EP3835399B1 - Hard surface cleaning composition - Google Patents

Description

The present invention relates to the use of a composition for cleaning a glass surface, in particular for reducing scratches on glass surfaces. Compositions for cleaning hard surfaces comprising a surfactant system, ie at least one surfactant, are known. Hard surfaces may show signs of wear over time. In particular, scratches form on the surface over time. These are perceived as annoying by the consumer. In addition, dirt can easily accumulate in the scratches, which can sometimes be difficult to remove. In addition, hard surfaces quickly stain when they come into contact with water. Stains and streaks can appear on hard surfaces, especially with hard water.

Compositions are known from the prior art which are used to reduce glass corrosion in automatic dishwashing, which should be mentioned U.S. 10,301,577 B2 , U.S. 9,994,796 B2 , U.S. 2016/186098 A1 , U.S. 2011/268802 A1 . Further compositions for cleaning glass surfaces are described in EP 3 020 793 A1 disclosed.

It was therefore the task to provide an agent for cleaning hard surfaces, which reduces the severity of scratches, in particular with regard to the depth of the scratches, when viewed without clouding occurring and, if possible, also imparting water-repellent properties to the surface. to prevent staining and/or streaking, especially when cleaning with hard water.

• ein Tensidsystem; ein erstes Polymer; und ein zweites Polymer, wobei
• das erste Polymer ein Polyethylenimin ist, und wobei das zweite Polymer ein Acrylat basiertes Polymer ist.

The invention relates to the use of a composition for cleaning a glass surface, comprising the step of applying the composition to a glass surface with a spray bottle, the composition having:

• a surfactant system; a first polymer; and a second polymer, wherein
• the first polymer is a polyethyleneimine, and the second polymer is an acrylate-based polymer.

In one embodiment, the first polymer is Lupasol PN60 or Polyquart PN60 (BASF).

The first polymer is preferably present in the composition in an amount of 0.001% to 0.5% by weight, more preferably in an amount of 0.001 to 0.1% by weight.

The first polymer is preferably in an amount of less than 0.5% by weight, in particular in an amount of less than 0.1% by weight, in particular in an amount of less than 0.05% by weight in the composition included.

An acrylate-based polymer is understood to mean a polymer which comprises acrylic acid or acrylic acid derivatives as monomer units, in particular acrylic acid and/or methacrylic acid monomers.

According to a preferred embodiment, the use of the composition is described, wherein the second polymer is present in an amount of 0.01% to 0.5% by weight, more preferably in an amount of 0.01 to 0.25% by weight. -% is included in the composition.

According to a preferred embodiment, the use of the composition is described, wherein
the surfactant is an anionic surfactant. Fatty alcohol sulfates or fatty alcohol sulfonates, alkane sulfonates or alkane sulfates or else sarcosinates are particularly preferred. In particular, the anionic surfactant is a fatty alcohol sulfate and/or fatty alcohol sulfonate and/or a lauroyl sarcosinate.

According to a preferred embodiment, the anionic surfactant is contained in an amount of 0.001% by weight to 10% by weight, more preferably in an amount of 0.001% by weight to 5% by weight, more preferably in an amount of 0.001% wt% to 1 wt%, more preferably in an amount of 0.01 wt% to 0.5 wt%.

According to a preferred embodiment, the use of the composition is described, wherein the pH of the composition is between 7 and 11, preferably 8-10. A pH of about 9 is particularly preferred.

According to a preferred embodiment, the use of the composition is described, wherein the second polymer is an acrylates/methacrylamidopropyl copolymer. In one embodiment, the second polymer is Polyquart 149 CP Acrylate/Methacrylamidopropyl-ClNa.

In particular, the use for cleaning flat and flat glass surfaces such as glass tables and glass windows is described.

The use of the composition according to the invention for cleaning a glass surface comprises the steps:
applying the composition to a glass surface; wherein the composition is applied with a spray bottle. The composition can then be spread on the surface, preferably with a textile, for example a wipe.

The use of the composition according to the invention for reducing scratches on a glass surface is also described.

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. polymers are 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 their derivatives which can be obtained, 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 can be found in 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 , is published and contains more than 9,000 INCI designations as well as 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 agent. 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.

Sophorolipids can also be used as further preferred surfactants. These are to be assumed to be anionic in the alkaline range and are therefore to be understood as anionic surfactants in the context of the present application.

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.

Examples of suitable amphoteric surfactants are 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. 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 0.001 to 10% by weight and particularly preferably 0.005 to 2.0% 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 preferred total amount of 0.1 to 2% 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. In addition, the solvents allow fetuses to be released.

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.

Very particular preference is given to using 1-butoxypropan-2-ol and/or ethanol and/or isopropanol 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.

Among the silicates are crystalline, layered sodium silicates of the general formula NaMSi _x O _2x+1 yH2O, 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 is 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 represent sodium and/or potassium ions, soda (sodium carbonate) and potash (potassium carbonate) are therefore 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 one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ in addition to higher-molecular 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, saccharic 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. For polymeric polycarboxylates The molar masses given 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. 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 to be particularly suitable. 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, especially 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 present 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. In particular, acids are used to adjust the pH correctly.

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, Sod ium 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-Polyphosphate, 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.

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 skin-feel-improving or skin-care additives (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 hydrolysates, 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 0.001 to 10% by weight, in particular 0.05 to 1% 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). For example, pine, citrus, jasmine, patchouli, rose or ylang-ylang oil can be used as such 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 greatest possible elimination of all - 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 maintained. 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.

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. A pH of about 9 is preferred.

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.

Experimental data are presented below. The information relates to the quantity of the specified raw material. If the proportion of the active substance deviates from 100%, a corresponding statement is made. V1 v2 E1 E2 E3 Water to 100 to 100 to 100 to 100 to 100 ethanol 4 4 4 4 4 1 butoxypropane 2ol 0.6 0.6 0.6 0.6 0.6 Fatty alcohol sulfate-Na C12-14 0.05 0.05 0.05 0.05 0.05 Ammonia, aqueous solution 0.025 0.025 0.025 0.025 0.025 perfume 0.01 0.01 0.01 0.01 0.01 Polymer 2: Acylate based polymer 22% 0.9 - 0.3 0.3 0.3 Polymer 1 polyethyleneimine 40% - 0.6 0.1 0.05 0.02 pH 9 9 9 9 9

V1 and V2 have only a single polymer, while the compositions E1 to E3 have two polymers, one of the polymers being a polyethyleneimine and the second polymer being an acrylate-based polymer. The first polymer was Polyquart PN60. The second polymer was Polyquart 149

Glass surfaces were scratched in a targeted and automated manner in order to ensure that the test results could be compared. This was checked microscopically. The compositions were then applied evenly to the glass panels and the glass panels were again examined microscopically and rated for scratch removal, transparency and water repellency versus untreated control panels. V1 v2 E1 E2 E3 scratch removal - o + ++ + transparency - - + + ++ water repellency ++ - + ++ ++

The more "+" there are, the better the performance of the composition with respect to the corresponding property. The more "-" there are, the poorer the performance of the composition on the corresponding property. An "o" denotes an average value of the performance of the respective composition with respect to the corresponding property.

Scratch removal describes the property of a composition to remove the previously created scratches or to reduce their severity, in particular with regard to the depth of the scratches, when viewed.

Transparency describes the property of removing scratches or reducing their severity, in particular with regard to the depth of the scratches, when viewed without clouding occurring.

Water repellency describes the property of modifying the surface in such a way that a kind of lotus effect occurs.

The compositions E1, E2 and E3 have significantly better values than the compositions V1 and V2.

C1 (only polymer 2) showed good water repellency, but only poor scratch removal, with the scratches also becoming milky/opaque in color.

Compositions with polyethyleneimines (PEI) for cleaning surfaces are known per se. A scratch removal ability has now been found in the above tests for C2 (only polymer 1: PEI). However, the water-repellent properties were significantly worse compared to C1.

In contrast, the composition E1 according to the invention shows consistently good scratch removal and transparency. The water repellency was also good. Scratch removal and transparency were further improved with E2 and E3 compared to E1, while the water-repellent properties were further improved at the same time.

The following additional compositions were obtained: E4 E5 E6 E7 E8 E9 Water Ad 100% Ad 100% Ad 100% Ad 100% Ad 100% Ad 100% ethanol 4 4 4 4 4 isopropanol 4 1 butoxypropane 2ol 0.6 0.6 0.6 0.6 0.6 Fatty alcohol sulfate-Na C12-14 0.05 0.03 0.03 0.03 0.05 Alkanes sulfonate-Na C13-17 sec 0.18 0.18 Lauroylsarcosinate-Na,N- 0.08 0.08 Ammonia, aqueous solution 0.025 0.025 0.025 0.025 perfume 0.01 0.01 0.01 0.01 Polymer 2: Acylate based polymer 22% 0.3 0.3 0.3 0.3 0.3 0.3 Polymer 1 polyethyleneimine 40% 0.05 0.05 0.05 0.05 0.05 0.05 pH 9 9 9 9 9 9

The compositions E4 to E9 given above were found to be superior to the comparison compositions C1 and C2 with regard to scratch removal and simultaneous transparency. E4 to E9 all showed excellent water repellency (++).

In addition, the above-mentioned compositions with amine oxide and a fatty alcohol ethoxylate with 7 EO units as additional surfactants were provided in an amount of 0.2% by weight in each case.

Claims (7)

1. Use of a composition for cleaning a glass surface comprising the step of applying the composition to a glass surface with a spray bottle,

   the composition comprising:

   a surfactant system;

   a first polymer; and

   a second polymer, wherein

   the first polymer is a polyethyleneimine, and wherein

   the second polymer is an acrylate-based polymer.
2. Use according to claim 1, wherein the second polymer is present in the composition in an amount of from 0.01 wt% to 0.5 wt%, more preferably in an amount of from 0.01 to 0.1 wt%.
3. Use according to any one of the preceding claims, wherein the first polymer is present in an amount of less than 0.1% by weight in the composition.
4. Use according to any one of the preceding claims, wherein
   the surfactant is an anionic surfactant.
5. Use according to any one of the preceding claims, wherein the pH of the composition is between 7 and 11, preferably 8 to 10.
6. Use according to any one of the preceding claims, wherein
   the second polymer is an acrylate/methacrylamidopropyl copolymer.
7. Use according to any one of the preceding claims, wherein the composition is used for cleaning a glass surface and simultaneously reducing scratches on the glass surface.