 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, glycerine, urea, quaternized hydroxyethyl cellulose), additives for Improvement of the drainage and drying behavior or for stabilization. These auxiliaries and additives are contained, in particular, in amounts of usually 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. It can contain d-limonene 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). Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil, for example, can be used as such for the purposes of this invention. Also suitable are muscatel sage oil, chamomile oil, lavender oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden 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. Further fragrances usually used in detergents and cleaning agents are also suitable for use in the cleaning agent block according to the invention, for example further essential oils, esters, alcohols, aldehydes or terpenes.

Antimicrobial agents

Disinfection and sanitation represent a particular form of cleaning. In a corresponding particular 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.

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

According to the invention, for example, antimicrobial active ingredients from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their are suitable Derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores, active chlorine cleavage 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 surface-active compounds, 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, antimicrobially effective essential oils can be used, which at the same time ensure that the cleaning product is scented. Particularly preferred antimicrobial active ingredients are, however, 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 cleaning agent products according to the invention. The substances mentioned for the antimicrobial active ingredients can essentially be used as such.

Dyes

The cleaning agent product according to the invention can contain one or more dyes (INCI colorants) as further ingredients. Both water-soluble and oil-soluble dyes can be used as dyes, the compatibility with others on the one hand Ingredients, such as bleaching agents, 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 in accordance with INCI: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Phosphane, Nitromethylsuccinate, Potassium oxyethyl 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 are primarily used to control the consumption of the agent during use so that the intended service life is adhered to. 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, are preferably suitable as regulators.

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 solidified gel or in those from the core-shell Type in which an enzyme-containing core is covered with a protective layer that is impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by pouring or rolling granulation or in fluid-bed processes. Such granulates are advantageously low in dust, for example through the application of polymeric film-forming agents, and, owing to the coating, are stable in storage. In addition, enzyme stabilizers can be present in enzyme-containing cleaning products in order to protect an enzyme contained from damage such as, for example, inactivation, denaturation or disintegration due to physical influences, oxidation or proteolytic cleavage. Particularly suitable enzyme stabilizers, depending on the enzyme used, are: 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 a 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 the acids mentioned; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; as well as reducing agents and antioxidants such as sodium sulfite and reducing sugars. Further 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 by means of conventional 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. Preference is given to buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents). Particularly preferred buffer substances are citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate 2 H2O and tripotassium citrate H _{2 O.} The invention is described in more detail with reference to the following drawings and examples:

FIG. 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.

FIG. 2 shows the cleaning robot 1 including the cleaning cloth 10 in a view from the side. The cleaning agent is conveyed out of the cleaning agent tank 30 and first applied to the cleaning cloth 10 and then directly by means of the cleaning cloth 10 to the surface 5 to be cleaned. In the case of automatic surface cleaning by means of the cleaning robot 1, the cleaning agent is thus applied to the hard surface 5 when the robot moves, the wiping process taking place essentially at the same time as the cleaning agent is applied. In contrast to manual cleaning, the surfactants only have little time to accumulate on the surface of the cleaning agent film that has formed and thus to reduce the surface tension. In other words, during the automatic cleaning process, the cleaning agent generally 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 already taken place shortly after film formation.

The following table 1 shows the concentrated composition used:

Table 1 : The quantities 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 value in the (diluted) composition used was pH = 10.6.

Table 2:

The cleaning agent listed here as an example shows a surface tension of about 34 mN / cm when measured dynamically at 23 ° C. with a surface age of 0.3 seconds and is thus 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. Thus, early after film formation, there is a sufficiently strong reduction in surface tension and thus a preferred cleaning performance. However, the stated composition is only to be understood as an example and not restrictive. By changing individual constituents and dilution parameters of other compositions, the person skilled in the art will be able to adjust the surface tension (lowering the surface tension) according to the invention.

Claims

1. Cleaning robot (1) comprising a cleaning cloth (10) and a cleaning agent, wherein the cleaning robot (1) is designed to guide the cleaning cloth (10) over a hard surface (5) and the cleaning agent comprises at least one surfactant, characterized in that, 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, with dynamic measurement at 23 ° C. and a surface age of 0.3 seconds.

2. cleaning robot (1) according to claim 1, wherein the cleaning robot (1) is designed, the cleaning cloth (10) 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 Guide surface (5).

3. Cleaning robot (1) according to claim 1 or 2, wherein the change in the surface tension of the cleaning agent with dynamic measurement at 23 ° C is at least 2 mN / cm, preferably at least 5 mN / cm, within a surface life of 0.3 seconds.

4. Cleaning robot (1) according to one of the preceding claims, wherein the reduction in the surface tension of the cleaning agent with dynamic measurement at 23 ° C is at least 3 mN / cm, more preferably at least 5 mN / cm within a surface life of 0.3 seconds.

5. Cleaning robot (1) according to one of the preceding claims, wherein the cleaning robot (1) is designed to convey the cleaning agent out of a cleaning agent tank (30) and to 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 with dynamic measurement at 23 ° C with a surface age of 0.3 seconds, preferably has a surface tension of at most 40 mN / cm at most 38 mN / cm and particularly preferably at most 35 mN / cm.

7. A method for cleaning a surface using a cleaning robot according to one of the preceding claims, wherein the cleaning cloth (10) 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 (5) is performed.