EP2843034B1 - Cleaning agent with decalcification effect - Google Patents

Cleaning agent with decalcification effect Download PDF

Info

Publication number
EP2843034B1
EP2843034B1 EP14182845.9A EP14182845A EP2843034B1 EP 2843034 B1 EP2843034 B1 EP 2843034B1 EP 14182845 A EP14182845 A EP 14182845A EP 2843034 B1 EP2843034 B1 EP 2843034B1
Authority
EP
European Patent Office
Prior art keywords
cleaning agent
acid
skin
corrosive
agent according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP14182845.9A
Other languages
German (de)
French (fr)
Other versions
EP2843034A1 (en
Inventor
Kadira Nedic
Andreas Brakemeier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Werner and Mertz GmbH
Original Assignee
Werner and Mertz GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Werner and Mertz GmbH filed Critical Werner and Mertz GmbH
Publication of EP2843034A1 publication Critical patent/EP2843034A1/en
Application granted granted Critical
Publication of EP2843034B1 publication Critical patent/EP2843034B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
    • 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 invention relates to a detergent with decalcification and its use in particular as a sanitary cleaner or toilet cleaner for domestic or commercial applications.
  • WO 2007/092800 A2 describes a cleaning composition for cleaning soils on surfaces of microelectronic devices, wherein a composition contains 1% by weight of methanesulfonic acid, 10% by weight of citric acid and 9.2% of dodecylbenzenesulfonic acid.
  • CN101372649 A describes a sanitary cleaner using citric acid, methanesulfonic acid and a nonionic surfactant as well as an anionic surfactant.
  • Typical sanitary cleaners with high limescale solubility which can also be used efficiently to remove larger limescale structures, contain strong acids such as hydrochloric acid, phosphoric acid, sulfamic acid, formic acid, optionally also in combination or combined with weaker acids.
  • strong acids such as hydrochloric acid, phosphoric acid, sulfamic acid, formic acid, optionally also in combination or combined with weaker acids.
  • Such sanitary cleaners are usually very acidic (pH values ⁇ 2.0) and often have skin corrosive properties.
  • the corrosive action, especially of strong acids is often intensified in sanitary cleaners by the additional use of surfactants, which are used for the simultaneous removal of grease and lime soap residues as well as for surface wetting.
  • the object of the invention is to provide a cleaning agent with kalklösenden properties, which has no or only a slight skin corrosivity despite high descaling effect.
  • the agent should also have a high Kalkseifenentfemungshack and meet high ecological requirements.
  • detergents are proposed with an acid combination, which show high product performance and yet are user-friendly, being used as the base acids citric acid and / or lactic acid in combination with methanesulfonic acid, which at least one anionic surfactant is added.
  • methanesulfonic acid Due to its high acid strength, methanesulfonic acid is able to significantly increase the lime dissolving power or the rate of limescale removal of citric acid and / or lactic acid solutions already by adding low concentrations. Lactic acid and in particular citric acid are user-friendly due to their only moderate or weak skin irritating effect, but often have not sufficiently high lime-dissolving properties due to their only average acidity. Methanesulfonic acid, on the other hand, has skin-corrosive properties, but due to its high acidity, it increases the lime-dissolving properties of citric acid and / or lactic acid even in low concentrations. By suitable combination of the acid concentrations under control of the methanesulfonic acid fraction, the skin-irritating or corrosive effect of the descaling agent can be controlled.
  • anionic surfactants have a generally good skin compatibility.
  • anionic surfactants lead to a weakening of the skin corrosivity, in particular of the acid combinations indicated above, and thus show opposing properties, such as conventional nonionic surfactants.
  • Anionic surfactants obviously also reduce the aggressiveness of the acids to the skin.
  • the scouring capacity of the cleaning agent achieved with such anionic surfactants is significantly higher than the otherwise identically composed cleaning agent which, however, hitherto contains conventional nonionic surfactants whose use increases the skin corrosivity of an acidic cleaning agent. Furthermore, the achieved Kalkseifenlinatesti the cleaning agent when using anionic surfactants is often above that of the otherwise identical composition with conventional nonionic surfactants.
  • the cleaning agent according to the invention therefore contains an anionic surfactant or more anionic surfactants. It is also possible to provide mixtures with nonionic and / or amphoteric surfactants.
  • the concentration of citric acid and / or lactic acid with added methanesulfonic acid is advantageously adjusted so that a pH of ⁇ 2.0 results.
  • a strong acidic aqueous detergent having a pH ⁇ 1.5 and especially pH ⁇ 1.0 for the undiluted product, e.g. preferably 0.6 or 0.8, provided.
  • the detergents according to the invention are not skin corrosive according to the validated test method OECD 431.
  • Citric acid or lactic acid may be present in the range of 3 to 15% by weight and combined with 0.5 to 8% by weight, especially up to 5% by weight, preferably to 3% by weight of methanesulfonic acid.
  • the proportion of citric acid may be in particular 5 to 12 wt .-%.
  • Citric acid is preferably used in a proportion of 6 to 10 wt .-%, in particular 6 to 8 wt .-%.
  • a proportion of 4 to 10% by weight and more preferably to about 8% by weight is preferably used.
  • the concentration of methanesulfonic acid may be up to 8 wt .-% and is preferably limited to a maximum of 5 wt .-%, in particular to about 3 wt .-%.
  • the proportion of methanesulfonic acid is preferably 0.5 to 2.95% by weight, for example 2.5 to 2.95% by weight. Another preferred range is about 1.5 to 2.95 wt .-%.
  • a cleaning agent according to the invention for example formic acid, acetic acid, gluconic acid, glycolic acid, succinic acid, adipic acid, maleic acid, tartaric acid, malic acid, amidosulfonic acid or phosphoric acid and mixtures thereof
  • the agent according to the invention contains only citric acid and / or lactic acid and methanesulfonic acid
  • Anionic surfactants according to the invention may be aliphatic sulfates such as fatty alcohol sulfates, iso-alcohol sulfates (C8-C18), fatty alcohol ether sulfates (C8-C18), dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, ester sulfonates and lignos
  • alkylbenzenesulfonates sulfosuccinates (sulfosuccinic esters), sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates and alkyl (ether) phosphates and ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • the cleaning agent according to the invention contains an anionic surfactant or more anionic surfactants from the group of fatty alcohol sulfates or iso-alcohol sulfates (C8-C14) and fatty alcohol ether sulfates (C8-C14) and mixtures of these. Preference is given to n-octyl sulfate or iso-octyl sulfate.
  • Fatty alcohol sulfates or iso-alcohol sulfates are products of sulfation of corre sponding alcohols, while fatty alcohol ether sulfates are products of sulfation of alkoxylated alcohols
  • 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 (C8-C18)
  • n moles of ethylene oxide and one mole of alcohol give, depending on the reaction conditions, a complex mixture of addition products of different degrees of ethoxylation.
  • Another embodiment of the alkoxylation involves the use of mixtures of the alkylene oxides, preferably of 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 3 EO, for example 2 EO
  • EO ethylene oxide units
  • anionic surfactants are usually used as salts, but also as acid.
  • the salts are preferably alkali metal salts, alkaline earth metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or potassium salts, most preferably sodium salts such as octyl sulfate Na salt.
  • the total concentration of an anionic surfactant or surfactants in the cleaning agent is preferably in the range up to 5 wt .-%, preferably up to 3 wt .-%, particularly preferably up to 1 wt .-%, such as 0.75 to 0.95 wt %
  • the surfactants are preferably selected from the group of fatty alcohol sulfates or iso-alcohol sulfates (C8-C14) and fatty alcohol ether sulfates (C8-C14), in particular n-octyl sulfate (C8).
  • the detergent may comprise mixtures of these.
  • a detergent according to the invention comprises, for example, citric acid or lactic acid in the range of about 4 to 8% by weight in combination with about 0.5 to 2.95% by weight of methanesulfonic acid, the content of anionic surfactant being about 0.75 to 0.95 wt .-% is.
  • the pH value is ⁇ 1.5 and the cleaning agent is not skin corrosive according to OECD 431.
  • Preferred cleaning agents contain from 4 to 10% by weight, in particular from 6 to 8% by weight, preferably 7.1% by weight, of lactic acid, 0.5 to 2.95 wt .-%, preferably 2.8 wt .-% methanesulfonic acid and 0.8 to 0.95% by weight of an anionic surfactant, in particular n-octyl sulfate (C8), wherein the pH is ⁇ 1.5, in particular 0.6, wherein the cleaning agent is not skin corrosive.
  • an anionic surfactant in particular n-octyl sulfate (C8), wherein the pH is ⁇ 1.5, in particular 0.6, wherein the cleaning agent is not skin corrosive.
  • Another preferred cleaning agent contains 6 to 15 wt .-%, in particular 6 to 12 wt .-%, preferably 8 wt .-% citric acid, 0.5 to 2.95 wt .-%, methanesulfonic acid and 0.8 to 0.95% by weight of an anionic surfactant, in particular n-octylsulfate (C8), wherein the pH is ⁇ 1.5, in particular 0.6, wherein the cleaning agent is not skin corrosive
  • Another object of the invention is the use of anionic surfactants for damping the symbolkonosiven action of a strongly acidic decalcifying agent Especially when the agent based on citric acid and / or lactic acid with methanesulfonic acid, as stated above, is constructed, in addition to the damping of skin corrosive / skin-initiating Effect also achieved a high lime and Kalkseifenlinatecrypt the acid mixtures especially with n-octyl sulfate (C8).
  • the descaling agent according to the invention is particularly suitable for use as a sanitary or toilet cleaner
  • the cleaning agent according to the invention may comprise one or more of customary auxiliaries and additives, preferably selected from the group comprising water-soluble solvents, dyes, fragrances, disinfectants and preservatives, corrosion inhibitors, complexing agents for alkaline earth ions, sequestering agents and enzymes
  • customary auxiliaries and additives preferably selected from the group comprising water-soluble solvents, dyes, fragrances, disinfectants and preservatives, corrosion inhibitors, complexing agents for alkaline earth ions, sequestering agents and enzymes
  • suitable emulsifiers are added.
  • the cleaning agent may contain one or more water-soluble, organic solvents, preferably from the group of alcohols or glycols or glycol ethers.
  • the amounts preferably added are from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight.
  • Suitable water-soluble solvents are e.g. the alcohols ethanol, n-propanol, isopropanol, furthermore the ether compounds of ethylene glycol or diethylene glycol or propylene glycol or dipropylene glycol with methanol, ethanol, n- and iso-propanol, n- and iso-butanol, e.g.
  • Ethylene glycol butyl ether (BG), diethylene glycol ethyl ether (EDG), diethylene glycol butyl ether (BDG), propylene glycol methyl ether (PM), propylene glycol n-butyl ether (PnB, 3-butoxy-2-butanol), dipropylene glycol methyl ether (DPM), dipropylene glycol n-propyl ether (DPnP).
  • DPM propylene glycol n-butyl ether
  • DPM dipropylene glycol n-propyl ether
  • DPM dipropylene glycol n-propyl ether
  • DPM dipropylene glycol n-propyl ether
  • DPM dipropylene glycol n-propyl ether
  • DPM dipropylene glycol n-propyl ether
  • DPM dipropylene glycol n-propyl ether
  • DPM dipropylene glycol n-but
  • the cleaning agent may contain one or more perfumes, preferably in an amount of from 0.01 to 1% by weight, preferably from 0.05 to 0.5% by weight, particularly preferably from 0.1 to 0.3% by weight, and / or one or more dyes, preferably in an amount of from 0.0001 to 0.1% by weight, preferably from 0.0005 to 0.05% by weight, particularly preferably from 0.001 to 0.01% by weight
  • a particular form of cleaning is the disinfection.
  • the cleaning agent therefore contains one or more antimicrobial active substances. Disinfection is understood to mean the killing of infectious germs. The extent of disinfection depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial content or increasing dilution of the agent for use.
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, phenoxyethanol, lactic acid (if not already present as active ingredient), benzoic acid, salicylic acid and optionally antimicrobial quaternary surface-active compounds
  • the cleaning agent may contain one or more metal corrosion inhibitors, preferably in an amount of from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight, particularly preferably from 0.5 to 2% by weight
  • Suitable corrosion inhibitors are, for example, the following substances: cyclohexylamines, diammonium phosphates, dilithium oxalates, dimethylamino methylpropanol, dipotassium oxalates, dipotassium phosphates, disodium phosphates, disodium pyrophosphates, disodium tetrapropenyl succinates, hexoxyethyl diethylammonium, phosphates, nitromethanes, potassium silicates, sodium aluminates, sodium hexametaphosphates, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.
  • the cleaning agent may also contain one or more complexing agents, preferably in an amount of from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, particularly preferably from 0.5 to 3% by weight
  • complexing agents are ingredients that are capable of complexing and inactivating metal ions to prevent their detrimental effects on the stability or appearance of the agents, for example clouding.
  • Complexing 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.
  • Suitable are, for example, the following according to INCI designated complexing agents: Aminotrimethylene phosphonic acid, beta-alanines diacetic acid, calcium disodium EDIA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriamine pentamethylene phosphonic acid, dipotassium EDTA, disodium azacycloheptanes diphosphonates, 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 Tetra- methylene Phosphonate, Pentasodium Pentetate,
  • the agent may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They may be added to the composition according to the invention in any form established according to the prior art. In the case of liquid or gel-containing compositions, these include, in particular, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • enzymes preferably proteases, lipases, amylases, hydrolases and / or cellulases.
  • the method is based on the recommendation for quality assessment for bathroom cleaners (IKW, version 2002) and the recommendation for quality assessment of acidic toilet cleaners (IKW, version 1999)
  • the plates are then immersed in a defined volume of decalcifying liquid for 10 minutes (a 4-fold determination is made for statistical verification of the method). After thoroughly rinsing the patten with demineralized water and re-drying at 105 ° C, the weight loss of each marble slab is determined by weighing. The measured values from the multiple determinations are averaged and logged. The amount of marble removed (CaCO 3 ) corresponds to the lime-release capacity of the bath cleaner.
  • the temperature of the decalcifying liquid and the marble slabs should be between 20 and 23 ° C during the experiment.
  • Kalkseifenlieresti is based on the recommendation for quality evaluation for bathroom cleaners (IKW, version 2002)
  • a defined amount of a dirt suspension is applied. This consists of calcium stearate (lime soap), dye (carbon black) and a solvent After application, the tile is dried at 180 ° C. The solvent evaporates and the molten lime soap remains after cooling with its bound soot back as a solid, smooth layer. Weighing determines the amount of dirt applied.
  • the soiled surface is divided with a stencil into twelve equal rectangular fields (3 rows of 4 fields each).
  • the three rows are now wetted with the various sanitary cleaner.
  • the contact time of the cleaners on the 4 fields of a row varies from 10 min, 7.5 min, 5 min to 2.5 min. After these defined contact times graze the areas below running water with the help of a sponge cleaned.
  • the cleaning result on the individual fields is documented by means of a photo and assessed visually.
  • a high degree of Kalkseifenlettessti or Kalkseifenlinate shows up in as white areas as possible after the shortest possible contact times.
  • the Skin Ingression Test according to OECD 431 reliably identifies potential skin corrosive effects of substances or preparations.
  • This in vitro method utilizes epidermal 3D skin culture models from recultured human skin
  • the test substance / preparation acts simultaneously on a negative control (distilled water) and a positive control (8 mol / l potassium hydroxide) on the skin tissue.
  • a negative control distilled water
  • a positive control 8 mol / l potassium hydroxide
  • the enzyme activity in the skin tissue is determined via a color reaction.
  • Increasing skin tissue damage (“corrosion") leads to a decrease in enzyme activity or dye production.
  • the specific thresholds for residual enzyme activity or dye production are not reached after 3 minutes and 1 hour, the test substance is classified as "corrosive to the skin”. If these limit values are exceeded, the test substance is correspondingly classified as "non-corrosive to the skin”.
  • exemplary sanitary cleaners are preferably suitable for surface decalcification in the sanitary sector, eg for tiles, sinks, toilet bowls, urinals or fittings.
  • the cleaner in appropriate dilutions with water (1: 1 to 1: 3), the cleaner is of advantage in kettles, coffee machines, etc. for the removal of calcium deposits.
  • descaling agent no. 1 has a high calendering power based on the combination of lactic acid and methanesulfonic acid. Its lime soap dissolving power, however, remains very low due to lack of surfactants
  • the anionic surfactant maintains the high laking power of the otherwise identical but surfactant-free descaling agent. It also increases the Kalkseifenlettesstinum at the same time much stronger than the otherwise identical cleaning agent with a conventional nonionic surfactant addition also results only on addition of the anionic surfactant non-corrosive property.
  • Descaling agent # 4 has a high level of limescale associated with non-corrosive property, despite the pH of 0.6.
  • a comparison of the cleaning agents No. 5 and No. 6 shows the superior effect of an anionic surfactant in relation to a nonionic surfactant with respect to laking and lime soap power and non-corrosive property.
  • the skin irritation effect of detergent No. 6 is further reduced compared to descaling agent no.

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Description

Die Erfindung betrifft ein Reinigungsmittel mit Entkalkungswirkung und dessen Verwendung insbesondere als Sanitärreiniger bzw. WC-Reiniger für häusliche oder gewerbliche Anwendungen.The invention relates to a detergent with decalcification and its use in particular as a sanitary cleaner or toilet cleaner for domestic or commercial applications.

WO 2007/092800 A2 beschreibt eine Reinigungszusammensetzung zum Reinigen von Verschmutzungen an Oberflächen von mikroelektronischen Einrichtungen, wobei eine Zusammensetzung 1 Gew. % Methansulfonsäure, 10 Gew. % Zitronensäure und 9,2 % Dodecylbenzolsulfonsäure enthält. WO 2007/092800 A2 describes a cleaning composition for cleaning soils on surfaces of microelectronic devices, wherein a composition contains 1% by weight of methanesulfonic acid, 10% by weight of citric acid and 9.2% of dodecylbenzenesulfonic acid.

CN101372649 A beschreibt ein Sanitärreinigungsmittel unter Verwendung von Zitronensäure, Methansulfonsäure und einem nichtionischen Tensid sowie einem anionischen Tensid. CN101372649 A describes a sanitary cleaner using citric acid, methanesulfonic acid and a nonionic surfactant as well as an anionic surfactant.

Typische Sanitärreiniger mit hohem Kalklösevermögen, die sich auch zur Entfernung größerer Kalkaufbauten effizient einsetzen lassen, enthalten starke Säuren wie z.B. Salzsäure, Phosphorsäure, Amidosulfonsäure, Ameisensäure, gegebenenfalls auch in Kombination oder kombiniert mit schwächeren Säuren. Solche Sanitärreiniger sind in der Regel sehr sauer (pH-Werte < 2,0) und weisen häufig hautkorrosive Eigenschaften auf.
Die hautkorrosive Wirkung insbesondere von starken Säuren wird in Sanitärreinigern durch den zusätzlichen Einsatz von Tensiden, die zur gleichzeitigen Entfernung von Fettverschmutzungen und Kalkseifenrückständen sowie zur Oberflächenbenetzung eingesetzt werden, häufig noch verstärkt. Da viele Tenside die Haut für den Eintritt anderer Stoffe zugänglicher machen, führt die Kombination von Säuren mit Tensiden in vielen Fällen zu einer verstärkten irritierenden oder korrosiven Wirkung der Zubereitung im Vergleich zu einer entsprechenden Zubereitung ohne Tenside.
So führt in der Regel bereits der Zusatz von 0,1 Gew.-% eines nichtionischen Tensids zu einer signifikant erhöhten Hautreizung bzw. Hautkorrosivität gegenüber der Basiszubereitung ohne diesen Tensidzusatz, wie durch validierte in-vitro-Haukorrosionstest gemäß OECD 431 nachgewiesen werden kann.Typical sanitary cleaners with high limescale solubility, which can also be used efficiently to remove larger limescale structures, contain strong acids such as hydrochloric acid, phosphoric acid, sulfamic acid, formic acid, optionally also in combination or combined with weaker acids. Such sanitary cleaners are usually very acidic (pH values <2.0) and often have skin corrosive properties.
The corrosive action, especially of strong acids, is often intensified in sanitary cleaners by the additional use of surfactants, which are used for the simultaneous removal of grease and lime soap residues as well as for surface wetting. Since many surfactants make the skin more accessible to the ingress of other substances, the combination of acids with surfactants in many cases leads to an increased irritating or corrosive effect of the preparation compared to a corresponding preparation without surfactants.
Thus, the addition of 0.1% by weight of a nonionic surfactant generally already leads to significantly increased skin irritation or skin corrosivity compared to the base preparation without this surfactant additive, as can be demonstrated by validated in vitro skin corrosion test according to OECD 431.

Will man eine hohe Entkalkungsleistung eines Reinigungsmittels erzielen, so ergibt sich einerseits eine erhebliche Beeinträchtigung für den Anwender durch eine ansteigende Hautreizung bzw. Hautkorrosivität und andererseits der Nachteil einer höheren Umweltbelastung.If you want to achieve a high descaling performance of a cleaning agent, so there is a significant impact on the one hand for the user by increasing skin irritation or skin corrosivity and on the other hand, the disadvantage of higher environmental impact.

Aufgabe der Erfindung ist es, ein Reinigungsmittel mit kalklösenden Eigenschaften bereitzustellen, das trotz hoher Entkalkungswirkung keine oder nur eine geringe Hautkorrosivität aufweist.The object of the invention is to provide a cleaning agent with kalklösenden properties, which has no or only a slight skin corrosivity despite high descaling effect.

Vorzugsweise soll das Mittel zudem eine hohes Kalkseifenentfemungsvermögen aufweisen und hohen ökologischen Anforderungen gerecht werden.Preferably, the agent should also have a high Kalkseifenentfemungsvermögen and meet high ecological requirements.

Diese Aufgabe wird durch die Merkmale in den Ansprüchen 1 und 2 gelöst.This object is solved by the features in claims 1 and 2.

Erfindungsgemäß werden Reinigungsmittel mit einer Säurekombination vorgeschlagen, die eine hohe Produktleistung zeigen und dennoch anwenderfreundlich sind, wobei als Basissäuren Zitronensäure und/oder Milchsäure in Kombination mit Methansulfonsäure verwendet werden, denen wenigstens ein anionisches Tensid zugesetzt ist.According to the invention detergents are proposed with an acid combination, which show high product performance and yet are user-friendly, being used as the base acids citric acid and / or lactic acid in combination with methanesulfonic acid, which at least one anionic surfactant is added.

Methansulfonsäure ist aufgrund ihrer hohen Säurestärke in der Lage, das Kalklösevermögen bzw. die Kalklösegeschwindigkeit von Zitronensäure- und/oder Milchsäure-Lösungen bereits durch Zugabe geringer Konzentrationen signifikant zu erhöhen. Milchsäure und im besonderen Zitronensäure sind aufgrund ihrer nur mäßig bzw. schwach hautirritierenden Wirkung anwenderfreundlich, haben aber durch ihre nur mittlere Säurestärke häufig nicht ausreichend hohe kalklösende Eigenschaften. Methansulfonsäure dagegen besitzt hautkorrosive Eigenschaften, aber sie erhöht durch Ihre hohe Säurestärke bereits in geringer Konzentration die kalklösende Eigenschaft von Zitronensäure und/oder Milchsäure. Durch geeignete Kombination der Säurekonzentrationen unter Kontrolle des Methansulfonsäureanteils kann die hautirritierende bzw. hautkorrosive Wirkung des Entkalkungsmittels kontrolliert werden.Due to its high acid strength, methanesulfonic acid is able to significantly increase the lime dissolving power or the rate of limescale removal of citric acid and / or lactic acid solutions already by adding low concentrations. Lactic acid and in particular citric acid are user-friendly due to their only moderate or weak skin irritating effect, but often have not sufficiently high lime-dissolving properties due to their only average acidity. Methanesulfonic acid, on the other hand, has skin-corrosive properties, but due to its high acidity, it increases the lime-dissolving properties of citric acid and / or lactic acid even in low concentrations. By suitable combination of the acid concentrations under control of the methanesulfonic acid fraction, the skin-irritating or corrosive effect of the descaling agent can be controlled.

Es ist zwar bekannt, dass anionische Tenside eine allgemein gute Hautverträglichkeit aufweisen. Es hat sich aber überraschend gezeigt, dass anionische Tenside zu einer Abschwächung der Hautkorrosivität insbesondere der zuvor angegebenen Säurekombinationen führen und somit gegensätzliche Eigenschaften zeigen wie übliche nichtionische Tenside. Anionische Tenside dämpfen offensichtlich auch die Aggressivität der Säuren gegenüber der Haut.Although it is known that anionic surfactants have a generally good skin compatibility. However, it has surprisingly been found that anionic surfactants lead to a weakening of the skin corrosivity, in particular of the acid combinations indicated above, and thus show opposing properties, such as conventional nonionic surfactants. Anionic surfactants obviously also reduce the aggressiveness of the acids to the skin.

Das erzielte Kalkentfernungsvermögen des Reinigungsmittels liegt mit solchen anionischen Tensiden signifikant über dem ansonsten identisch zusammengesetzten Reinigungmittels, das jedoch bisher übliche nichtionische Tenside enthält, deren Einsatz die Hautkorrosivität eines sauren Reinigungsmittels erhöht.
Ferner liegt häufig auch das erzielte Kalkseifenlösevermögen des Reinigungsmittels bei Verwendung von anionischen Tensiden über dem der ansonsten identisch zusammengesetzten Zubereitung mit üblichen nichtionischen Tensiden.The scouring capacity of the cleaning agent achieved with such anionic surfactants is significantly higher than the otherwise identically composed cleaning agent which, however, hitherto contains conventional nonionic surfactants whose use increases the skin corrosivity of an acidic cleaning agent.
Furthermore, the achieved Kalkseifenlösevermögen the cleaning agent when using anionic surfactants is often above that of the otherwise identical composition with conventional nonionic surfactants.

Zur Verbesserung der Reinigungswirkung (Kalklösevermögen und/oder Kalkseifenlösevermögen) sowie zur Dämpfung hautkorrosiver Wirkungen enthält das erfindungsgemäße Reinigungsmittel deshalb ein anionisches Tensid oder mehrere anionische Tenside. Es können auch Gemische mit nichtionischen und/oder amphoteren Tensiden vorgesehen werden.To improve the cleaning effect (laking properties and / or Kalkseifenlösevermögen) and for damping skin corrosive effects, the cleaning agent according to the invention therefore contains an anionic surfactant or more anionic surfactants. It is also possible to provide mixtures with nonionic and / or amphoteric surfactants.

Die Konzentration von Zitronensäure und/oder Milchsäure mit zugesetzter Methansulfonsäure wird vorteilhafterweise so eingestellt, dass sich ein pH-Wert von < 2,0 ergibt. Besonders bevorzugt wird ein stark saures wässriges Reinigungsmittel mit einem pH-Wert < 1,5 und insbesondere pH < 1,0 für das unverdünnte Produkt, wie z.B. bevorzugt 0,6 oder auch 0,8, vorgesehen.The concentration of citric acid and / or lactic acid with added methanesulfonic acid is advantageously adjusted so that a pH of <2.0 results. Particularly preferred is a strong acidic aqueous detergent having a pH <1.5 and especially pH <1.0 for the undiluted product, e.g. preferably 0.6 or 0.8, provided.

Dadurch ist es möglich, Sanitärreiniger mit hohen Säuregehalten bzw. starken Säuren im extremen pH-Bereich (pH < 2,0) und somit mit sehr hoher Entkalkungsleistung zu realisieren. Die Reinigungsmittel nach der Erfindung sind gemäß validiertem Testverfahren OECD 431 nicht hautkorrosiv.This makes it possible to realize sanitary cleaners with high acid contents or strong acids in the extreme pH range (pH <2.0) and thus with a very high descaling performance. The detergents according to the invention are not skin corrosive according to the validated test method OECD 431.

Zitronensäure oder Milchsäure kann im Bereich von 3 bis 15 Gew.-% vorliegen und mit 0,5 bis 8 Gew.- %, insbesondere bis 5 Gew.-%, bevorzugt bis 3 Gew.-% Methansulfonsäure kombiniert werden.Citric acid or lactic acid may be present in the range of 3 to 15% by weight and combined with 0.5 to 8% by weight, especially up to 5% by weight, preferably to 3% by weight of methanesulfonic acid.

Der Anteil an Zitronensäure kann insbesondere 5 bis 12 Gew.-% betragen. Bevorzugt wird Zitronensäure mit einem Anteil von 6 bis 10 Gew.-%, insbesondere 6 bis 8 Gew.-% verwendet.
Im Falle von Milchsäure wird bevorzugt ein Anteil von 4 bis 10 Gew.-% und weiter bevorzugt bis etwa 8 Gew.-% verwendet.The proportion of citric acid may be in particular 5 to 12 wt .-%. Citric acid is preferably used in a proportion of 6 to 10 wt .-%, in particular 6 to 8 wt .-%.
In the case of lactic acid, a proportion of 4 to 10% by weight and more preferably to about 8% by weight is preferably used.

Die Konzentration der Methansulfonsäure kann bis zu 8 Gew.-% betragen und wird vorzugsweise auf maximal 5 Gew.-%, insbesondere auf ca. 3 Gew.-% begrenzt.
Der Anteil an Methansulfonsäure liegt bevorzugt bei 0,5 bis 2,95 Gew.-%, z.B. bei 2,5 bis 2,95 Gew. %. Ein weiterer bevorzugter Bereich liegt bei ca. 1,5 bis 2,95 Gew.-%.The concentration of methanesulfonic acid may be up to 8 wt .-% and is preferably limited to a maximum of 5 wt .-%, in particular to about 3 wt .-%.
The proportion of methanesulfonic acid is preferably 0.5 to 2.95% by weight, for example 2.5 to 2.95% by weight. Another preferred range is about 1.5 to 2.95 wt .-%.

Es können weitere, organische oder anorganische Säuren in einem erfindungsgemäßen Reinigungsmittel enthalten sein, beispielsweise Ameisensäure, Essigsäure, Gluconsäure, Glycolsäure, Bernsteinsäure, Adipinsäure, Maleinsäure, Weinsäure, Äpfelsäure, Amidosulfonsäure oder Phosphorsäure sowie Gemische derselben In einer bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel jedoch lediglich Zitronensäure oder/und Milchsäure sowie Methansulfonsäure
Anionische Tenside gemäß der Erfindung können aliphatische Sulfate wie Fettalkoholsulfate, iso-Alkoholsulfäte (C8-C18), Fettalkoholethersulfate (C8-C18), Dialkylethersulfäte, Monoglyceridsulfate und aliphatische Sulfonate wie Alkansulfonate, Olefinsulfonate, Ethersulfonate, Estersulfonate und Ligninsulfonate sein. Ebenfalls im Rahmen der vorliegenden Erfindung verwendbar sind Alkylbenzolsulfonate, Sulfosuccinate (Sulfobernsteinsäuteester), Sulfosuccinamate, Sulfosuccinamide, Fettsäureisethionate, Acylaminoalkansulfonate (Fettsäuretauride), Fettsäuresarcosinate und Alkyl- (ether)phosphate sowie α-Sulfofettsäuresalze, Acylglutamate, Monoglyceriddisulfate und Alkylether des Glycerindisulfats. Das erfindungsgemäße Reinigungsmittel enthält ein anionisches Tensid oder mehrere anionische Tenside aus der Gruppe der Fettalkoholsulfate bzw iso-Alkoholsulfate (C8-C14) und Fettalkoholethersulfate (C8-C14) sowie Gemische von diesen. Bevorzugt wird n-Octylsulfat bzw iso-Octylsulfat.
Fettalkoholsulfate bzw. iso-Alkoholsulfäte sind Produkte aus Sulfatierreaktionen an entspre chenden Alkoholen, während Fettalkoholethersulfate Produkte aus Sulfatieneaktionen an alkoxylierten Alkoholen sind Dabei versteht der Fachmann allgemein unter alkoxylierten Alkoholen die Reaktionsprodukte von Alkylenoxid, bevorzugt Ethylenoxid, mit Alkoholen, im Sinne der vorliegenden Erfindung bevorzugt mit längerkettigen Alkoholen (C8-C18) In der Regel entsteht aus n Molen Ethylenoxid und einem Mol Alkohol, abhängig von den Reaktionsbedingungen, ein komplexes Gemisch von Additionsprodukten unterschiedlicher Ethoxylierungsgrade Eine weitere Ausführungsform der Alkoxylierung besteht im Einsatz von Gemischen der Alkylenoxide, bevorzugt des Gemisches von Ethylenoxid und Propylenoxid. Bevorzugte Fettalkoholethersulfate sind die Sulfate niederethoxylierter Fettalkohole mit 1 bis 4 Ethylenoxideinheiten (EO), insbesondere 1 bis 3 EO, beispielsweise 2 EO
Die anionischen Tenside werden üblicherweise als Salze, aber auch als Säure eingesetzt. Bei den Salzen handelt es sich bevorzugt um Alkalimetallsalze, Erdalkalimetallsalze, Ammoniumsalze sowie Mono-, Di- bzw Trialkanolammoniumsalze, beispielsweise Mono-, Di- bzw Triethanolammoniumsalze, insbesondere um Lithium-, Natrium-, Kalium- oder Ammoniumsalze, besonders bevorzugt Natrium- oder Kaliumsalze, äußerst bevorzugt Natriumsalze wie z.B. Octylsulfat-Na-Salz.Other organic or inorganic acids may be present in a cleaning agent according to the invention, for example formic acid, acetic acid, gluconic acid, glycolic acid, succinic acid, adipic acid, maleic acid, tartaric acid, malic acid, amidosulfonic acid or phosphoric acid and mixtures thereof In a preferred embodiment, however, the agent according to the invention contains only citric acid and / or lactic acid and methanesulfonic acid
Anionic surfactants according to the invention may be aliphatic sulfates such as fatty alcohol sulfates, iso-alcohol sulfates (C8-C18), fatty alcohol ether sulfates (C8-C18), dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, ester sulfonates and lignosulfonates. Also useful in the present invention are alkylbenzenesulfonates, sulfosuccinates (sulfosuccinic esters), sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates and alkyl (ether) phosphates and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate. The cleaning agent according to the invention contains an anionic surfactant or more anionic surfactants from the group of fatty alcohol sulfates or iso-alcohol sulfates (C8-C14) and fatty alcohol ether sulfates (C8-C14) and mixtures of these. Preference is given to n-octyl sulfate or iso-octyl sulfate.
Fatty alcohol sulfates or iso-alcohol sulfates are products of sulfation of corre sponding alcohols, while fatty alcohol ether sulfates are products of sulfation of alkoxylated alcohols The skilled worker generally understands 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 (C8-C18) As a rule, n moles of ethylene oxide and one mole of alcohol give, depending on the reaction conditions, a complex mixture of addition products of different degrees of ethoxylation. Another embodiment of the alkoxylation involves the use of mixtures of the alkylene oxides, preferably of 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 3 EO, for example 2 EO
The anionic surfactants are usually used as salts, but also as acid. The salts are preferably alkali metal salts, alkaline earth metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or potassium salts, most preferably sodium salts such as octyl sulfate Na salt.

Die Gesamtkonzentration eines anionischen Tensids oder mehrerer anionischer Tenside im Reinigungsmittel liegt vorzugsweise im Bereich bis 5 Gew.-%, bevorzugt bis zu 3 Gew.-%, besonders bevorzugt bis 1 Gew.-%, wie z.B. 0,75 bis 0,95 Gew. -%
Die Tenside sind bevorzugt aus der Gruppe der Fettalkoholsulfate oder iso-Alkoholsulfäte (C8-C14) und Fettalkoholethersulfate (C8-C14) ausgewählt, im Besonderen n-Octylsulfat (C8) Das Reinigungsmittel kann Gemische von diesen aufweisen.The total concentration of an anionic surfactant or surfactants in the cleaning agent is preferably in the range up to 5 wt .-%, preferably up to 3 wt .-%, particularly preferably up to 1 wt .-%, such as 0.75 to 0.95 wt %
The surfactants are preferably selected from the group of fatty alcohol sulfates or iso-alcohol sulfates (C8-C14) and fatty alcohol ether sulfates (C8-C14), in particular n-octyl sulfate (C8). The detergent may comprise mixtures of these.

Ein Reinigungsmittel nach der Erfindung weist beispielsweise Zitronensäure oder Milchsäure im Bereich von etwa 4 bis 8 Gew.-% in Verbindung mit etwa 0,5 bis 2,95 Gew.-% Methansulfonsäure auf, wobei der Anteil an anionischem Tensid bei etwa 0,75 bis 0,95 Gew.-% liegt. Der pH-Wert beträgt dabei <1,5 und das Reinigungsmittel ist nach OECD 431 nicht hautkorrosiv.A detergent according to the invention comprises, for example, citric acid or lactic acid in the range of about 4 to 8% by weight in combination with about 0.5 to 2.95% by weight of methanesulfonic acid, the content of anionic surfactant being about 0.75 to 0.95 wt .-% is. The pH value is <1.5 and the cleaning agent is not skin corrosive according to OECD 431.

Bevorzugte Reinigungsmittel enthalten 4 bis 10 Gew.-%, insbesondere 6 bis 8 Gew.-%, bevorzugt 7,1 Gew.-% Milchsäure,
0,5 bis 2,95 Gew.-%, bevorzugt 2,8 Gew.-% Methansulfonsäure und
0,8 bis 0,95 Gew -% eines anionischen Tensids, insbesondere n-Octylsulfat (C8),
wobei der pH-Wert < 1,5 -, insbesondere 0,6 beträgt, wobei das Reinigungsmittel nicht hautkorrosiv ist.Preferred cleaning agents contain from 4 to 10% by weight, in particular from 6 to 8% by weight, preferably 7.1% by weight, of lactic acid,
0.5 to 2.95 wt .-%, preferably 2.8 wt .-% methanesulfonic acid and
0.8 to 0.95% by weight of an anionic surfactant, in particular n-octyl sulfate (C8),
wherein the pH is <1.5, in particular 0.6, wherein the cleaning agent is not skin corrosive.

Ein weiteres bevorzugtes Reinigungsmittel enthält 6 bis 15 Gew.-%, insbesondere 6 bis 12 Gew.-%, bevorzugt 8 Gew.-% Zitronensäure,
0,5 bis 2,95 Gew.-%, Methansulfonsäure und
0,8 bis 0,95 Gew.-% eines anionischen Tensids, insbesondere n-Octylsulfat (C8),
wobei der pH-Wert < 1,5 insbesondere 0,6 beträgt, wobei das Reinigungsmittel nicht hautkorrosiv istAnother preferred cleaning agent contains 6 to 15 wt .-%, in particular 6 to 12 wt .-%, preferably 8 wt .-% citric acid,
0.5 to 2.95 wt .-%, methanesulfonic acid and
0.8 to 0.95% by weight of an anionic surfactant, in particular n-octylsulfate (C8),
wherein the pH is <1.5, in particular 0.6, wherein the cleaning agent is not skin corrosive

Ein weiterer Gegenstand der Erfindung ist die Verwendung anionischer Tenside zur Dämpfung der hautkonosiven Wirkung eines stark sauren Entkalkungsmittels Insbesondere wenn das Mittel auf der Basis von Zitronensäure und/oder Milchsäure mit Methansulfonsäure, wie zuvor angegeben, aufgebaut ist, wird neben der Dämpfung der hautkorrosiven/hautinitierenden Wirkung zudem auch ein hohes Kalklöse- und Kalkseifenlösevermögen der Säuremischungen vor allem mit n-Octylsulfat (C8) erreicht.Another object of the invention is the use of anionic surfactants for damping the hautkonosiven action of a strongly acidic decalcifying agent Especially when the agent based on citric acid and / or lactic acid with methanesulfonic acid, as stated above, is constructed, in addition to the damping of skin corrosive / skin-initiating Effect also achieved a high lime and Kalkseifenlösevermögen the acid mixtures especially with n-octyl sulfate (C8).

Das erfindungsgemäße Entkalkungsmittel eignet sich insbesondere zur Verwendung als Sanitär- oder WC-ReinigerThe descaling agent according to the invention is particularly suitable for use as a sanitary or toilet cleaner

Hilfs- und ZusatzstoffeAuxiliaries and additives

Das erfindungsgemäße Reinigungsmittel kann einen oder mehrere von üblichen Hilfs- und Zusatzstoffen enthalten, vorzugsweise ausgewählt aus der Gruppe umfassend wasserlösliche Lösemittel, Farbstoffe, Duftstoffe, Desinfektions- und Konservierungsmittel, Korrosionsinhibitoren, Komplexbildner für Erdalkaliionen, Sequestriermittel und Enzyme Zur Emulgierung der Parfümöle können bei Bedarf zudem geeignete Emulgatoren zugesetzt werden.The cleaning agent according to the invention may comprise one or more of customary auxiliaries and additives, preferably selected from the group comprising water-soluble solvents, dyes, fragrances, disinfectants and preservatives, corrosion inhibitors, complexing agents for alkaline earth ions, sequestering agents and enzymes For emulsifying the perfume oils, it is also possible, if required suitable emulsifiers are added.

Wasserlösliche LösemittelWater-soluble solvents

Das Reinigungsmittel kann ein oder mehrere wasserlösliche, organische Lösemittel, vorzugsweise aus der Gruppe der Alkohole oder Glycole bzw. Glycolether enthalten. Die bevorzugt zugesetzten Mengen betragen 0,05 bis 10 Gew.%, insbesondere bevorzugt 0,1 bis 5 Gew.% Geeignete wasserlösliche Lösemittel sind z.B. die Alkohole Ethanol, n-Propanol, isoPropanol, ferner die Etherverbindungen von Ethylenglycol oder Diethylenglycol bzw. Propylenglycol oder Dipropylenglycol mit Methanol, Ethanol, n- und iso- Propanol, n- und isoButanol, z.B. Ethylenglycolbutylether (BG), Diethylenglycolethylether (EDG), Diethylenglycolbutylether (BDG), Propylenglycolmethylether (PM), Propylenglycol-n-butylether (PnB, 3-Butoxy-2-butanol), Dipropylenglycolmethylether (DPM), Dipropylenglycol-n-propylether (DPnP), Dipropylenglycol-n-butylether (DPnB) Ferner können auch die Dietherverbindungen aus den genannten Glycolen und Alkoholen eingesetzt werden sowie Mischungen der genannten Lösemittel.The cleaning agent may contain one or more water-soluble, organic solvents, preferably from the group of alcohols or glycols or glycol ethers. The amounts preferably added are from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight. Suitable water-soluble solvents are e.g. the alcohols ethanol, n-propanol, isopropanol, furthermore the ether compounds of ethylene glycol or diethylene glycol or propylene glycol or dipropylene glycol with methanol, ethanol, n- and iso-propanol, n- and iso-butanol, e.g. Ethylene glycol butyl ether (BG), diethylene glycol ethyl ether (EDG), diethylene glycol butyl ether (BDG), propylene glycol methyl ether (PM), propylene glycol n-butyl ether (PnB, 3-butoxy-2-butanol), dipropylene glycol methyl ether (DPM), dipropylene glycol n-propyl ether (DPnP). , Dipropylene glycol n-butyl ether (DPnB) Furthermore, the diether compounds from the said glycols and alcohols can be used as well as mixtures of said solvents.

Farb-und DuftstoffeDyes and perfumes

Das Reinigungsmittel kann einen oder mehrere Duftstoffe, vorzugsweise in einer Menge von 0,01 bis 1 Gew.-%, bevorzugt 0,05 bis 0,5 Gew.-%, besonders bevorzugt 0,1 bis 0,3 Gew.-%, und/oder ein oder mehrere Farbstoffe, vorzugsweise in einer Menge von 0,0001 bis 0,1 Gew - %, bevorzugt 0,0005 bis 0,05 Gew.-%, besonders bevorzugt 0,001 bis 0,01 Gew.-%, enthaltenThe cleaning agent may contain one or more perfumes, preferably in an amount of from 0.01 to 1% by weight, preferably from 0.05 to 0.5% by weight, particularly preferably from 0.1 to 0.3% by weight, and / or one or more dyes, preferably in an amount of from 0.0001 to 0.1% by weight, preferably from 0.0005 to 0.05% by weight, particularly preferably from 0.001 to 0.01% by weight

Desinfektions- und KonservierungsmittelDisinfectant and preservative

Eine besondere Form der Reinigung stellt die Desinfektion dar. In einer entsprechenden besonderen Ausführungsform der Erfindung enthält das Reinigungsmittel daher einen oder mehrere antimikrobielle Wirkstoffe Als Desinfektion wird die Abtötung von Infektionskeimen verstanden. Das Ausmaß der Desinfektion ist von der antimikrobiellen Wirkung des angewendeten Mittels abhängig, die mit abnehmendem Gehalt an antimikrobiellem Wirkstoff bzw. zunehmender Verdünnung des Mittels zur Anwendung abnimmt.A particular form of cleaning is the disinfection. In a corresponding particular embodiment of the invention, the cleaning agent therefore contains one or more antimicrobial active substances. Disinfection is understood to mean the killing of infectious germs. The extent of disinfection depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial content or increasing dilution of the agent for use.

Bevorzugte antimikrobielle Wirkstoffe werden vorzugsweise ausgewählt aus der Gruppe umfassend Ethanol, n-Propanol, i-Propanol, Phenoxyethanol, Milchsäure (sofern nicht schon als Wirkstoff enthalten), Benzoesäure, Salicylsäure und gegebenenfalls antimikrobielle quaternäre oberflächenaktive VerbindungenPreferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, phenoxyethanol, lactic acid (if not already present as active ingredient), benzoic acid, salicylic acid and optionally antimicrobial quaternary surface-active compounds

Korrosionsinhibitorencorrosion inhibitors

Weiterhin kann das Reinigungsmittel einen oder mehrere Metall-Korrosionsinhibitoren, vorzugsweise in einer Menge von 0,1 bis 5 Gew.-%, bevorzugt 0,5 bis 3 Gew.-%, besonders bevorzugt 0,5 bis 2 Gew.-%, enthaltenFurthermore, the cleaning agent may contain one or more metal corrosion inhibitors, preferably in an amount of from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight, particularly preferably from 0.5 to 2% by weight

Geeignete Korrosionsinhibitoren sind beispielsweise folgende Substanzen: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphate, Nitromethane, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.Suitable corrosion inhibitors are, for example, the following substances: cyclohexylamines, diammonium phosphates, dilithium oxalates, dimethylamino methylpropanol, dipotassium oxalates, dipotassium phosphates, disodium phosphates, disodium pyrophosphates, disodium tetrapropenyl succinates, hexoxyethyl diethylammonium, phosphates, nitromethanes, potassium silicates, sodium aluminates, sodium hexametaphosphates, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrites, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.

Komplexbildner und SequestriermittelComplexing agent and sequestering agent

Auch kann das Reinigungsmittel ein oder mehrere Komplexbildner, vorzugsweise in einer Menge von 0,1 bis 10 Gew.-%, bevorzugt 0,2 bis 5 Gew.-%, besonders bevorzugt 0,5 bis 3 Gew.- %, enthalten
Komplexbildner / Sequestriermittel sind Inhaltsstoffe, die Metallionen zu komplexieren und inaktivieren vermögen, um ihre nachteiligen Wirkungen auf die Stabilität oder das Aussehen der Mittel, beispielsweise Trübungen zu verhindern. Einerseits ist es dabei wichtig, die mit zahlreichen Inhaltsstoffen inkompatiblen Calcium- und Magnesiumionen der Wasserhärte zu komplexieren Die Komplexierung der Ionen von Schwermetallen wie Eisen oder Kupfer verzögert andererseits die oxidative Zersetzung der fertigen Mittel. Zudem unterstützen die Komplexbildner die Reinigungswirkung.The cleaning agent may also contain one or more complexing agents, preferably in an amount of from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, particularly preferably from 0.5 to 3% by weight
Chelants / sequestrants are ingredients that are capable of complexing and inactivating metal ions to prevent their detrimental effects on the stability or appearance of the agents, for example clouding. On the one hand, it is important to add calcium and magnesium ions that are incompatible with numerous ingredients to the water hardness Complexing the ions of heavy metals such as iron or copper, on the other hand, delays the oxidative decomposition of the finished agents. In addition, the complexing agents support the cleaning effect.

Geeignet sind beispielsweise die folgenden gemäß INCI bezeichneten Komplexbildner: Aminotrimethylene Phosphonsäure, Beta-Alanine Diacetic Acid, Calcium Disodium EDIA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetra- methylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxide, Ribonic Acid, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA-Polyphos-phate, 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 und Trisodium Phosphate.Suitable are, for example, the following according to INCI designated complexing agents: Aminotrimethylene phosphonic acid, beta-alanines diacetic acid, calcium disodium EDIA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriamine pentamethylene phosphonic acid, dipotassium EDTA, disodium azacycloheptanes diphosphonates, 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 Tetra- methylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Potassium Citrate , Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, So Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

Enzymeenzymes

Das Mittel kann auch Enzyme enthalten, vorzugsweise Proteasen, Lipasen, Amylasen, Hydrolasen und/oder Cellulasen Sie können dem erfindungsgemäßen Mittel in jeder nach dem Stand der Technik etablierten Form zugesetzt werden. Hierzu gehören bei flüssigen oder gelförmigen Mitteln insbesondere Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren versetzt.The agent may also contain enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They may be added to the composition according to the invention in any form established according to the prior art. In the case of liquid or gel-containing compositions, these include, in particular, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

Zur Charakterisierung der Leistungsfähigkeit der Reinigungsmittel und zur Bestimmung seiner Hautkorrosivität wurden nachfolgend beschriebene Methoden eingesetzt.To characterize the performance of the detergents and to determine its skin corrosiveness, methods described below were used.

Kalklösevermögen:Kalklösevermögen:

Die Methode ist angelehnt an die Empfehlung zur Qualitätsbewertung für Badezimmerreiniger (IKW, Fassung 2002) und die Empfehlung zur Qualitätsbewertung für saure WC-Reiniger (IKW, Fassung 1999)The method is based on the recommendation for quality assessment for bathroom cleaners (IKW, version 2002) and the recommendation for quality assessment of acidic toilet cleaners (IKW, version 1999)

Durchführung:Execution:

Mit Ethanol entfettete und unter fließendem Wasser mit einer Bürste gereinigte Marmorplatten einheitlicher Dimension werden bei 105°C für 60 min getrocknet und nach dem Erkalten auf einer Analysenwaage (+/- 1 mg) ausgewogen.Slabs of degreased with ethanol and cleaned under running water with a brush uniformly sized marble slabs are dried at 105 ° C for 60 min and weighed after cooling on an analytical balance (+/- 1 mg).

Anschließend weiden die Platten für 10 Minuten in ein definiertes Volumen der Entkalkungsflüssigkeit eingetaucht (zur statistischen Absicherung der Methode wird eine 4-fach Bestimmung durchgeführt). Nach gründlichem Abspülen der Patten mit demineralisiertem Wasser und einer erneuten Trocknung bei 105°C wird der Gewichtsverlust jeder Marmorplatte durch Wiegen bestimmt. Die Messwerte aus den Mehrfachbestimmungen werden gemittelt und protokolliert. Die abgetragene Menge an Marmor (CaCO3) entspricht dem Kalklösevermögen des Badreinigers.
Die Temperatur der Entkalkungsflüssigkeit sowie der Marmorplatten sollte während der Versuchsdurchführung zwischen 20 und 23°C betragen.The plates are then immersed in a defined volume of decalcifying liquid for 10 minutes (a 4-fold determination is made for statistical verification of the method). After thoroughly rinsing the patten with demineralized water and re-drying at 105 ° C, the weight loss of each marble slab is determined by weighing. The measured values from the multiple determinations are averaged and logged. The amount of marble removed (CaCO 3 ) corresponds to the lime-release capacity of the bath cleaner.
The temperature of the decalcifying liquid and the marble slabs should be between 20 and 23 ° C during the experiment.

Kalklöseseifenlösevermögen:Kalklöseseifenlösevermögen:

Die Methode für das Kalkseifenlösevermögen ist angelehnt an die Empfehlung zur Qualitätsbewertung für Badezimmerreiniger (IKW, Fassung 2002)The method for the Kalkseifenlösevermögen is based on the recommendation for quality evaluation for bathroom cleaners (IKW, version 2002)

Durchführung:Execution:

Auf eine gereinigte, weiße Fliese wird mit Hilfe einer Airbrush-Pistole eine definierte Menge einer Schmutzsuspension aufgebracht. Diese besteht aus Calciumstearat (Kalkseife), Farbstoff (Ruß) und einem Lösemittel Nach dem Auftragen wird die Fliese bei 180°C getrocknet Dabei verdunstet das Lösemittel und die geschmolzene Kalkseife bleibt nach dem Abkühlen samt gebundenem Ruß als feste, glatte Schicht zurück. Durch Wiegen wird die aufgetragene Schmutzmenge bestimmt.On a cleaned, white tile with the help of an airbrush gun, a defined amount of a dirt suspension is applied. This consists of calcium stearate (lime soap), dye (carbon black) and a solvent After application, the tile is dried at 180 ° C. The solvent evaporates and the molten lime soap remains after cooling with its bound soot back as a solid, smooth layer. Weighing determines the amount of dirt applied.

Anschließend wird die so beschmutzte Oberfläche mit einer Schablone in zwölf gleichgroße, rechteckige Felder eingeteilt (3 Reihen zu je 4 Feldern). Die drei Reihen werden nun mit dem verschiedenen Sanitärreiniger benetzt. Die Einwirkzeit der Reiniger auf den 4 Feldern einer Reihe variiert von 10 min, 7,5 min, 5 min bis 2,5 min. Nach diesen definierten Kontaktzeiten weiden die Flächen unten fließendem Wasser mit Hilfe eines Schwamms gereinigt. Das Reinigungsergebnis auf den Einzelfeldern wird mittels Foto dokumentiert und visuell beurteilt. Ein hoher Grad an Kalkseifenlösevermögen bzw. Kalkseifenlösegeschwindigkeit zeigt sich in möglichst weißen Flächen nach möglichst kurzen Kontaktzeiten.Then the soiled surface is divided with a stencil into twelve equal rectangular fields (3 rows of 4 fields each). The three rows are now wetted with the various sanitary cleaner. The contact time of the cleaners on the 4 fields of a row varies from 10 min, 7.5 min, 5 min to 2.5 min. After these defined contact times graze the areas below running water with the help of a sponge cleaned. The cleaning result on the individual fields is documented by means of a photo and assessed visually. A high degree of Kalkseifenlösevermögen or Kalkseifenlösegeschwindigkeit shows up in as white areas as possible after the shortest possible contact times.

Hautinitationstest gemäß OECD 431:Skin Injury Test according to OECD 431:

Im Hautinitationstest gemäß OECD 431 werden mögliche hautkorrosive Wirkungen von Stoffen oder Zubereitungen zuverlässig ermittelt. Dieses in-vitro-Verfahren nutzt epidermale 3D-Hautkulturmodelle aus rekultivierter menschlicher HautThe Skin Ingression Test according to OECD 431 reliably identifies potential skin corrosive effects of substances or preparations. This in vitro method utilizes epidermal 3D skin culture models from recultured human skin

Die Versuchssubstanz/-zubereitung wirkt zeitgleich zu einer Negativ-Kontrolle (destilliertes Wasser) sowie einer Positiv-Kontrolle (8 mol/l Kaliumhydroxid) auf das Hautgewebe ein. Nach 3min sowie 1 Std. Einwirkzeit der Testsubstanz wird die Enzymaktivität im Hautgewebe über eine Farbreaktion bestimmt. Zunehmende Hautgewebsschädigung ("Korrosion") führt zu einer abnehmenden Enzymaktivität bzw. FarbstofProduktion. Bei Unterschreitung spezifischer festgelegter Schwellenwerten für die Rest-Enzymaktivität bzw. -Farbstoffproduktion nach 3 min sowie 1 Std wird die Testsubstanz als "hautkorrosiv" eingestuft Bei Überschreitung dieser Grenzwerte wird die Testsubstanz entsprechend als "nicht hautkorrosiv" eingestuft.The test substance / preparation acts simultaneously on a negative control (distilled water) and a positive control (8 mol / l potassium hydroxide) on the skin tissue. After 3 minutes and 1 hour exposure time of the test substance, the enzyme activity in the skin tissue is determined via a color reaction. Increasing skin tissue damage ("corrosion") leads to a decrease in enzyme activity or dye production. When the specific thresholds for residual enzyme activity or dye production are not reached after 3 minutes and 1 hour, the test substance is classified as "corrosive to the skin". If these limit values are exceeded, the test substance is correspondingly classified as "non-corrosive to the skin".

Weitere Angaben zu erfindungsgemäßen Mitteln sind auch den nachfolgenden Beispielen zu entnehmen.Further information on agents according to the invention can also be found in the following examples.

Diese beispielhaften Sanitärreiniger sind vorzugsweise zur Flächenentkalkung im Sanitärbereich, z.B. für Fliesen, Waschbecken, Toilettenbecken, Urinalen oder Armaturen geeignet. In entsprechenden Verdünnungen mit Wasser (1:1 bis 1:3) ist der Reiniger darüber hinaus in Wasserkochern, Kaffeemaschinen usw zur Entfernung von Kalkablagerungen von Vorteil.These exemplary sanitary cleaners are preferably suitable for surface decalcification in the sanitary sector, eg for tiles, sinks, toilet bowls, urinals or fittings. In addition, in appropriate dilutions with water (1: 1 to 1: 3), the cleaner is of advantage in kettles, coffee machines, etc. for the removal of calcium deposits.

Beispiel 1:Example 1:

Stark saurer Sanitärreiniger auf Basis Milchsäure/Methansulfonsäure (jeweils Gew.-%)Strongly acidic sanitary cleaner based on lactic acid / methanesulfonic acid (in each case% by weight) Nr.1Number 1 Nr.2No. 2 Nr.3No.3 Milchsäure (Säure 1)Lactic acid (acid 1) 7,1%7.1% 7,1%7.1% 7,1%7.1% Methansulfonsäure (Säure 2)Methanesulfonic acid (acid 2) 2,8%2.8% 2,8%2.8% 2,8%2.8% Octylsulfat-Na-Salz (anion Tensid)Octyl sulfate Na salt (anionic surfactant) -- -- 0,95%0.95% Fettalkohol C10-6 EO (nichtion Tensid)Fatty alcohol C10-6 EO (nonionic surfactant) -- 0,95%0.95% -- ParfümPerfume -- 0,15%0.15% 0,15%0.15% Fettalkohol C10-6 EO (Patfümemulgator)Fatty alcohol C10-6 EO (patulem emulsifier) -- -- 0,1%0.1% Farbstoff (rot)Dye (red) 0,001%0.001% 0,001%0.001% 0,001%0.001% Wasserwater ad 100%ad 100% ad 100%ad 100% ad 100%ad 100% pH-Wert (20°C, konz.)pH value (20 ° C, conc.) 0,60.6 0,60.6 0,60.6 Kalklösevermögen waagerecht [mg CaCO3]Leaching properties horizontal [mg CaCO 3 ] 26502650 24302430 26402640 Kalkseifenlösevermögen (5 min)Kalkseifenlösevermögen (5 min) 1%1% 50%50% 100%100% OECD 431OECD 431 "hautkorrosiv""Hautkorrosiv" "hautkorrosiv""Hautkorrosiv" "nicht hautkorrosiv""not corrosive"

Das Beispiel zeigt, dass das Entkalkungsmittel Nr. 1 ein hohes Kalklösevermögen basierend auf der Kombination von Milchsäure und Methansulfonsäure aufweist Sein Kalkseifenlösevermögen bleibt aufgrund fehlender Tenside jedoch sehr geringThe example shows that descaling agent no. 1 has a high calendering power based on the combination of lactic acid and methanesulfonic acid. Its lime soap dissolving power, however, remains very low due to lack of surfactants

Ein erfindungsgemäßes Reinigungsmittel nach Nr.3 mit einem Zusatz von 0,95 Gew.-% des angegebenen anionischen Tensids zeigt im Vergleich zu dem Reinigungsmittel Nr.2, das den gleichen Anteil eines nichtionischen Tensids enthält, ein höheres Kalklösevermögen in Verbindung mit erhöhtem Kalkseifenlösevermögen und zusätzlich nicht hautkorrosive EigenschaftAn inventive detergent according to No. 3 with an addition of 0.95 wt .-% of the stated anionic surfactant shows in comparison to the detergent No.2, which contains the same proportion of a nonionic surfactant, a higher lime release power in conjunction with increased Kalkseifenlösevermögen and additionally not corrosive property

Das anionische Tensid erhält somit - anders als ein übliches nichtionisches Tensid - das hohe Kalklösevermögen des ansonsten identischen, jedoch tensidfreien Entkalkungsmittels aufrecht. Es erhöht zudem gleichzeitig das Kalkseifenlösevermögen deutlich stärker, als das ansonsten identische Reinigungsmittel mit einem üblichen nichtionischen Tensid Zudem resultiert nur bei Zugabe des anionischen Tensids eine nicht hautkorrosive Eigenschaft.Thus, unlike a conventional nonionic surfactant, the anionic surfactant maintains the high laking power of the otherwise identical but surfactant-free descaling agent. It also increases the Kalkseifenlösevermögen at the same time much stronger than the otherwise identical cleaning agent with a conventional nonionic surfactant addition also results only on addition of the anionic surfactant non-corrosive property.

Beispiel 2:Example 2:

Stark saure Sanitärreiniger auf Basis Zitronensäure/Methansulfonsäure (jeweils Gew.-%)Strongly acidic sanitary cleaner based on citric acid / methanesulfonic acid (in each case% by weight) Nr 4No. 4 Nr.5No.5 Nr 6No. 6 Zitronensäure (Säure 1)Citric acid (acid 1) 8%8th% 8%8th% 8%8th% Methansulfonsäure (Säure 2)Methanesulfonic acid (acid 2) 2,95%2.95% 2,95%2.95% 2,95%2.95% Octylsulfat-Na-Salz (anion Tensid)Octyl sulfate Na salt (anionic surfactant) -- -- 0,95%0.95% Fettalkohol C10-6 EO (nichtion Tensid)Fatty alcohol C10-6 EO (nonionic surfactant) -- 0,95%0.95% -- ParfümPerfume -- 0,15%0.15% 0,15%0.15% Fettalkohol C10-6 EO (Parfümemulgator)Fatty alcohol C10-6 EO (perfume emulsifier) -- -- 0,1%0.1% Farbstoff(rot)Dye (red) 0,001%0.001% 0,001%0.001% 0,001%0.001% Wasserwater ad 100%ad 100% ad 100%ad 100% ad 100%ad 100% pH-Wert (20°C, konz)pH value (20 ° C, conc.) 0,60.6 0,60.6 0,60.6 Kalklösevermögen waagerecht [mg CaCO3]Leaching properties horizontal [mg CaCO 3 ] 24502450 19001900 24702470 Kalkseifenlösevermögen (5 min)Kalkseifenlösevermögen (5 min) 1%1% 40%40% 80%80% Kalkseifenlösevermögen (10 min)Calcium soap dissolving power (10 min) 1%1% 80%80% 98%98% OECD 431OECD 431 "nicht hautkonosiv""not cutaneous" "hautkorrosiv""Hautkorrosiv" "nicht hautkorrosiv""not corrosive"

Das Entkalkungsmittel Nr.4 weist ein hohes Kalklöseveimögen in Verbindung mit nicht hautkorrosiver Eigenschaft auf trotz des pH-Wertes von 0,6.Descaling agent # 4 has a high level of limescale associated with non-corrosive property, despite the pH of 0.6.

Ein Vergleich der Reinigungsmittel Nr.5 und Nr.6 zeigt die überlegene Wirkung eines anionischen Tensids im Verhältnis zu einem nichtionischen Tensid hinsichtlich Kalklösevermögen sowie Kalkseifenlösevermögen und nicht hautkorrosiver Eigenschaft Die hautirritierende Wirkung von Reinigungsmittel Nr. 6 ist zudem gegenüber Entkalkungsmittel Nr. 4 weiter reduziert.A comparison of the cleaning agents No. 5 and No. 6 shows the superior effect of an anionic surfactant in relation to a nonionic surfactant with respect to laking and lime soap power and non-corrosive property. The skin irritation effect of detergent No. 6 is further reduced compared to descaling agent no.

Claims (12)

  1. Cleaning agent, comprising
    a combination of 3-15 wt.% citric acid and from 0.5 to 5 wt.% methanesulfonic acid in combination with at least one anionic surfactant from the group of C8-C14 fatty alcohol sulfates or C8-C14 iso-alcohol sulfates, and/or C8-C14 fatty alcohol ether sulfates, wherein the cleaning agent is not skin-corrosive according to validated test method OECD 431.
  2. Cleaning agent, comprising
    a combination of 3-15 wt.% lactic acid and from 0.5 to 5 wt.% methanesulfonic acid in combination with at least one anionic surfactant from the group of C8-C14 fatty alcohol sulfates or C8-C14 iso-alcohol sulfates, and/or C8-C14 fatty alcohol ether sulfates, wherein the cleaning agent is not skin-corrosive according to validated test method OECD 431.
  3. Cleaning agent according to Claim 1, containing from 3 to 10 wt.%, and in particular from 3 to 8 wt.%, citric acid.
  4. Cleaning agent according to Claim 2, containing from 1 to 10 wt.%, and in particular from 1 to 8 wt.%, lactic acid.
  5. Cleaning agent according to any one of the preceding claims, containing from 0.5 to 3 wt.% methanesulfonic acid.
  6. Cleaning agent according to any one of the preceding claims, having a pH < 2.0, preferably pH < 1.5, and in particular pH < 1.0.
  7. Cleaning agent according to Claim 1 or 2, wherein the anionic surfactant is an octyl sulfate (C8).
  8. Cleaning agent according to any one of the preceding claims, which contains and anionic surfactant or a plurality of anionic surfactants up to 5 wt.%, preferably up to 3 wt.%, and in particular to 1 wt.%, of the total concentration.
  9. Cleaning agent according to any one of the preceding claims, containing one or more auxiliaries or additives conventionally used in cleaning agents, preferably selected from the group comprising water-soluble solvents, colourants, fragrances, disinfectants or preservatives, corrosion inhibitors, complexing agents, sequestering agents and/or enzymes.
  10. Cleaning agent according to any one of the preceding Claims 2 and 4 to 9, containing
    from 1 to 10 wt.%, preferably from 4 to 10 wt.%, in Particular from 4 to 8 wt.%, preferably 7.1 wt.%, lactic acid,
    from 0.5 to 2.95 wt.%, preferably from 1.5 to 2.95 wt.%, in particular 2.8 wt.%, methanesulfonic acid, and
    from 0.8 to 0.95 wt.% n-octyl sulfate (C8),
    wherein the pH is < 1.5, in particular < 1.0, the cleaning agent being not skin corrosive.
  11. Cleaning agent according to any one of the preceding Claims 1, 3 and 5 to 9, containing
    from 8 to 15 wt.%, preferably from 5 to 12 wt.%, in particular from 6 to 8 wt.%, preferably 8 wt.%, citric acid,
    from 0.5 to 2.95 wt.%, preferably from 1.5 to 2.95 wt.%, methanesulfonic acid, and
    from 0.8 to 0.95 wt.% n-octyl sulfate (C8),
    wherein the pH is < 1.0, the cleaning agent being not skin corrosive.
  12. Use of an anionic surfactant according to any one of the preceding claims for reducing the skin-corrosive effect of a strongly acidic decalcifying agent as a sanitary cleaner or WC cleaner.
EP14182845.9A 2013-08-30 2014-08-29 Cleaning agent with decalcification effect Active EP2843034B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102013217325.3A DE102013217325A1 (en) 2013-08-30 2013-08-30 Detergent with descaling effect

Publications (2)

Publication Number Publication Date
EP2843034A1 EP2843034A1 (en) 2015-03-04
EP2843034B1 true EP2843034B1 (en) 2018-01-31

Family

ID=51421965

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14182845.9A Active EP2843034B1 (en) 2013-08-30 2014-08-29 Cleaning agent with decalcification effect

Country Status (2)

Country Link
EP (1) EP2843034B1 (en)
DE (1) DE102013217325A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112020005885A2 (en) * 2017-09-26 2020-09-29 Ecolab Usa Inc. antimicrobial, virucide, solid antimicrobial and solid virucide compositions, and methods for using an antimicrobial composition and inactivating a virus.
US11273625B2 (en) 2018-12-21 2022-03-15 The Clorox Company Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene
MX2021011796A (en) 2019-04-02 2021-10-13 Clorox Co Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene.

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69329398T2 (en) * 1993-11-29 2001-04-12 Procter & Gamble Scale removal compositions
ES2156147T3 (en) * 1994-02-03 2001-06-16 Procter & Gamble COMPOSITIONS TO ELIMINATE CAL INCRUSTATIONS.
TW200734448A (en) * 2006-02-03 2007-09-16 Advanced Tech Materials Low pH post-CMP residue removal composition and method of use
WO2009124314A1 (en) * 2008-04-04 2009-10-08 Ecolab Inc. Limescale and soap scum removing composition containing methane sulfonic acid
CN101372649B (en) * 2008-09-24 2010-12-22 北京洛娃日化有限公司 Acidic bathroom detergent
FR2939146B1 (en) * 2008-11-28 2012-11-16 Arkema France USE OF ALKANE SULFONIC ACID FOR RUST REMOVAL
MX349860B (en) * 2011-04-14 2017-08-16 Basf Se Method of dissolving and/or inhibiting the deposition of scale on a surface of a system.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
DE102013217325A1 (en) 2015-03-05
EP2843034A1 (en) 2015-03-04

Similar Documents

Publication Publication Date Title
DE69827845T2 (en) Cleaning agents for ceramic and porcelain surfaces as well as suitable procedures
AT393688B (en) ACID, LIQUID CLEANING AGENT FOR CERAMIC PLATES AND METHOD FOR THE PRODUCTION THEREOF
EP2494025B1 (en) Antimicrobial cleaning agent for hard surfaces
EP2970828B1 (en) Cleaners for hard surfaces comprising phosphoric acid esters of a polyether-modified alkyl alcohol
DD295865A5 (en) LIQUID CLEANING AGENT
DE112006001146T5 (en) Household cleaning composition
EP2843034B1 (en) Cleaning agent with decalcification effect
DE2840463C2 (en) Using a liquid agent to clean hard surfaces
DE102013226446A1 (en) Microemulsions with biosurfactants
EP1335965B1 (en) Treatment of surfaces for temporarily improving their dirt removal behavior
EP1781765B1 (en) Use of a cleaning agent exhibiting faecal stain repelling properties
EP1619237B1 (en) Aqueous cleaning concentrates for rough preferably profiled tiles and plates
DE202013103933U1 (en) Detergent with descaling effect
JP3441885B2 (en) Toilet cleaner composition
EP4066644A1 (en) Disinfecting cleaner, method for its preparation and its use
EP1232236B1 (en) Use of formulations for treating surfaces for temporarily improving dirt-removing behavior
JP6158065B2 (en) Cleaning composition for hard surface
EP3835399B1 (en) Hard surface cleaning composition
DE2445710A1 (en) DETERGENT MIXTURE AND METHOD OF PREPARING THE SAME
DE10124288A1 (en) Aqueous hard surface cleaning composition, especially for tiles, containing alkali metal hypochlorite, carbonate and hydroxide, surfactant and hydrotrope, plus amine oxide phosphonic acid to improve gloss after cleaning
DE102016225903A1 (en) Hard surface cleaner with long-lasting fragrance and shine
DE10124289A1 (en) Aqueous hard surface cleaning composition, especially for tiles, containing alkali metal hypochlorite and hydroxide, betaine and hydrotrope, plus amine oxide phosphonic acid to improve gloss after cleaning
WO2016102389A1 (en) Polymers for cleaners with surface-modifying effect
DE102005063065A1 (en) Corrosion inhibition of liquid hypochlorite detergent
DE19748379A1 (en) Process for cleaning floors

Legal Events

Date Code Title Description
17P Request for examination filed

Effective date: 20140829

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

R17P Request for examination filed (corrected)

Effective date: 20150902

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20170914

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 967405

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502014007078

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180430

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180531

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180430

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180501

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502014007078

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20181102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20180829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180829

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140829

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180131

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180829

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180131

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20230823

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20230831

Year of fee payment: 10

Ref country code: AT

Payment date: 20230818

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230821

Year of fee payment: 10

Ref country code: DE

Payment date: 20230907

Year of fee payment: 10

Ref country code: BE

Payment date: 20230822

Year of fee payment: 10