EP3164477B1 - Agent de lavage contenant un inhibiteur de corrosion du verre - Google Patents

Agent de lavage contenant un inhibiteur de corrosion du verre Download PDF

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Publication number
EP3164477B1
EP3164477B1 EP15731970.8A EP15731970A EP3164477B1 EP 3164477 B1 EP3164477 B1 EP 3164477B1 EP 15731970 A EP15731970 A EP 15731970A EP 3164477 B1 EP3164477 B1 EP 3164477B1
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Prior art keywords
cleaning
cleaning agent
glass
acid
weight
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EP15731970.8A
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German (de)
English (en)
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EP3164477A1 (fr
Inventor
Alexander Schulz
Inga Kerstin Vockenroth
Nicole BODE
Peter Schmiedel
Danuta Bedrunka
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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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • 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
    • C11D2111/18—Glass; Plastics

Definitions

  • the present invention relates to a cleaning agent with which glass corrosion can be reduced or even avoided, particularly during machine cleaning.
  • the detergent is a dishwashing detergent for machine cleaning of dishes.
  • the present invention also relates to a method for cleaning objects with a glass surface using the cleaning agent according to the invention.
  • the task of cleaning agents is usually to clean dirty surfaces. On the one hand, they should remove stubborn dirt. On the other hand, the cleaned surfaces should not be attacked. In particular in the case of objects which have a surface made of glass, it is often problematic that the glass is attacked, so that glass corrosion occurs. Glass corrosion is a frequently occurring problem, particularly when washing dishes using conventional dishwashing detergents.
  • the washing liquor in which dishes are cleaned with conventional dishwashing detergents usually has a pH of 8.0 or more. Many types of glass customary on the market are attacked here and thus show signs of cloudiness over the course of many washing cycles, which are referred to as glass corrosion.
  • cleaning agents and, in particular, dishwashing detergents have a low phosphate content or even manage completely without phosphates.
  • Necessary substitutes for this are complexing agents, which, however, attack the glass surfaces to be cleaned WO 99/05248 and WO 2014/027181 A1 known.
  • the object of the present invention is to provide a dishwashing detergent for cleaning objects with glass surfaces, the purpose of which is to reduce or at least reduce the glass corrosion caused in particular by complexing agents.
  • the cleaning performance of the product with regard to the removal of soiling should not be adversely affected.
  • PDADMAC polydiallyldimethylammonium chloride
  • the cleaning agent according to the invention comprises PDADMAC in a proportion of 0.01 to 1% by weight.
  • a proportion of less than 0.01% by weight of PDADMAC in a cleaning agent does not lead to any noticeable reduction in glass corrosion.
  • a proportion of 1% by weight can easily be incorporated into cleaning agents. At the same time, this results in a significant reduction in glass corrosion.
  • a proportion of 50% by weight can also be incorporated into a cleaning agent without its cleaning performance being adversely affected. However, a proportion exceeding this does not lead to any further improvement with regard to glass corrosion.
  • the cleaning agent according to the invention comprises at least one surfactant.
  • the cleaning agent can comprise one or more surfactants.
  • the at least one surfactant is preferably selected from the group comprising nonionic surfactants, cationic surfactants, anionic surfactants, zwitterionic surfactants and mixtures thereof.
  • the cleaning agent can therefore preferably comprise one or more nonionic surfactants.
  • it comprises a nonionic surfactant together with, for example, an anionic surfactant.
  • Other combinations of the surfactants are also included according to the invention.
  • the cleaning agent according to the invention contains at least one nonionic surfactant.
  • All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants (nonionic surfactants).
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol , which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • Another class of preferably used nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half that.
  • polyhydroxy fatty acid amides of the following formula, in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the following formula in which R stands for a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms, R 1 for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R 2 for a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R stands for a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms
  • R 1 for a linear, branched or cyclic alkyl radical or an aryl
  • [Z] is preferably obtained by reductive amination of a reduced sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
  • the cleaning agents according to the invention in particular cleaning agents for automatic dishwashing, particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical mean values which, for a specific product, can correspond to a whole number or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants made from C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide were obtained per mole of alcohol, used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol with 16 to 20 carbon atoms
  • C 18 alcohol preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature are particularly preferred.
  • Suitable nonionic surfactants which have melting points or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Nonionic surfactants which have a waxy consistency at room temperature are also preferred.
  • Nonionic surfactants from the group of alkoxylated alcohols particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO nonionic surfactants, are also used with particular preference.
  • the nonionic surfactant which is solid at room temperature, preferably has propylene oxide units (PO) in the molecule.
  • PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule are up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic Make up surfactants.
  • Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • structurally complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) non-ionic surfactants are also characterized by good foam control.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight.
  • Low-foaming non-ionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants in the context of the present invention.
  • surfactants with EO-AO-EO-AO blocks are again preferred, one to ten EO or AO groups being bonded to one another before a block from the other groups follows.
  • nonionic surfactants of the general formula preferably in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 -alkyl or -alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another for whole numbers from 1 to 6 are available.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or radicals which are methyl-branched in the 2-position or linear and methyl-branched radicals in a mixture, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R 1 in the above formula represents an alkyl radical with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • butylene oxide in particular comes into consideration as the alkylene oxide unit, which is contained in the preferred nonionic surfactants alternating with the ethylene oxide unit.
  • R 2 or R 3 are selected independently of one another from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are also suitable.
  • nonionic surfactants which have a C 9-15 -alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • These surfactants have the required low viscosity in aqueous solution and can be used with particular advantage according to the invention.
  • R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 in which R 1 and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 -alkyl or -alkenyl radical;
  • A, A ', A "and A"' independently of one another for a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and
  • w, x, y and z stand for values between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferred
  • Nonionic surfactants of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH) R are very particularly preferred 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof denotes and x and z for values between 0 and 40 and y for a value of at least 15, preferably from 15 to 120, particularly preferably from 20 to 80.
  • the cleaning agent contains, based on its total weight, nonionic surfactant of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH) R 2 in amounts from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1 , 0 to 6% by weight.
  • nonionic surfactant of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH) R 2 in amounts from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1 , 0 to 6% by weight.
  • those end-capped poly (oxyalkylated) nonionic surfactants according to the formula R 1 O [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 to 22, in particular, are preferred with 6 to 16 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof, and y denotes a value between 15 and 120, preferably 20 to 100, in particular 20 to 80.
  • Hydroxy mixed ethers for example belong to the group of non-ionic surfactants of the general formula C 6-22 -CH (OH) CH 2 O (EO) -C 2-26 20-120, for example, the C 8-12 fatty alcohol (EO) 22 -2 hydroxydecyl ether and the C 4-22 fatty acid (EO) 40-80 -2-hydroxy acid ethers.
  • a preferred automatic dishwashing agent according to the invention is characterized in that the low-foaming nonionic surfactant used is a surfactant of the general formula R 1 CH (OH) CH 2 O- (CH 2 CH 2 O) 20-120 - R 2 , where R 1 and R 2 independently of one another represent a linear or branched aliphatic hydrocarbon radical having 2 to 20, in particular 4 to 16, carbon atoms.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] Y CH 2 CH (OH) R 2 , in which R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 4, preferably 0.5 to 1.5, and y stands for a value of at least 15 stands.
  • surfactants of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 are also preferred, in which R 1 is a linear or branched aliphatic Hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for a value between 1 and 40 and y stands for a value between 15 and 40, the alkylene units [CH 2 CH (CH 3 ) O] and [CH 2 CH 2 O] are randomized, that is, in the form of a statistical, random distribution.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 , in which R 1 and R 2 stand for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R 3 for H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different from R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2.
  • R 1 and R 2 are preferred linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, —CH 3 or —CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x is 2.
  • the value 3 for x has been chosen as an example and can be larger, the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
  • R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants, in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 stands for H and x assumes values of 6 to 15.
  • Nonionic surfactants of the general formula are preferred here R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y -CH 2 CH (OH) -R 2 , where R, R 1 and R 2 independently of one another represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms; x and y independently represent values between 1 and 40
  • R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reacting alkyl diols HO-CHR-CH 2 -OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close off the free OH functions with the formation of a dihydroxy ether.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 in which R 3 and R 4 stand for H and the indices x and y independently of one another assume values from 1 to 40, preferably from 1 to 15.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 in which the radicals R 1 and R 2 represent, independently of one another, saturated alkyl radicals having 4 to 14 carbon atoms and the indices x and y, independently of one another, assume values from 1 to 15 and in particular from 1 to 12.
  • Such compounds of the general formula are also preferred R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 , in which one of the radicals R 1 and R 2 is branched.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y OR 2 in which the indices x and y assume values from 8 to 12 independently of one another.
  • the specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned nonionic surfactants represent statistical mean values which, for a specific product, can be a whole number or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but rather of mixtures, which can result in mean values and fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the general formulas mentioned above, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different ones of the general formulas mentioned above .
  • Nonionic surfactants which have a melting point above room temperature are particularly preferred.
  • the proportion by weight of the nonionic surfactant in the total weight of the cleaning agent according to the invention is from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight. .
  • Preferred cleaning agents are further characterized in that they contain less than 1.0% by weight and in particular no anionic surfactant, since the addition of anionic surfactants has a positive effect on the tablet (phase) properties, in particular their hardness, friability and Post-curing behavior has proven to be disadvantageous.
  • the cleaning agent is preferably in the form of a shaped body, in particular a tablet.
  • the cleaning agent according to the invention further comprises one or more complexing agents.
  • the complexing agents have the particular task of complexing Ca and Mg ions from the rinse water. This task is carried out by phosphates. Since phosphates contribute to the desrophication of water, these are replaced by complexing agents. Suitable complexing agents are known to the person skilled in the art. For example, silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids, phosphonates or ion exchangers can be used as complexing agents.
  • the complexing agent is preferably water-soluble.
  • Organic complexing agents which can be present in the cleaning agent according to the invention are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and their derivatives and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Particularly preferred cleaning agents according to the invention in particular automatic dishwashing agents, contain one or more salts of citric acid, that is to say citrates, as one of their essential complexing agents.
  • Citrates can be used in combination with carbonates and / or hydroxycarbonates.
  • Particularly preferred cleaning agents are characterized in that the dishwashing detergent contains at least one further phosphorus-free complexing agent in addition to citrate, the further phosphorus-free complexing agent preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate IDS) and ethylenediamine disuccinate (EDDS), particularly preferably made from MGDA and GLDA, the proportion by weight of the complexing agents, based on the total weight of the cleaning agent, preferably 5 to 80% by weight, preferably 15 to 75% by weight and in particular 30 to 70% by weight % By weight.
  • the combination of at least three builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular automatic dishwashing agents.
  • Agents according to the invention can furthermore contain phosphonate (s) as complexing agents.
  • Phosphonates which can be used according to the invention are preferably selected from aminotrimethylene phosphonic acid (ATMP); Ethylenediaminetetra (methylenephosphonic acid) (EDTMP); Diethylenetriamine pen-ta (methylenephosphonic acid) (DTPMP); 1-hydroxyethane-1,1-diphosphonic acid (HEDP); 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC); Hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and nitrilotri (methylenephosphonic acid) (NTMP), with 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP) being used with particular preference.
  • Phosphonate (s) are used in agents according to the invention preferably in amounts of 0.5 to 20% by weight, in particular 0.5
  • the complexing agent is selected from the group that includes citric acid and its salts, methylglycidineacetic acid (MGDA), 1-hydroxyethane (1,1-diphosphonic acid) (HEDP) and mixtures thereof.
  • MGDA methylglycidineacetic acid
  • HEDP 1-hydroxyethane (1,1-diphosphonic acid)
  • these complexing agents are particularly preferred when the cleaning agent is one which is free from phosphates.
  • Such a cleaning agent is preferred according to the invention.
  • These complexing agents are able to replace the lack of phosphate in phosphate-free cleaning agents and thus contribute to a good cleaning performance.
  • the glass corrosion caused by the complexing agents can be significantly reduced or even avoided by the PDADMAC added according to the invention.
  • the cleaning agent further comprises zinc acetate as a corrosion inhibitor.
  • the agent preferably contains further corrosion inhibitors.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, silver protectants being particularly important in the field of machine dishwashing.
  • the known substances of the prior art can be used.
  • silver protectants selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes. Benzotriazole and / or alkylaminotriazole are particularly preferred.
  • Examples of the 3-amino-5-alkyl-1,2,4-triazoles to be used with preference according to the invention include: propyl, butyl, pentyl, heptyl, octyl, nonyl and decyl -, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-kla-realkyl-, - Phenyl-, -p-Tolyl-, - (4-tert.Butylphenyl) -, - (4-Methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-Methy1-2-fury1) -, - (5-0xo-2-pyrrolidiny1) -, -3-amino-1,2,4-triazole.
  • the alkylamino-1,2,4-triazoles or their physiologically tolerable salts are used in dishwashing detergents in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04 % By weight used.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acids.
  • 5-pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-Versatic-10-klarealky1-3-amino-1,2,4-triazoles and mixtures are particularly effective of these substances.
  • detergent formulations often contain agents containing active chlorine, which can significantly reduce the corrosion of the silver surface.
  • organic redox-active compounds containing oxygen and nitrogen in particular such as di- and trivalent phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds, are used.
  • Complex and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are also frequently used.
  • transition metal salts selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, are preferred here.
  • Complexes of cobalt or manganese chlorides and manganese sulphate. Zinc compounds can also be used to prevent corrosion on the wash ware.
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, the metals preferably in one of the oxidation states II, 111, IV, V or VI are present.
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation include all of the usual single, double or triple negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate.
  • metal complexes are compounds which consist of a central atom and one or more ligands and, if appropriate, also one or more of the anions mentioned above.
  • the central atom is one of the above metals in one of the above oxidation states.
  • the ligands are neutral molecules or anions that are mono- or polydentate; the term "ligands" in the context of the invention is for example in " Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507 If the charge of the central atom and the charge of the ligand (s) do not add to zero in a metal complex, either one or more of the above anions or one or more of the above-mentioned anions is provided, depending on whether there is a cationic or an anionic charge excess Cations, for example sodium, potassium, ammonium ions, for charge equalization.
  • suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (11) stearate, Mn (II) acetylacetonate, Mn (11) [1-hydroxyethane-1,1-diphosphonate ], V 2 0 5 , V 2 0 4 , V0 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 , and their mixtures, see above that the metal salts and / or metal complexes selected from the group MnSO 4 Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (11) 41-hydroxyethane-1,1-di-phosphonate] , V 2 0 5 , V 2 0 4 , V0 2 , TiOSO 4 , K
  • metal salts or metal complexes are generally commercially available substances that can be used in detergents or cleaning agents for the purpose of silver corrosion protection without prior cleaning.
  • the mixture of pentavalent and tetravalent vanadium (V 2 0 5 , V0 2 , V 2 0 4 ) known from S0 3 production (contact process) is suitable, as is that obtained by diluting a Ti (SO 4 ) 2 - Solution resulting titanyl sulfate, TiOSO 4 .
  • the inorganic redox-active substances are preferably coated, that is to say completely covered with a waterproof material that is easily soluble at cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials that are applied by known processes, such as Sandwik melt coating processes from the food industry, are paraffins, micro-waxes, waxes of natural origin such as carnauba wax, candellilla wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fatty acids.
  • the coating material which is solid at room temperature, is applied in a molten state to the material to be coated, for example by hurling finely divided material to be coated in a continuous stream through a spray zone of the molten coating material that is also continuously generated.
  • the melting point must be chosen so that the coating material dissolves easily or melts quickly during the silver treatment.
  • the melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.
  • Corrosion inhibitors are preferably contained in the present invention in a proportion of from 0.05 to 1% by weight, in particular from 0.1 to 0.3% by weight.
  • the corrosion inhibitor includes zinc acetate.
  • the agents according to the invention can contain further ingredients.
  • these include, for example, other surfactants, additives to improve the drainage and drying behavior, to adjust the viscosity, to stabilize and other auxiliaries and additives common in hand dishwashing detergents, such as UV stabilizers, perfume, Pearlescent agents, dyes, corrosion inhibitors, preservatives, organic salts, disinfectants, enzymes, pH adjusters and additives that improve or care for the skin.
  • Polymers suitable as additives are in particular maleic acid-acrylic acid copolymer sodium salt (for example Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid sodium salt (for example Sokalan® CP 10 from BASF, Ludwigshafen (Germany) )), modified polycarboxylate sodium salt (for example Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet® L-7608 from BASF, Ludwigshafen (Germany)) and polyether siloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide segments (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren® 5840®, Tegopre
  • Builder substances suitable as additives are in particular polyaspartic acid sodium salt, ethylenediamine triacetate coconut alkylacetamide (for example Rewopol® CHT 12 from Evonik, Essen (Germany)), methylglycinediacetic acid tri-sodium salt and acetophosphonic acid.
  • Mixtures with surfactant or polymer additives show synergisms in the case of Tegopren® 5843 and Tegopren® 5863.
  • the use of Tegopren types 5843 and 5863 is, however, less preferred when used on hard surfaces made of glass, in particular glass dishes, since these silicone surfactants can be absorbed onto glass.
  • the additives mentioned are dispensed with.
  • a preferred cleaning agent in particular dishwashing detergent, furthermore comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst.
  • cleaning agents according to the invention contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate.
  • Further bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which provide H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • bleaches from the group of organic bleaches can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as, for example, dibenzoyl peroxide.
  • Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.
  • Sodium percarbonate is particularly preferred because of its good bleaching performance.
  • a particularly preferred oxygen bleach is sodium percarbonate.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry 0- and / or N-acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups are suitable. Polyacylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • TAED tetraacetylethylenediamine
  • the bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru-amine complexes can also be used as bleach catalysts.
  • Manganese complexes in the II, III, IV or IV oxidation state which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference.
  • Ligands are preferably used which have nitrogen donor functions.
  • bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN ) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane Me TACN
  • 2-methyl-1,4,7-triazacyclononane Me TA
  • Suitable manganese complexes are, for example, [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 2 ( ⁇ -OAc) 1 (TACN ) 2 ] (BPh 4 ) 2 , [Mn IV 4 ( ⁇ -O) 6 (TACN) 4 ] (ClO 4 ) 4 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN ) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn IV 2 ( ⁇ -O) 3 ( Me-TACN) 2 ] (PF 6 ) 2 and [Mn IV 2 ( ⁇ -O) 3 (Me / Me-TACN) 2 ] (PF 6 ) 2 (with OAc
  • one or more other customary auxiliaries and additives in particular UV stabilizers, perfume, pearlescent agents (INCI Opacifying Agents; for example glycol distearate, for example Cutina® AGS from Cognis, or mixtures containing this, for example Euperlane® from Cognis), dyes, corrosion inhibitors, preservatives (for example the technical 2-bromo-2-nitropropane-1,3-diol (CAS 52-51-7), also known as Bronopol, which is known as Myacide® BT or Boots Bronopol BT from from Boots is commercially available), disinfectants, pH adjusters and additives that improve or care for the skin feel (for example, dermatologically active substances such as vitamin A, vitamin B2, vitamin B12, vitamin C, vitamin E, D-panthenol, sericerin, collagen partial -Hydrolyzate, various vegetable protein partial hydrolyzates, protein hydrolyzate-fatty acid condensates, liposomes, cholesterol, vegetable and animal oils oils oils
  • the cleaning agent according to the invention is preferably used for manual and / or machine cleaning of objects with glass surfaces.
  • it is used for machine cleaning of objects with glass surfaces.
  • Objects with glass surfaces in the context of the present invention are all objects which have a surface that includes glass. This includes items that are made entirely of glass. For example, these are (drinking) glasses, pots or bowls made of glass or decorative glass objects.
  • the glasses can be colored or decorated in some other way. However, the glasses can also be without any colored decorations.
  • glass is all types of glasses, such as soda-lime glass, borosilicate glass or lead glass.
  • the glasses are preferably soda lime glasses.
  • automatic dishwashing agents are compositions which can be used for cleaning soiled dishes in an automatic dishwashing process.
  • the automatic dishwashing agents according to the invention thus differ, for example, from the automatic rinsing agents, which are always used in combination with automatic dishwashing agents and do not develop any cleaning effect of their own.
  • the cleaning agents according to the invention are preferably in the form of a shaped body, in particular a compact, especially a tablet.
  • they can also be combined with other forms of offer, in particular in combination with solid supply forms such as powder, granules or extrudates or in combination with liquid supply forms based on water and / or organic solvents.
  • the shaped body can, for example, also be granules that are contained in a bag or a casting mold.
  • Agents according to the invention can be packaged as single-phase or multiphase products.
  • Automatic dishwashing detergents with one, two, three or four phases are particularly preferred.
  • Machine dishwashing detergents, characterized in that they are in the form of a prefabricated dosage unit with two or more phases, are particularly preferred.
  • Particularly preferred are, in particular, two- or multiphase tablets, for example two-layer tablets, in particular two-layer tablets with a recess and a shaped body located in the recess.
  • Cleaning agents according to the invention are preferably pre-packaged into metering units. These metering units preferably comprise the amount of washing or cleaning-active substances necessary for a cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial shape are particularly preferably selected so that the pre-assembled units can be metered via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
  • the cleaning agents according to the invention in particular the prefabricated metering units, have a water-soluble envelope.
  • the object on which the present invention is based is achieved by a method for cleaning objects with a glass surface, in which a previously described cleaning agent is brought into contact with the glass surface and the surface is processed in a known manner.
  • the cleaning takes place with a cleaning machine, especially a dishwasher.
  • the washing liquor formed from cleaning agent and water preferably has a pH in the range from 7.5 to 12, in particular from 8 to 11, particularly preferably from 9.5 to 10.5. Corrosion of the glass surfaces usually occurs in these pH value ranges.
  • the alkaline cleaning solution causes the glass swells. Complexing agents contained in the cleaning agent can then attack the glass structure. With PDADMAC this attack of the complexing agents on the swollen glass structure is prevented or at least significantly reduced.
  • the method according to the invention is preferably a machine cleaning method; for this purpose, the glass objects or objects with a glass surface to be cleaned are placed, for example, in a commercially available dishwasher and cleaned using the specified programs.
  • the cleaning agent according to the invention can, however, also be used for manual cleaning of dishes and objects with glass surfaces.
  • the temperature at which the cleaning is carried out is in particular in the range from 5 to 90.degree. C., particularly from 20.degree. C. to 80.degree. C., particularly preferably from 40.degree. C. to 60.degree. Good cleaning can take place at these temperatures. Soiling from the surfaces can be easily removed. In terms of environmentally friendly cleaning, however, lower temperatures, in particular those in the range from 40 ° C. to 60 ° C., are preferred.
  • the cleaning agent according to the invention enables phosphates to be replaced in cleaning agents by combining complexing agents such as, in particular, MGDA, citric acid or HEDP in combination with a polymer, namely PDADMAC.
  • complexing agents such as, in particular, MGDA, citric acid or HEDP
  • PDADMAC a polymer
  • this enables environmentally friendly cleaning.
  • legal requirements that require phosphate-free cleaning agents from 2017 can be complied with.
  • PDADMAC makes it possible to reduce or even essentially avoid the glass corrosion that occurs, especially at alkaline pH values.
  • the object on which the present invention is based is therefore achieved by using PDADMAC in an amount of 0.01 to 1% by weight in a cleaning agent, in particular in a phosphate-free cleaning agent, especially for the machine cleaning of objects with a glass surface to reduce glass corrosion, especially at alkaline pH values.
  • a phosphate-free cleaning agent was produced with the following composition: raw materials P-free formula areas Wt% g / job Na citrate 15.00 - 20.00 3.00 - 4,000 Phosphonate (HEDP) 0.00 - 7.50 0.00 - 1,500 MGDA 5.00 - 25.00 1.00 - 5,000 Na disilicate 10.00 - 35.00 2.00 - 7,000 soda 12.50 - 25.00 2.50 - 5,000 Na percarbonate 10.00 - 15.00 2.00 - 3,000 Bleach catalyst (Mn-based) 0.02 - 0.50 0.003 - 0.100 TAED 2.00 - 3.00 0.40 - 0.600
  • Nonionic surfactant (20-40E0 end-cap mgl) 2.50 - 10.00 0.50 - 2,000 Polycarboxylate 5.00 - 10.00 1.00 - 2,000 cationic co-polymer 0.25 - 0.75 0.05 - 0.150 cross-linked PVP 0.00 - 1.50 0.00 - 0.300 Protease 1.50 -
  • This cleaning agent was a phosphate-free cleaning agent for the machine cleaning of dishes. Both the% by weight and the active amount in g / job (g per cleaning cycle) are given. A solid cleaning agent was produced which was available in the form of a table with a weight of 17 g to 20 g, in particular 17 g.
  • the detergent was dissolved in tap water at a concentration of 6 g / l.
  • 0.6 g / l PDADMAC and 0.06 g / l PDADMAC were added.
  • a proportion of 0.6 g / l corresponded to 10% by weight of the dishwashing detergent.
  • the addition of 0.6 g / l PDADMAC corresponded to 1% by weight of the dishwashing detergent.
  • a quartz-crystal microbalance was used to determine the extent to which glass corrosion occurs.
  • the measuring principle of a QCM works by determining the oscillation frequency of a quartz crystal. As soon as a substance is adsorbed on this quartz crystal, which represents the sensor, or desorbed from the sensor, this causes a change in the resonance frequency. This change in frequency can be detected and converted into a change in mass.
  • a glass-coated sensor was also rinsed with a cleaning agent according to the invention which comprised 10% by weight or 1% by weight of PDADMAC.
  • the process of overflowing the sensor took place at 60 ° C. in a QCM from Q-Sense (Stockholm, Sweden).
  • the cleaning agent removed the glass coating from the sensor (removal of mass). This removal of mass from the sensor corresponds to the extent of glass corrosion.
  • the start of the mass removal, measured from the moment the sensor is overflushed with the cleaning agent, and the amount of mass removal represent the parameters with which the intensity of the glass corrosion can be determined. The later the removal of mass begins and / or the lower the removal of mass, the less the glass is attacked by the cleaning agent.
  • the determination of the point in time t from which a mass removal took place corresponds to the period from the beginning of the overflushing of the sensor with the cleaning agent up to the moment at which a clear mass removal was recognizable.
  • the information is given here in minutes.
  • the mass removal was determined relative to the original mass value. The information is therefore given here in%.
  • Rinsing with a cleaning agent that did not contain PDADMAC resulted in a loss of mass of the sensor of more than 50% of the glass layer after less than 30 minutes.
  • PDADMAC the occurrence of the loss of mass could be delayed three times later.
  • the loss of mass was initially around 50% here as well.
  • a limit value developed both in the comparative example and in the cleaning agent according to the invention, which contained 1% by weight of PDADMAC. No further glass removal took place here. However, for the cleaning agent without PDADMAC, this limit value was below the limit value for the cleaning agent according to the invention with PDADMAC. Without PDADMAC, around 10% more glass was removed from the sensor at the end, i.e. in the range of the limit value, than with the cleaning agent according to the invention.
  • a second cleaning agent according to the invention which contained 10% by weight PDADMAC, was tested.
  • the first loss of mass only occurred after a period of time that was 4 to 6 times longer than without PDADMAC.
  • a maximum value was reached after a certain amount of material had been removed. This was again about 10 to 20% less than in the case of the cleaning agent according to the invention, which contained 1% by weight of PDADMAC.
  • a cleaning agent according to the invention which has PDADMAC therefore enables a significant reduction in glass corrosion. On the one hand, this occurs much later and ensures less loss of mass over time. The glass corrosion therefore only occurs after a large number of rinsing cycles. In addition, the extent of glass corrosion is reduced compared to cleaning agents known in the prior art.

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Claims (7)

  1. Agent de nettoyage comprenant au moins un tensioactif, un ou plusieurs agents complexants, du PDADMAC (chlorure de polydiallyldiméthylammonium) et de l'acétate de zinc comme inhibiteur de corrosion, caractérisé en ce que l'agent de nettoyage est un détergent de vaisselle automatique et en ce que cet agent de nettoyage comprend du PDADMAC dans une proportion de 0,01 à 1 % en poids.
  2. Agent de nettoyage selon la revendication 1, caractérisé en ce que l'agent complexant est choisi dans le groupe comprenant l'acide citrique et ses sels, le MGDA, le HEDP et leurs mélanges.
  3. Agent de nettoyage selon l'une des revendications 1 à 2, caractérisé en ce qu'il ne contient pas de phosphates.
  4. Utilisation d'un agent de nettoyage selon l'une des revendications 1 à 3 pour le nettoyage manuel et/ou automatique d'objets à surface en verre, en particulier pour le nettoyage automatique d'objets à surface en verre.
  5. Procédé de nettoyage d'objets à surface en verre, selon lequel un agent de nettoyage selon l'une des revendications 1 à 3 est mis en contact avec la surface en verre.
  6. Procédé selon la revendication 5, caractérisé en ce que la température à laquelle le nettoyage est effectué est comprise entre 5° C et 90 °C, en particulier entre 20 °C et 80 °C, particulièrement entre 40 °C et 60 °C.
  7. Utilisation de PDADMAC en une quantité de 0,01 à 1 % en poids dans un agent de nettoyage pour le nettoyage automatique de surfaces en verre afin de réduire la corrosion du verre.
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