EP2970828B1 - Cleaners for hard surfaces comprising phosphoric acid esters of a polyether-modified alkyl alcohol - Google Patents

Description

The present invention relates to hard surface cleaners containing surfactants and phosphoric acid esters of a polyether-modified alkyl alcohol and to their use for hard surface cleaning and hard surface gloss.

Conventional gloss additives for hard surface cleaning formulations are based on wax / acrylic polymer additives that do not support cleaning. Such care products, which produce gloss while having a repair effect, are often provided as waxy compositions and require the application and subsequent, if necessary, repeated polishing in order to achieve a gloss and repair effect. Such agents leave a solid film that seals the surface. In particular, on floor coverings, however, such compositions can lead to visible roads due to different mechanical stress. As a result, uneven surfaces are smoothed, and although a gloss is produced, the surface is also visibly changed in its properties. In most cases, treated just matted or textured surfaces look painted and not refreshed and new. Currently available formulations are expensive and the ingredients are often not water soluble.

The publication US 6,403,546 B1 discloses compositions for cleaning and enhancing shine on floors wherein a plasticizer causes both cleansing and increased gloss, and the plasticizer is tributoxyethyl phosphate.

In order to simplify the application, it would be desirable to provide additives for general purpose cleaners which, even at low levels without polishing, cause a gloss and repair effect on hard surfaces such as ceramics, porcelain, stone, glass and laminate with no streaks or stickiness Leave surfaces.

• besitzt, wobei R¹, R², R³ und R⁴ gleich oder verschieden sein können und ausgewählt werden aus R-O-(SO)_a-(EO)_b-(PO)_c-(BO)_d- und -OH,
  wobei,
• SO =
  
• EO = -CH₂-CH₂-O-,
• PO = -CH-CH₃-CH₂-O- und
• BO = -CH(CH₂CH₃)-CH₂-O- und
• mit der Maßgabe, dass mindestens einer, bevorzugt mindestens 2, insbesondere 3, besonders bevorzugt 4 der Reste R¹, R², R³ und R⁴ nicht OH sind,
  wobei
• a = 1 bis 20, bevorzugt 2,2 bis 10, mehr bevorzugt 2,5 bis 7, besonders bevorzugt 3 bis 5,
• b = 1 bis 100, bevorzugt 3 bis 40, mehr bevorzugt 4 bis 15, besonders bevorzugt 8 bis 12,
• c = 0 bis 10, insbesondere 0,
• d = 0 bis 10, insbesondere 0 und
• R ausgewählt wird aus verzweigten oder linearen, gesättigten oder ungesättigten Alkylresten mit 8 bis 20 Kohlenstoffatomen, bevorzugt lineare, gesättigte mit 8 bis 16, insbesondere 10 bis 14, Kohlenstoffatomen.

This object is achieved by a surfactant-based cleaning agent for hard surfaces containing as a gloss additive at least one phosphoric acid ester of a polyether-modified alkyl alcohol or its salt in an amount of 0.1 to 3 wt.%, Wherein the phosphoric acid ester of a polyether-modified alkyl alcohol general formula 1:

• wherein R ¹ , R ² , R ³ and R ^{4 may be the} same or different and are selected from RO- (SO) _a - (EO) _b - (PO) _c - (BO) _d - and -OH,
  in which,
• SO =
  
• EO = -CH ₂ -CH ₂ -O-,
• PO = -CH-CH ₃ -CH ₂ -O- and
• BO = -CH (CH ₂ CH ₃ ) -CH ₂ -O- and
• with the proviso that at least one, preferably at least 2, in particular 3, more preferably 4 of the radicals R ¹ , R ² , R ³ and R ^{4 are} not OH,
  in which
• a = 1 to 20, preferably 2.2 to 10, more preferably 2.5 to 7, particularly preferably 3 to 5,
• b = 1 to 100, preferably 3 to 40, more preferably 4 to 15, particularly preferably 8 to 12,
• c = 0 to 10, in particular 0,
• d = 0 to 10, especially 0 and
• R is selected from branched or linear, saturated or unsaturated alkyl radicals having 8 to 20 carbon atoms, preferably linear, saturated with 8 to 16, in particular 10 to 14, carbon atoms.

An advantage of the invention is that the phosphoric acid esters, even if they are contained in low concentrations in cleaning agents, cause a gloss effect. Another advantage of the invention is that the phosphoric acid ester-containing detergents of the invention leave neither a lubricating or iridescent effect nor a sticky film on the surface. Another advantage of the invention is that the phosphoric acid ester-containing cleaning agents can also be used with hard water. Another advantage of the invention is that the detergents containing the phosphoric acid esters reduce staining on surfaces when drying formulations and the drying times are not significantly prolonged compared to detergents that do not contain phosphoric acid esters. Yet another advantage of the invention is that aqueous detergents containing the phosphoric acid esters and surfactants have very good stability.

The detergent formulations according to the invention containing the phosphoric acid esters according to the invention are described below by way of example, without the invention being restricted to these exemplary embodiments. Given below, ranges, general formulas, or classes of compounds are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by removing individual values (ranges) or compounds can be. Be in the context of the present invention, compounds such. As polyethers, which may have several units repeatedly, they 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, averaged over all corresponding compounds.

In the context of the present invention are fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms. The former are particularly preferred for their vegetable base as based on renewable raw materials for environmental reasons, but without limiting the teaching of the invention to them. In particular, the oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.

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

Substances which also serve as ingredients of cosmetic products are referred to below, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English, plant ingredients are listed only after Linne in Latin, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names 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 , which publishes more than 9,000 INCI names and references to more than 37,000 trade names and technical names, including related distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes, such as polymeric ethers, and one or more functions, such as surfactants-cleansing agents, which are further explained and discussed below possibly also referred to.

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

Unless otherwise stated, amounts given are percentages by weight (% by weight) of the total composition. These percentages refer to active contents.

In various embodiments of the invention preferably 2, more preferably 3, most preferably 4 of the radicals R ¹ , R ² , R ³ and R ^{4 are} RO- (SO) _a - (EO) _b - (PO) _c - (BO) _d - , R may be unequal or the same in the radicals R ¹ , R ² , R ³ and R ⁴ .

Particularly preferred phosphoric acid esters according to the invention are characterized in that a = 2.5 to 5, b = 4 to 12 and c = d = 0. In further preferred embodiments, a = 3.0 to 3.3, b = 4 to 11, for example 4, 6, 10 or 11, preferably 8 to 11, and c = d = 0.

Particularly advantageous phosphoric acid esters according to the invention are characterized in that R is selected from linear, saturated alkyl radicals having 8 to 16, in particular 10 to 14, carbon atoms. Most preferably, R is a mixture of linear, saturated alkyl radicals having 12 and 14 carbon atoms.

Depending on the pH of the cleaning agent, the phosphoric acid esters can also be present in partially or completely neutralized form as salts. In particular embodiments, alkali metal and alkaline earth metal ions and optionally substituted ammonium ions can serve as counterions in various embodiments.

The phosphoric acid esters contained in the detergents according to the invention can be prepared by processes known to those skilled in the art, as described, for example, in US Pat EP0940406 are described. The phosphoric acid esters according to the invention are preferably prepared by the process described below. Essentially, the process comprises alkoxylation steps. Corresponding instructions for carrying out alkoxylations are found by the person skilled in the art, for example in US Pat DE10054462 , of the WO1992012950 and the WO2005026273 ,

• A) Bereitstellen von mindestens einem verzweigten oder linearen, gesättigten oder ungesättigten Alkylalkohol mit 8 bis 20 Kohlenstoffatomen oder Mischungen mehrerer solcher Alkylalkohole,
• B) Umsetzen mit, bezogen auf den mindestens einen Alkylalkohol, 2,2 bis 10 Mol, bevorzugt 2,5 bis 7 Mol, besonders bevorzugt 3 bis 4 Mol, Styroloxid bei einer Temperatur von 80 bis 150 °C, bevorzugt 100 bis 140 °C, insbesondere 110 bis 130 °C, und einem Druck von 0,4 bis 1,2 bar, bevorzugt 0,6 bis 1 bar, besonders bevorzugt 0,7 bis 0,9 bar,
• C) Umsetzen mit, bezogen auf den mindestens einen Alkylalkohol, 3 bis 20 Mol, bevorzugt 4 bis 15 Mol, besonders bevorzugt 8 bis 12 Mol, Ethylenoxid bei einer Temperatur von 80 bis 130 °C, bevorzugt 100 bis 125 °C, insbesondere 110 bis 120 °C, und einem Druck von 0,5 bis 6,0 bar, bevorzugt 0,6 bis 3,0 bar, besonders bevorzugt 0,8 bis 1,5 bar,
• D) Umsetzen mit, bezogen auf den mindestens einen Alkylalkohol, 0 bis 10 Mol, bevorzugt 0 Mol, Propylenoxid bei einer Temperatur von 80 bis 130 °C, bevorzugt 100 bis 125 °C, insbesondere 110 bis 120 °C, und einem Druck von 0,5 bis 6,0 bar, bevorzugt 0,6 bis 3 bar, besonders bevorzugt 0,8 bis 1,5 bar,
• E) Umsetzen mit, bezogen auf den mindestens einen Alkylalkohol, 0 bis 10 Mol, bevorzugt 0 Mol, Butylenoxid bei einer Temperatur von 80 bis 130 °C, bevorzugt 100 bis 125 °C, insbesondere 110 bis 120 °C, und einem Druck von 0,5 bis 6,0 bar, bevorzugt 0,6 bis 3,0 bar, besonders bevorzugt 0,8 bis 1,5 bar,
• F) Umsetzen mit, bezogen auf den mindestens einen Alkylalkohol, 0,1 bis 1,0 Mol, bevorzugt 0,1 bis 0,5 Mol, besonders bevorzugt 0,2 bis 0,3 Mol Polyphosphorsäure P₄O₁₀ bei einer Temperatur von 50 bis 110 °C, bevorzugt 60 bis 100 °C, insbesondere 70 bis 90 °C, und einem Druck von 0,4 bis 1,2 bar, bevorzugt 0,6 bis 1 bar, besonders bevorzugt 0,7 bis 0,9 bar und gegebenenfalls
• H) Aufreinigen des erhaltenen Phosphorsäureesters.

The process for preparing phosphoric acid esters suitable for use in the detergents according to the invention comprises the process steps

• A) providing at least one branched or linear, saturated or unsaturated alkyl alcohol having 8 to 20 carbon atoms or mixtures of a plurality of such alkyl alcohols,
• B) Reacting with, based on the at least one alkyl alcohol, 2.2 to 10 mol, preferably 2.5 to 7 mol, particularly preferably 3 to 4 mol, of styrene oxide at a temperature of 80 to 150 ° C, preferably 100 to 140 ° C, in particular 110 to 130 ° C, and a pressure of 0.4 to 1.2 bar, preferably 0.6 to 1 bar, particularly preferably 0.7 to 0.9 bar,
• C) Reacting with, based on the at least one alkyl alcohol, 3 to 20 mol, preferably 4 to 15 mol, particularly preferably 8 to 12 mol, of ethylene oxide at a temperature of 80 to 130 ° C, preferably 100 to 125 ° C, in particular 110 to 120 ° C, and a pressure of 0.5 to 6.0 bar, preferably 0.6 to 3.0 bar, particularly preferably 0.8 to 1.5 bar,
• D) reacting with, based on the at least one alkyl alcohol, 0 to 10 mol, preferably 0 mol, propylene oxide at a temperature of 80 to 130 ° C, preferably 100 to 125 ° C, in particular 110 to 120 ° C, and a pressure of 0.5 to 6.0 bar, preferably 0.6 to 3 bar, more preferably 0.8 to 1.5 bar,
• E) Reacting with, based on the at least one alkyl alcohol, 0 to 10 mol, preferably 0 mol, butylene oxide at a temperature of 80 to 130 ° C, preferably 100 to 125 ° C, in particular 110 to 120 ° C, and a pressure of 0.5 to 6.0 bar, preferably 0.6 to 3.0 bar, more preferably 0.8 to 1.5 bar,
• F) Reacting with, based on the at least one alkyl alcohol, 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol, particularly preferably 0.2 to 0.3 mol of polyphosphoric acid P ₄ O ₁₀ at a temperature of 50 to 110 ° C, preferably 60 to 100 ° C, in particular 70 to 90 ° C, and a pressure of 0.4 to 1.2 bar, preferably 0.6 to 1 bar, particularly preferably 0.7 to 0.9 bar and if necessary
• H) Purification of the resulting phosphoric acid ester.

The process steps D), E) and H) of the process are optional, this being expressed in process step D) and E) by the term "reaction with 0 mol" of alkylene oxide.

The alcohol provided in process step A) of the process is preferably selected from linear, saturated primary alkyl alcohols having 8 to 16, in particular 10 to 14, carbon atoms or mixtures of such alcohols, particularly preferably the alcohol is a mixture of linear, saturated primary alkyl alcohols with 12 and 14 carbon atoms.

In the process steps B to E of the process, the alkoxylation is carried out in the presence of catalysts, preferably basic (alkaline) catalysts such as Alkalimethanolaten, sodium hydroxide and / or potassium hydroxide. Particular preference is given to sodium and potassium methoxide, which are preferably used advantageously in amounts of catalyst of from 0.1 to 5.0% by weight, preferably from 0.2 to 0.8% by weight, calculated as the solids and based on the reaction product obtained.

It is advantageous and thus preferred to carry out the process anhydrous, wherein the term "anhydrous" in connection with the present invention, an amount of less than 0.5 wt .-% water based on the total reaction mixture is understood. It is likewise advantageous to carry out the process solvent-free, therefore without the addition of solvents.

A particularly preferred process is characterized in that in process step B) 3 to 4 mol, in process step C) 8 to 12 mol and in process step D) and E) 0 mol-in each case based on the alkyl alcohol - of the respective alkylene oxide are used.

The phosphoric acid esters which can be prepared by the process can be mixtures of phosphoric acid esters which, in addition to the above-described phosphoric acid esters of the general formula 1, also contain those phosphoric acid esters in which at least one of the P-O-P bond has been cleaved.

In the cleaning agents according to the invention, the phosphoric acid esters in an amount of 0.1 to 3 wt .-%, preferably 0.3 to 0.9 wt .-%, more preferably about 0.6 wt .-% based on the ready-to-use detergent ,

Detergents according to the invention are in particular aqueous formulations, the term "aqueous" meaning a water content of at least 30, preferably 80, more preferably 90% by weight of water, based on the total formulation.

In addition to the phosphoric acid esters, the cleaning agents according to the invention contain at least one surfactant, preferably selected from the group consisting of anionic, nonionic, cationic and amphoteric surfactants and mixtures thereof.

The surfactants contained in the detergent may be any surfactant known for use in detergents. In a preferred embodiment, the at least one surfactant is selected from the group of nonionic surfactants, anionic surfactants, amphoteric surfactants, cationic surfactants and mixtures thereof.

Nonionic surfactants in the invention may 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, in particular the glycerides, such as alkyl polyglycosides and fatty acid glucamides. Particular preference is given to the alkylpolyglycosides, in particular the alkylpolyglucosides, the alcohol particularly preferably 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, the fatty alcohol alkoxylates (fatty alcohol polyglycol ethers) are also preferred, especially with ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C _{8-22 -alcohols} having a degree of alkoxylation up to 30, preferably ethoxylated C _{12- 22} fatty alcohols having 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.

Additionally or independently of the nonionic surfactant, the cleaning agent according to the invention may contain at least one anionic surfactant. Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic 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, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

Preferred in the context of the present invention are the linear alkylbenzenesulfonates, 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, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, in the context of the present invention preferably with longer-chain alcohols. As a rule, a complex mixture of addition products of 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 is the use of 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 alkylbenzenesulfonates, preference is given in particular to those having about 12 C atoms in the alkyl moiety, for example linear sodium C _10-18 -alkylbenzenesulfonate. Preferred olefin sulfonates have a carbon chain length of 14 to 16.

The anionic surfactants are preferably used as sodium salts, but may also be present as other alkali metal or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, eg Dodecylbenzenesulfonic.

In addition to the previously mentioned types of surfactant, the agent according to the invention may also contain cationic surfactants and / or amphoteric surfactants.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO ^- , in which R ^{iii is} an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R ^iv and R ^{v are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyl-dimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -alkylamidopropyl-dimethylcarboxymethylbetain. 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 are} four identical or different, in particular two long and two short-chain, alkyl radicals and X ^{- are} an anion, in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. Through the use of quaternary surface-active compounds with antimicrobial action, the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.

The total surfactant content of such, preferably aqueous, detergent formulation is preferably 0.1 to 40 wt .-% and particularly preferably 0.1 to 12.0 wt .-%, based on the total formulation.

Other ingredients commonly included in hard surface cleaners may also be included in the cleanser. This group of other potential ingredients includes, but is not limited to, acids, bases, organic solvents, salts, chelants, fillers, builders, bleaches, and mixtures thereof.

Water-soluble salts

The cleaning agent according to the invention may further comprise one or more water-soluble salts in a total amount of from 0.1 to 75% by weight. These may 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, bicarbonates, nitrates, nitrites, phosphates and / or oxides of the alkali metals, alkaline earth metals, aluminum and / or transition metals; Furthermore, ammonium salts can be used. Particularly preferred are halides and sulfates of the alkali metals; Preferably, the at least one inorganic salt is therefore 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 the carboxylic acids. Preferably, the salts are 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 hard surface cleaning agent. In addition to water, in a preferred embodiment it may contain one or more further 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.

The solvents are used in the context of the teaching of the invention as needed in particular as a hydrotrope and viscosity regulator. They work solubilizing in particular for surfactants and electrolyte 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 with increasing amount of solvent. Finally, as the amount of solvent increases, the clouding and clearing point of the composition according to the invention decreases.

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

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

Exemplary solvents are the following according to INCI compounds: buteth-3, butoxy diglycol, 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, hexylenes glycol, isobutoxypropanol, isopentyldiol, isopropyl alcohol (isopropanol), 3-methoxybutanol, methoxydiglycol, methoxyethanol, methoxyisopropanol, methoxymethylbutanol, methoxy PEG- 10, methylal, methyl alcohol, methyl hexyl ether, methyl propanediol, 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 Pro pyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.

Also preferred are longer-chain polyalkylene glycols, in particular polypropylene glycols. Particularly preferred are about the PPG-400 or the PPG-450, but also Polypropylene glycols with larger chain lengths can be used in the context of this invention.

Preferably, the solvent is selected from the group comprising ethanol, propanol, isopropanol, ethylene glycol, butyl glycol, propylene glycol, polypropylene glycols and mixtures thereof.

The most preferred solvents are the C 2 and C 3 alcohols, ethanol, n-propanol and / or isopropanol, and the polyalkylene glycols, especially polypropylene glycols, in particular the PPG-400.

As a solubilizer, in particular for perfume and dyes, for example, alkanolamines can be used in addition to the solvents described above.

Builder

Furthermore, the cleaning agent according to the invention may contain all builders (builders) customarily employed in detergents and cleaners, in particular silicates, carbonates, organic cobuilders and also the phosphates.

Crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} · yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, are among the silicates is and preferred values for x are 2, 3 or 4. In addition, it is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ module of 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, to which also water glass is to be counted. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. Furthermore, zeolites can be used as builders, preferably zeolite A and / or P. However, zeolite X and mixtures of A, X and / or P are also suitable.

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

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates have particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate) in the detergent and cleaning industry the greatest importance. "Alkalimetallphosphate" is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight representatives. Suitable phosphates are the sodium dihydrogen phosphate, NaH ₂ PO ₄ , the disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , the trisodium phosphate, sodium tertiary phosphate, Na ₃ PO ₄ , the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , as well as by Condensation of NaH ₂ PO ₄ and KH ₂ PO ₄ , respectively, results in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and the chain-like types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

As organic cobuilders it is possible in particular to include polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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, methylglycinediacetic acid, sugar acids and mixtures thereof. In addition to the salts, the acids can also be used per se.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol. The molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of 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 molecular weight relative to free acids is generally 2000 to 100000 g / mol.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

Further preferred copolymers preferably contain 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 salts and derivatives thereof, besides polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C 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. Preferably, these are hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine-N, N'-disuccinate (EDDS), are further suitable co-builders, 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 may optionally also be present 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 aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs are preferably used as aminoalkane phosphonates Question. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth ions may be included as co-builders in the particulate agents.

acids

To enhance the cleaning performance against lime, one or more acids and / or salts thereof may be included. The acids are preferably produced from renewable raw materials. Suitable acids are therefore in particular organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and mixtures thereof. In addition, however, it is also possible to use the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or else sulfamic acid or mixtures thereof. 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 wt .-%, particularly preferably 0.2 to 5 wt .-%.

bases

In detergent blocks of the invention may continue to contain alkalis. Suitable bases in agents according to the invention are preferably those from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide. In addition, however, it is also possible to use ammonia and / or alkanolamines having up to 9 C atoms in the molecule, preferably the ethanolamines, in particular monoethanolamine.

complexing

Chelating agents ( INCI ), also called sequestering agents, are ingredients that are capable of complexing and inactivating metal ions to prevent their adverse effects on the stability or appearance of the detergents of the present invention, for example, clouding. On the one hand, it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents. In addition, the complexing agents support the cleaning effect.
For example, the following complexing agents designated as INCI are suitable: aminotrimethylene phosphonic acid, beta-alanines 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, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin , Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Chitosan Methylene Phosphonates, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonates, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphates, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasil ikat, 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.

bleach

According to the invention, bleaching agents can be added to the cleaning product. Suitable bleaching agents include peroxides, peracids and / or perborates, more preferably sodium percarbonate or phthalimidoperoxyhexanoic acid. On the other hand, chlorine-containing bleaching agents, such as trichloroisocyanuric acid or sodium dichloroisocyanurate, are less suitable for acidic detergents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents. Under certain circumstances, a bleach activator may be required in addition to the bleaching agent.

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

Auxiliaries and additives

In addition to the components mentioned so far, the composition according to the invention may contain one or more further auxiliary agents and additives customary in hard surface cleaners. These include, for example, organic stabilizers (especially sugars, sugar alcohols, glycerol, glycols and polymers thereof), hydrophobicity mediators (such as paraffin), UV stabilizers, perfume oils, antimicrobial agents, pearlescing agents (INCI Opacifying Agents, for example glycol distearate, eg Cutina® BASF AG, or mixtures containing this, for example the Euperlane® from BASF), further opacifiers, dyes, corrosion inhibitors, bitter substances, preservatives (for example the technical 2-bromo-2-nitropropane-1, also referred to as bronopol, 3-diol ( CAS 52-51-7 ), which is commercially available, for example, as Myacide® BT or Boots Bronopol BT from the company Boots, or Bronopolhaltige mixtures such as Preventol® ( ex Lanxess) or Parmetol® ( ex Schülke & Mayr)), disinfectants, enzymes, pH adjusters , Fragrances and skin feel-improving or skin-care additives (eg dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial hydrolyzate, various vegetable protein partial hydrolyzates, Protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soybean oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, algae extracts, etc., allantoin, AHA complexes, glycerol, urea, quaternized hydroxyethylcellulose ), Additives for improving the drainage and drying behavior or for stabilization. These auxiliaries and additives are contained in particular in amounts of usually not more than 5 wt .-%.

fragrances

The product according to the invention may contain one or more fragrances, preferably in an amount of from 0.01 to 10% by weight, in particular from 0.05 to 8% by weight, particularly preferably from 0.1 to 5% by weight. As a perfume component, d-limonene may be contained. In another embodiment, the detergent block according to the invention thereby contains a perfume of essential oils (also referred to as essential oils). Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil, for example, can be used as such in the context of this invention. Also suitable are Muskateller sage oil, chamomile oil, lavender oil, clove oil, balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil. Other fragrances usually used in detergents and cleaners are also suitable for use in the detergent block of the invention, such as other essential oils, esters, alcohols, aldehydes, or terpenes.

Antimicrobial agents

A special form of cleaning is disinfection and sanitation. In a corresponding particular embodiment of the invention, the cleaning agent therefore contains one or more antimicrobial agents, preferably in an amount of 0.01 to 1 wt .-%, preferably 0.02 to 0.8 wt .-%, in particular 0.05 to 0.5 wt .-%, particularly preferably 0 , 1 to 0.3 wt .-%, most preferably 0.2 wt .-%.

The terms disinfection, sanitation, antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention. While disinfection in the narrower sense of the medical practice means the killing of - in theory all - infectious germs, sanitation is to be understood as the greatest possible elimination of all - including the saprophytic - normally harmless to humans saprophytic - germs. Here, the extent of disinfection or sanitation depends on the antimicrobial effect of the applied agent, which decreases with decreasing content of antimicrobial agent or increasing dilution of the agent for use.

For example, antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention 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 releasing agents 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'-methylenebis (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-tetraazatetradecandiimidamide, 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 provide for a scenting of the cleaning product. 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 may also be included in detergent products of the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.

dyes

As further ingredients, the detergent product according to the invention may contain one or more dyes ( INCI Colorants). As dyes, both water-soluble and oil-soluble dyes can be used, on the one hand the compatibility with other ingredients, such as bleaches, is observed and on the other hand, the dye used should not be substantive to the metal and ceramic even with prolonged exposure. The dyes are preferably present in an amount of 0.0001 to 0.1 wt .-%, in particular 0.0005 to 0.05 wt .-%, particularly preferably 0.001 to 0.01 wt .-%, contained.

corrosion inhibitors

Suitable corrosion inhibitors ( INCI Corrosion Inhibitors) are, for example, the following named according to INCI : Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphates, Nitromethanes, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.

Abspülregulatoren

The designated as Abspülregulatoren substances serve primarily to control the consumption of funds during use so that the intended life is met. 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 having molecular weights between 10,000 and 50,000.

enzymes

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

Furthermore, enzyme-containing cleaning products may be present in enzyme-containing cleaning products in order to protect a contained enzyme from damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage. Suitable enzyme stabilizers, in each case depending on the enzyme used, are in particular: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, for example substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with reduced C-terminus), amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known in the art. Preference is given to using combinations of stabilizers, for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

PH value

The pH of the compositions according to the invention can be adjusted by means of customary pH regulators, for example citric acid or NaOH. Here, it is preferable that the agent has a pH in a range of 5 to 11.5, preferably 7 to 11.3.

In order to adjust and / or stabilize the pH, the composition according to the invention may further comprise one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 3 wt .-%, in particular 0.01 to 2 wt .-%, particularly preferably 0.05 to 1 wt .-%, most preferably 0.1 to 0.5 wt .-%, for example, 0.2 wt .-%. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (INCI chelating agents). Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate.2H ₂ O and tripotassium citrate H ₂ O.

Another object of the present invention is the use of the cleaning agent according to the invention for the production of gloss on a surface, preferably on a hard surface, which is particularly preferably not absorbent. In the use according to the invention, paper is preferably excluded.

The use according to the invention on surfaces is particularly suitable for hard surfaces, such as floors, including tiles, laminates, parquet, cork floors, marble, stone and porcelain stoneware floors, and household ceramics such as WCs, sinks, bidets, shower trays and bathtubs, but also for doorknobs, Fittings, sinks made of ceramic or stainless steel, furniture such as tables, chairs, shelves, shelves, windows, cookware, crockery and cutlery.

Also encompassed by the present invention is a method of producing gloss on a surface, preferably on a hard surface, which is particularly preferably nonabsorbent. The method includes applying the detergent of the invention to the surface.

In the context of the use according to the invention or the method according to the invention, the application of the cleaning agent by pouring / pouring, spraying or otherwise wetting the surface with the liquid detergent or a solution of the detergent, preferably in water, if it is a solid detergent, take place. The cleaning agent can be applied, for example, with a brush, a sponge or a cloth and then rubbed. After application, excess quantities can be taken up with a sponge or cloth and the surface then dried in air.

Examples Example 1: Gloss and repair effect on different surfaces

The gloss and repair effect of 0.6 wt .-% of a polymer according to formula I with a = 3.3, b = 10, c = d = 0 and R = C12-C14 (polymer A) in a nonionic and an anionic Base formulation according to Table 1 was tested on three different substrates, white tiles, black tiles and laminate. The tiles were damaged by the repeated use of alkaline cleaners or abrasives (micro scratches). Table 1: Basic formulations, the amounts of all components are given in wt .-% active substance component Nonionic base recipe Anionic base recipe C12-C18 fatty alcohol ethoxylate (7EO) 4.0 1.0 citric acid monohydrate 0.4 0.6 soda 0.2 0.2 ethanol 2.0 2.0 alkylbenzenesulfonate - 2.85 Fatty alcohol ethoxylate (5 EO) - 1.0 Palm kernel oil fatty acids - 0.4 NaOH - 0.73 Auxiliaries and additives 0.08 0.78 water Ad 100 Ad 100 PH value 7 10

1. 1. 5 mL der verdünnten Rezeptur (12g/l, Leitungswasser) wurden auf ein Tuch aufgetragen, das in einem Rahmen fixiert war
2. 2. Das Tuch wurde dann mit einer "Standardkraft" auf das Substrat gepresst und mit einer konstanten Kraft über das Substrat gezogen
3. 3. Das Substrat wurde für 1 h getrocknet
4. 4. Die Schritte 1.-3. wurden fünfmal wiederholt und anschließend der Glanz des Substrates unter Verwendung eines Dr. Lang-Reflektometers, REFO60®, gemessen.

The test procedure was as follows:

1. 1. 5 mL of the diluted formulation (12 g / L, tap water) was applied to a cloth fixed in a frame
2. 2. The cloth was then pressed onto the substrate with a "standard force" and pulled across the substrate with a constant force
3. 3. The substrate was dried for 1 h
4. 4. The steps 1.-3. were repeated five times and then the luster of the substrate using a Dr. med. Long reflectometer, REFO60®, measured.

As shown in Table 2, on all substrates an increase in gloss due to the addition of the polymer was observed. The change in gloss is given as an absolute value. With the human eye a difference of Δ2 is recognizable. Table 2: Gloss effect (Δ) Nonionic basis Anionic base Without polymer A With polymer A Without polymer A With polymer A White tiles (damaged) 3.3 7.9 7.4 18.4 Black tiles (damaged) 2.9 4.4 4.8 14.5 laminate 0.3 2.0 0.5 3.0

Example 2: Adsorption of the polymer and its concentration dependence a) Laser reflectometer

In the following, the chemical adsorption of the polymer A to a test substrate was investigated. The substrate used here was an oxidized silicon wafer onto which the anionic formulation was applied. The adsorption was measured by means of an in-situ laser reflectometer (Wageningen University). Table 3: Concentration dependence of adsorption Anionic base + 0.3% by weight of polymer A + 0.6% by weight of polymer A + 0.9% by weight of polymer A Adsorbed matter (%) 1.87 6.80 9.57 8.32

By means of 3 rinsing cycles it could be confirmed that the polymer A does not build further on the surface.

b) dip test

A damaged black tile was dipped five times in a diluted formulation (12g / l, tap water) and then the gloss values were measured using a Dr. med. Long Reflectometer, REFO60®, both immediately and after rinsing. Table 4: Adsorption and gloss Anionic base with rinse Anionic base without rinsing Anionic base + 0.6% by weight of polymer A with rinse Anionic base + 0.6% by weight of polymer A without rinsing Adsorbed matter (%) 1.87 4.0 9.57 15.0 gloss change 1.2 2.8 3.4 5.9

Example 3: Gloss and Repair Effect a) repair effect

From the surface of a damaged black tile atomic force micrographs were taken before and after applying the diluted (12 g / l) product (anionic base + 0.6 wt.% Polymer A) five times. The photographs clearly show the repair effect of the composition according to the invention.

b) adhesion minimization by repair effect

Furthermore, the adhesion was measured on a tile (damaged or undamaged) before and after applying the composition of the invention in a vertical and a horizontal measuring arrangement.

The results show that after the treatment with the agent according to the invention, the friction force on the damaged tile is up to 50% lower, which is an indication of the repair effect of the composition.

Claims (10)

1. A cleaning agent for hard surfaces, containing at least one surfactant and 0.1 to 3 wt.% of at least one phosphoric acid ester of a polyether-modified alkyl alcohol or salt thereof, characterized in that the phosphoric acid ester of a polyether-modified alkyl alcohol has general formula 1:

   

   where R¹, R², R³ and R⁴ may be the same or different and are selected from

   R-O-(SO)a-(EO)b-(PO)c-(BO)d- and -OH, where,

   SO =

   

   EO = -CH₂-CH₂-O-,

   PO = -CH(CH₃)-CH₂-O- and

   BO = -CH(CH₂CH₃)-CH₂-O-- and

   with the proviso that at least one, preferably at least 2, in particular 3, particularly preferably 4 of the functional groups R¹, R², R³ and R⁴ are not OH,
   where

   a = 1 to 20, preferably 2.2 to 10, more preferably 2.5 to 7, particularly preferably 3 to 5,

   b = 1 to 100, preferably 3 to 40, more preferably 4 to 15, particularly preferably 8 to 12,

   c = 0 to 10, in particular 0,

   d = 0 to 10, in particular 0 and

   R is selected from branched or linear, saturated or unsaturated alkyl functional groups having 8 to 20 carbon atoms, preferably linear, saturated alkyl functional groups having 8 to 16, in particular 10 to 14 carbon atoms.
2. The cleaning agent according to claim 1, characterized in that the agent contains the at least one phosphoric acid ester of a polyether-modified alkyl alcohol in an amount of from 0.3 to 0.9 wt.%, particularly preferably approximately 0.6 wt.%.
3. The cleaning agent according to one of claims 1 or 2, characterized in that

   (1) the agent is in solid form; or

   (2) the agent is in liquid form.
4. The cleaning agent according to one of claims 1 to 3, characterized in that the at least one surfactant is selected from the group consisting of non-ionic surfactants, anionic surfactants, amphoteric surfactants, cationic surfactants, and mixtures thereof, preferably non-ionic surfactants and/or anionic surfactants.
5. The cleaning agent according to one of claims 1 to 4, characterized in that it contains at least one further component selected from the group consisting of acids, bases, organic solvents, salts, complexing agents, fillers, builders, bleaching agents, bleach activators, auxiliaries and additives, and mixtures thereof.
6. The cleaning agent according to one of claims 1 to 5, characterized in that the cleaning agent is a liquid, aqueous cleaning agent.
7. The cleaning agent according to one of claims 1 to 5, characterized in that the cleaning agent is a cleaning agent in powder form.
8. The cleaning agent according to one of claims 1 to 7, characterized in that the pH of the cleaning agent is in the range of from 5 to 11.5, preferably from 7 to 11.3.
9. The use of a cleaning agent according to one of claims 1 to 8 for producing a shine on a hard, preferably non-absorbent surface cleaned therewith.
10. A method for producing shine on a hard, preferably non-absorbent surface, characterized in that the cleaning agent according to one of claims 1 to 8 is applied to the surface and is optionally rubbed thereon.