EP2970828B1 - Reinigungsmittel für harte oberflächen enthaltend phosphorsäureester eines polyether-modifizierten alkylalkohols - Google Patents

Reinigungsmittel für harte oberflächen enthaltend phosphorsäureester eines polyether-modifizierten alkylalkohols Download PDF

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Publication number
EP2970828B1
EP2970828B1 EP14708897.5A EP14708897A EP2970828B1 EP 2970828 B1 EP2970828 B1 EP 2970828B1 EP 14708897 A EP14708897 A EP 14708897A EP 2970828 B1 EP2970828 B1 EP 2970828B1
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Prior art keywords
cleaning agent
acid
agent according
bis
sodium
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German (de)
English (en)
French (fr)
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EP2970828A1 (de
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Kaoru Tachikawa
Kerstin Ziganke
Stefan Karsten
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/362—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • 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.
  • 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.
  • 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.
  • the oxo alcohols or their derivatives which are obtainable, for example, by the ROELEN's oxo synthesis can also be used correspondingly.
  • 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.
  • the indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
  • 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 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.
  • the phosphoric acid esters can also be present in partially or completely neutralized form as salts.
  • 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 ,
  • 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.
  • the alkoxylation is carried out in the presence of catalysts, preferably basic (alkaline) catalysts such as Alkalimethanolaten, sodium hydroxide and / or potassium hydroxide.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • DP degree of oligomerization
  • fatty alcohol alkoxylates 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.
  • EO ethylene oxide
  • PO propylene oxide
  • the cleaning agent according to the invention may contain at least one anionic surfactant.
  • 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.
  • 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 ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • sulfosuccinates sulfosuccinic esters
  • sulfosuccinic mono- and di-C 8 -C 18 -alkyl esters sulfosuccinamates
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • quaternary surface-active compounds in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • 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.
  • 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.
  • 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.
  • the salts are selected from the group comprising formate, acetate, propionate, citrate, malate, tartrate, succinate, malonate, oxalate, lactate and mixtures thereof.
  • the cleaning agent according to the invention is an aqueous hard surface cleaning agent.
  • 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,
  • 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.
  • 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.
  • alkanolamines can be used in addition to the solvents described above.
  • 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.
  • builders customarily employed in detergents and cleaners, in particular silicates, carbonates, organic cobuilders and also the phosphates.
  • 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.
  • the term "amorphous" is also understood to mean “X-ray amorphous”.
  • zeolites can be used as builders, preferably zeolite A and / or P.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • alkali metal ions are sodium and / or potassium ions, particularly preferred are soda (sodium carbonate) and potash (potassium carbonate).
  • alkali metal phosphates are particularly 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.
  • 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.
  • NTA nitrilotriacetic acid
  • 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.
  • the acids can also be used per se.
  • 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.
  • 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.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • 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 ,
  • copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • 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.
  • these are hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • Oxydisuccinates and other derivatives of disuccinates 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.
  • IDS iminodisuccinates
  • HDIS hydroxyiminodisuccinates
  • HDIS hydroxyiminodisuccinates
  • 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.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • 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.
  • 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.
  • all compounds capable of forming complexes with alkaline earth ions may be included as co-builders in the particulate agents.
  • 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 .-%.
  • 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.
  • ammonia and / or alkanolamines having up to 9 C atoms in the molecule preferably the ethanolamines, in particular monoethanolamine.
  • Chelating agents 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.
  • it is important to complex the incompatible with numerous ingredients calcium and magnesium ions of water hardness.
  • the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents.
  • the complexing agents support the cleaning effect.
  • 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
  • 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.
  • 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.
  • a bleach activator may be required in addition to the bleaching agent.
  • 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.
  • 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.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU tetraacet
  • 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.
  • composition according to the invention may contain one or more further auxiliary agents and additives customary in hard surface cleaners.
  • auxiliary agents and additives customary in hard surface cleaners 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 Bronopol restroom mixtures such as Prevento
  • 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.
  • a perfume component d-limonene may be contained.
  • 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.
  • 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.
  • 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 .-%.
  • 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.
  • 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
  • Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group.
  • antimicrobially effective essential oils can be used, which at the same time provide for a scenting of the cleaning product.
  • 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 may also be included in detergent products of the invention. As such, essentially the substances mentioned in the antimicrobial agents can be used.
  • the detergent product according to the invention may contain one or more dyes ( INCI Colorants).
  • 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.
  • Suitable 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.
  • 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.
  • 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.
  • capsules are prepared by methods known per se, for example by shaking or rolling granulation or in Applied to fluid-bed processes.
  • Such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • 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 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
  • 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.
  • the pH of the compositions according to the invention can be adjusted by means of customary pH regulators, for example citric acid or NaOH.
  • the agent has a pH in a range of 5 to 11.5, preferably 7 to 11.3.
  • 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 .-%.
  • 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.
  • paper is preferably excluded.
  • surfaces are 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.
  • hard surfaces such as floors, including tiles, laminates, parquet, cork floors, marble, stone and porcelain stoneware floors
  • 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.
  • 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.
  • 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
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP14708897.5A 2013-03-15 2014-03-11 Reinigungsmittel für harte oberflächen enthaltend phosphorsäureester eines polyether-modifizierten alkylalkohols Active EP2970828B1 (de)

Applications Claiming Priority (3)

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DE102013204615 2013-03-15
DE102013204824.6A DE102013204824A1 (de) 2013-03-15 2013-03-19 Reinigungsmittel für harte Oberflächen enthaltend Phosphorsäureester eines Polyether-modifizierten Alkylalkohols
PCT/EP2014/054646 WO2014139984A1 (de) 2013-03-15 2014-03-11 Reinigungsmittel für harte oberflächen enthaltend phosphorsäureester eines polyether-modifizierten alkylalkohols

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EP2970828B1 true EP2970828B1 (de) 2018-06-06

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DE (1) DE102013204824A1 (es)
ES (1) ES2681981T3 (es)
WO (1) WO2014139984A1 (es)

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JP5800044B2 (ja) * 2014-02-13 2015-10-28 栗田工業株式会社 蒸気発生設備のスケール除去方法及びスケール除去剤
US10030216B2 (en) 2015-06-12 2018-07-24 Crossford International, Llc Systems and methods for cooling tower fill cleaning with a chemical gel
US9404069B1 (en) 2015-06-12 2016-08-02 Crossford International, Llc Systems and methods for cooling tower fill cleaning with a chemical gel
US9963381B2 (en) 2015-07-24 2018-05-08 Infineon Technologies Ag Method for finishing a glass product and glass product
DE102016225903A1 (de) 2016-12-21 2018-06-21 Henkel Ag & Co. Kgaa Reinigungsmittel für harte Oberflächen mit langanhaltender Duft- und Glanzwirkung
US10927397B2 (en) 2018-10-16 2021-02-23 Sterilex, Llc Compositions, devices and methods for detecting biofilms
MX2021012399A (es) 2019-04-12 2021-12-10 Ecolab Usa Inc Limpiador antimicrobiano multiuso y métodos de fabricación y uso de este.
CN112354528B (zh) * 2020-11-09 2021-12-14 海南大学 一种海水提铀用磷酸功能化海绵复合材料及其制备方法

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DE4101740A1 (de) 1991-01-22 1992-07-23 Henkel Kgaa Verfahren zur herstellung von fettalkoholpolyalkylenglycolethern
ES2187083T3 (es) * 1998-02-19 2003-05-16 Goldschmidt Ag Th Esteres de acido fosforico y su utilizacion como agentes dispersantes.
DE10029648C1 (de) * 2000-06-15 2002-02-07 Goldschmidt Ag Th Blockcopolymere Phosphorsäureester, deren Salze und deren Verwendung als Emulgatoren und Dispergiermittel
DE10054462B4 (de) 2000-11-03 2005-02-17 Basf Ag Kontinuierliches Verfahren zur Alkoxylierung in der Flüssigphase
US6403546B1 (en) * 2001-01-31 2002-06-11 S. C. Johnson Commercial Markets, Inc. Floor cleaner and gloss enhancer
DE10341725A1 (de) 2003-09-10 2005-04-21 Basf Ag Festes wasserfreies Kompositmaterial
WO2013004302A1 (en) * 2011-07-05 2013-01-10 Ecolab Inc. Acid marble cleaner

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US9518246B2 (en) 2016-12-13
KR102128136B1 (ko) 2020-06-30
ES2681981T3 (es) 2018-09-17
EP2970828A1 (de) 2016-01-20
KR20150127234A (ko) 2015-11-16
DE102013204824A1 (de) 2014-09-18
US20150376551A1 (en) 2015-12-31
WO2014139984A1 (de) 2014-09-18

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