EP3164477A1 - Cleaning agent comprising a glass corrosion inhibitor - Google Patents

Cleaning agent comprising a glass corrosion inhibitor

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Publication number
EP3164477A1
EP3164477A1 EP15731970.8A EP15731970A EP3164477A1 EP 3164477 A1 EP3164477 A1 EP 3164477A1 EP 15731970 A EP15731970 A EP 15731970A EP 3164477 A1 EP3164477 A1 EP 3164477A1
Authority
EP
European Patent Office
Prior art keywords
cleaning
glass
cleaning agent
acid
nonionic surfactants
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.)
Granted
Application number
EP15731970.8A
Other languages
German (de)
French (fr)
Other versions
EP3164477B1 (en
Inventor
Alexander Schulz
Inga Kerstin Vockenroth
Nicole BODE
Peter Schmiedel
Danuta Bedrunka
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3164477A1 publication Critical patent/EP3164477A1/en
Application granted granted Critical
Publication of EP3164477B1 publication Critical patent/EP3164477B1/en
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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, in particular during machine cleaning.
  • the cleaning agent is in particular a dishwashing detergent for machine cleaning of dishes.
  • the present invention relates to a method for cleaning objects with glass surface using the cleaning agent according to the invention.
  • the task of cleaning agents is usually the cleaning of dirty surfaces. They should on the one hand remove stubborn stains. On the other hand, however, 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. Especially when machine washing dishes with conventional dishwashing detergents, glass corrosion is a common problem. Usually, the wash liquor used to clean dishes with conventional dishwashing detergents has a pH of 8.0 or more. Many commercially available types of glass are attacked here and thus show in the course of many rinse cycles turbidity phenomena, which are referred to as glass corrosion.
  • detergents 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.
  • the object of the present invention is now to provide a cleaning agent, in particular a dishwashing detergent for cleaning articles with glass surfaces, wherein the particular caused by complexing glass corrosion is to be reduced or at least reduced.
  • a cleaning agent in particular a dishwashing detergent for cleaning articles with glass surfaces, wherein the particular caused by complexing glass corrosion is to be reduced or at least reduced.
  • the cleaning performance of the product should not be adversely affected with regard to the removal of stains.
  • PDADMAC polydiallyldimethylammonium chloride
  • the object underlying the present invention is therefore achieved by a cleaning agent comprising at least one surfactant, one or more complexing agents and PDADMAC.
  • the cleaning agent according to the invention preferably comprises PDADMAC in a proportion of 0.01 to 50 wt .-%, in particular from 0.01 to 30 wt .-%, preferably from 0.01 to 12 wt .-%, particularly preferably from 0.01 to 1% by weight.
  • a proportion of less than 0.01% by weight of PDADMAC in a detergent does not result in any appreciable reduction in glass corrosion.
  • a proportion of 1 wt .-% can be well incorporated in cleaning agents. At the same time thereby a significant reduction of the glass corrosion is achieved.
  • a proportion of 50 wt .-% can also be incorporated into a cleaning agent, without its cleaning performance is adversely affected. However, a further amount does not lead to any further improvement with respect to the glass corrosion.
  • the cleaning agent according to the invention comprises at least one surfactant.
  • the cleaning agent may 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. Therefore, according to the invention, the cleaning agent may preferably comprise one or more nonionic surfactants. However, it is also possible that it comprises a nonionic surfactant together with, for example, an anionic surfactant. Other combinations of the surfactants are included according to the invention.
  • the cleaning agent according to the invention contains at least one nonionic surfactant.
  • nonionic surfactants nonionic surfactant
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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.
  • nonionic surfactants 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 having from 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 may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • Further suitable surfactants are polyhydroxy fatty acid amides of the following formula
  • R is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [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
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms
  • Ci-4-alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example 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 catalyst.
  • the cleaning agents according to the invention in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in in which the alcohol radical can be linear 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 having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol.
  • the preferred ethoxylated alcohols include, for example, C 12-14-alcohols with 3 EO or 4 EO, Csn-alcohol with 7 EO, cis-s 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 Ci2-i4-alcohol with 3 EO and Ci 2-i s-alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • NRE narrow rank ethoxylates
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants which are prepared from C 6-2o-monohydroxyalkanols or C 6-2o-alkylphenols or C 6-2o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 6-2o-alcohol), preferably a cis-alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 6-2o-alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • a cis-alcohol preferably a cis-alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called ā€œnarrow ranks ethoxylatesā€ are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that these s, preferably above 35 Pa Ā«s and in particular above 40 Pa Ā» s have a viscosity above 20 Pa. " Nonionic surfactants which have waxy consistency at room temperature are also preferred. Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units (PO) in the molecule.
  • PO propylene oxide units
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight 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 up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as
  • Polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic 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 blends comprising 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R 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 -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R -OH and ethylene or alkylene oxide.
  • the radical R in the above formula may vary depending on the origin of the alcohol.
  • the group R has an even number of carbon atoms and is usually unbranched, the linear groups being selected from alcohols of native origin containing from 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol , are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • nonionic surfactants in which R in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3) 2 are suitable.
  • nonionic surfactants having a C9-alkyl group having 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 according to the invention with particular preference.
  • R is -CH (OH) CH 2 O- (AO) w- (A'0) x- (A "0) y - (A '" 0) z R 2 , in which R and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-4 -alkyl or -alkenyl radical;
  • A, ā‡ ', A "and A'" independently of one another are radicals 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 are values between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferred according to the invention.
  • nonionic surfactants of the general formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] zCH 2 CH (OH) R 2 , where R is a linear or branched aliphatic radical Hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y is a value of at least 15, preferably from 15 to 120, particularly preferably from 20 to 80.
  • the detergent contains, based on its total weight, nonionic surfactant of the general formula
  • R 0 [CH 2 CH 2 O] yCH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 16, carbon atoms or mixtures thereof R 2 is a linear or branched hydrocarbon radical having 2 to 26, in particular having 4 to 20, carbon atoms or mixtures thereof and y is a value between 15 and 120 preferably 20 to 100, in particular 20 to 80 stands.
  • nonionic surfactants include, for example, hydroxy mixed ethers of the general formula C6-22-CH (OH) CH20 (EO) 2o-i 2o-C2-26, for example the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o-8o-2-hydroxyalkyl ether.
  • a machine dishwashing detergent preferred according to the invention is characterized in particular by using as low-foaming nonionic surfactant a surfactant of the general formula R CH (OH) CH 2 O- (CH 2 CH 2 O) 2o-i 2 -R 2 , where R and R 2 are independently of one another linear or branched aliphatic hydrocarbon radical having 2 to 20, in particular 4 to 16, carbon atoms.
  • surfactants of the formula R 0 [CH 2 CH (CH 3 ) O] X [CH 2 CH 2 O] YCH 2 CH (OH) R 2 , in which R is a linear or branched aliphatic hydrocarbon radical having 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 represents values between 0.5 and 4, preferably 0.5 to 1.5, and y represents a value of at least 15.
  • R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] yCH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R 2 is a linear or branched one Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units randomized [CH 2 CH (CH 3) O] and [CH 2 CH 2 O], that is in Form a random statistical distribution.
  • the group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula
  • R and R 2 independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] kCH (OH) [CH 2 ] jOR 2 in which R and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 Carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is between 1 and 30 , k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] kCH (OH) [CH 2 ] jOR 2 may be different.
  • R and R 2 are preferred linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -Ch 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 alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R ā‡ R 2 and R 3 are as defined above and x represents 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 and R 2 have 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactants are nonionic surfactants of the general formula R 0 (AlkO) xM (OAlk) y OR 2 , where
  • R and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
  • Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and
  • M is an alkyl radical from the group CH 2, CHR 3, CR 3 R 4, CH 2 CHR 3 and CHR 3 CHR 4, wherein R 3 and R 4 independently represent a branched or unverzwe temperate, saturated or unsaturated alkyl radical having 1 to 18 Carbon atoms.
  • Nonionic surfactants of the general formula are preferred here.
  • R is -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 and R 2 are independently an alkyl or alkenyl radical of 6 to 22 carbon atoms; x and y independently represent values between 1 and 40 Particular preference is given here to compounds of the general formula
  • R is -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 wherein R is a linear saturated alkyl radical of 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms; n and m independently of one another have values of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.
  • nonionic surfactant is selected from nonionic surfactants of the general formula
  • R -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y O -R 2 , in which R and R 2 independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms;
  • R 3 and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
  • x and y independently represent values between 1 and 40.
  • Compounds of the general formula R -O (CH 2 CH 2 O) xCR 3 R 4 (OCH 2 CH 2 ) yO-R 2 in which R 3 and R 4 are H and the indices x and y independently of one another have values from 1 to 2 are preferred 40, preferably from 1 to 15 accept.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical average values which, for a specific product, may be an integer or a fractional number. Due to the methods II trade products of the formulas mentioned are usually not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation averages and resulting broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • the proportion by weight of the nonionic surfactant in the total weight of the cleaning agent according to the invention in a preferred embodiment is from 0.1 to 20% by weight, more 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 wt .-% and in particular no anionic surfactant, since the addition of anionic surfactants with respect to the tablet (phase) properties, in particular their hardness, friability and Post-hardening has proved 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 furthermore 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 fulfilled by phosphates. Since phosphates contribute to the deoxidation of waters, they are replaced by complexing agents. Suitable complexing agents are known to the person skilled in the art. For example, silicates, aluminum silicates (in particular zeolites), salts of organic di- and polycarboxylic acids, phosphonates or ion exchangers can be used as complexing agents.
  • the complexing agent is water-soluble.
  • Organic complexing agents which may 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 meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA) and derivatives thereof and mixtures thereof.
  • NTA nitrilotriacetic acid
  • MGDA methylglycine diacetic acid
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • Particularly preferred cleaning agents according to the invention in particular automatic dishwashing agents, contain as one of their essential complexing agents one or more salts of citric acid, ie citrates.
  • Citrates can be used in combination with carbonates and / or hydroxycarbonates.
  • Particularly preferred cleaning agents are characterized in that the dishwashing detergent contains, in addition to citrate, at least one further phosphorus-free complexing agent, wherein the further phosphorus-free complexing agent is preferably selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic diacetic acid (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate ( IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA and GLDA, wherein the weight fraction of the complexing agent, based on the total weight of the cleaning agent, preferably 5 to 80 wt .-%, preferably 15 to 75 wt .-% and in particular 30 to 70 Wt .-% is.
  • the combination of at least three builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance
  • Compositions according to the invention can furthermore contain phosphonate (s) as complexing agent.
  • Phosphonates which can be used according to the invention are preferably selected from aminotrimethylenephosphonic acid (ATMP); Ethylenediaminetetra (methylenephosphonic acid) (EDTMP); Diethylene triamine penta (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
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta (methylenephosphonic acid)
  • Phosphonate (s) are preferably used in inventive compositions in amounts of 0.5 to 20 wt .-%, in particular from 0.5 to 10 wt .-% and especially from 0.5 to 8 wt .-%.
  • the complexing agent is selected from the group comprising citric acid and its salts, methyl glycidylacetic acid (MGDA), 1-hydroxyethane- (1, 1-diphosphonic acid) (HEDP) and mixtures thereof.
  • MGDA methyl glycidylacetic acid
  • HEDP 1-hydroxyethane- (1, 1-diphosphonic acid)
  • these complexing agents are particularly preferred when a cleaning agent is one which is free of 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 detergents in its effect 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 present invention attached PDADMAC.
  • the cleaning agent preferably further comprises one or more corrosion inhibitors.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art.
  • silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • Examples of the 3-amino-5-alkyl-1, 2,4-triazoles preferably used according to the invention may be: propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl -, undecyl, - dodecyl, - isononyl, - versatic-10-kla-realkyl, - phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - (4-methoxyphenyl) -, - (2-, 3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-fury1) -, - (5-oxo-2-pyrrolidinyl) -1, 3-amino-1, 2,4-triazole.
  • the alkylamino-1, 2,4-triazoles or their physiologically tolerable salts in a concentration of 0.001 to 10 wt.%, Preferably 0.0025 to 2 wt.%, Particularly preferably 0.01 to 0.04 % By weight used.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds are used.
  • compound and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • 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, wherein the metals preferably in one of the oxidation states II, 1 1 1, IV, V or VI.
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as, for example, stearate.
  • Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the above-mentioned. Anions exist.
  • the central atom is one of the o.g. 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 explained in more detail, for example, in "Rƶmpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507". If, in a metal complex, the charge of the central atom and the charge of the ligand (s) do not complete to zero, then, depending on whether there is a cationic or an anionic charge surplus, either one or more of the above mentioned obeys.
  • 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 MnSC, Mn (II) citrate, Mn (1 1) stearate, Mn (II) acetylacetonate, Mn (1 1) [1-hydroxyethane-1, 1- diphosphonate], V2O5, V2O4, V0 2 , TiOSC, K 2 TiF 6 , K 2 ZrF 6 , C0SO 4, Co (NO 3 ) 2, Ce (NO 3 ) 3, and mixtures thereof, such that the metal salts and / or metal complexes selected from the group MnSCU Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (1 1) 41-hydroxyethane-1, 1-
  • metal salts or metal complexes are generally commercially available substances which can be used for the purpose of silver corrosion protection without prior purification in detergents or cleaners.
  • the mixture of pentavalent and tetravalent vanadium (V2O5, VO2, V2O4) known from SCh production (contact method) is suitable, as well as the titanyl sulfate, TiOSC, formed by diluting a Ti (SO4) 2 solution.
  • the inorganic redox-active substances are preferably coated, that is to say completely coated with a water-tight material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.
  • the coating material which is solid at room temperature is applied in the molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a likewise continuously produced spray zone of the molten coating material.
  • the melting point must be selected so that the coating material dissolves easily during the silver treatment or melts quickly.
  • the melting point should ideally be in the range between 45 Ā° C and 65 Ā° C and preferably in the range 50 Ā° C to 60 Ā° C.
  • corrosion inhibitors are preferably contained in an amount of 0.05 to 1% by weight, in particular of 0.1 to 0.3% by weight.
  • the corrosion inhibitor is zinc acetate.
  • compositions according to the invention may contain further ingredients.
  • these include, for example, other surfactants, additives for improving the drainage and drying behavior, for adjusting the viscosity, for stabilization and other auxiliary substances and additives customary in hand dishwashing detergents, for example UV stabilizers, perfume, Pearlescing agents, dyes, corrosion inhibitors, preservatives, organic salts, disinfectants, enzymes, pH adjusters, and skin feel enhancing or conditioning additives.
  • Polymers suitable as additives maleic acid-acrylic acid copolymer Na salt are, in particular (for example Sokalan Ā® CP 5 from the company BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na-salt (for example Sokalan Ā® CP 10 from BASF, Ludwigshafen (Germany )), modified polycarboxylate-Na-salt (for example Sokalan Ā® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide-modified heptamethyltrisiloxane (such as Silwet Ā® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide-modified heptamethyltrisiloxane (For example, Silwet Ā® L-7608 BASF, Ludwigshafen (Germany)) and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether
  • suitable builders are especially polyaspartic acid Na salt, Ethylendiamintriacetatkokosalkylacetamid (eg RewopolĀ® Ā® CHT 12 from Evonik, Essen (Germany)), methylglycine-trisodium salt and acetophosphonic.
  • Blends with surfactant or polymeric additives exhibit synergism 5863 in the case of Tegopren 5843 and Tegopren Ā® Ā®.
  • the use of Tegopren grades 5843 and 5863 is less preferred when applied to hard surfaces of glass, especially glassware, since these can apply silicone surfactants to glass.
  • the additives mentioned are dispensed with.
  • a preferred cleaning agent, in particular dishwashing agent further comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst.
  • Preferred cleaning agents according to the invention include an oxygen bleaching agent from the group of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate.
  • Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • sodium percarbonate is particularly preferred.
  • a particularly preferred oxygen bleach is sodium percarbonate.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with 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 salt 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 ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, II I, IV or IV which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (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).
  • macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (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
  • Suitable manganese complexes are, for example, [ ā‡ ā‡ ā‡ 2 ( ā‡ -0) ā‡ ( ā‡ - ā‡ ) 2 ( ā‡ ) 2 ] ( ā‡ 4) 2, [Mn m Mn lv ( ā‡ -0) 2 ( ā‡ -OAc) 1 (TACN ) 2] (BPh4) 2, [ ā‡ ' ā‡ 4 ( ā‡ - 0) 6 (TACN) 4 ] (CI0 4 ) 4, [ ā‡ ā‡ ā‡ 2 ( ā‡ -0) ā‡ ( ā‡ - ā‡ ) 2 ( ā‡ - ā‡ ) 2 ] ( ā‡ ā‡ 4) 2, [ ā‡ ā‡ ' ā‡ ' ā‡ ( ā‡ -0) ā‡ ( ā‡ - ā‡ ( ā‡ - ā‡ -
  • auxiliaries and additives in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina Ā® AGS from Cognis, or mixtures comprising, for example, the Euperlane Ā® from..
  • UV stabilizers for example glycol distearate, for example Cutina Ā® AGS from Cognis, or mixtures comprising, for example, the Euperlane Ā® from.
  • Bronopol 2-bromo-2-nitropropane-1, 3-diol for example, as Myacide Ā® BT or Boots Bronopol BT of the company Boots is commercially available
  • disinfectants 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 hydrolysates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soya oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, Algae extracts, etc., allantoin, AHA complexes) in amounts of usually not more than 5% by weight.
  • 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 hydroly
  • the cleaning agent according to the invention is preferably used for manual and / or mechanical cleaning of objects with glass surfaces.
  • it is used for machine cleaning of articles with glass surfaces.
  • Articles with glass surfaces in the sense of the present invention are all objects which have a surface comprising glass. This includes such items that are made entirely of glass.
  • these are (drinking) glasses, pots or bowls made of glass or decorative glass objects.
  • the glasses may have a color infƤrbtechnik or otherwise processed decorative.
  • the glasses can be without any colored decorations.
  • Glass in the context of the present invention are all types of glasses, such as soda lime glass, borosilicate glass or lead glass.
  • the glasses are soda-lime glasses.
  • Automatic dishwashing detergents are compositions which can be used to clean soiled dishes in a dishwasher automatic dishwashing process.
  • the automatic dishwasher detergents according to the invention differ, for example, from the machine rinse aid agents, which are always used in combination with automatic dishwashing detergents and do not develop their own cleaning action.
  • the cleaning agents according to the invention are preferably in the form of a shaped body, in particular a compactate, in particular a tablet.
  • they can also be used in combination with other forms of offer, in particular in combination with solid forms such as powders, granules or extrudates or in combination with liquid formulations based on water and / or organic solvents.
  • the shaped body may, for example, also be a granulate which is contained in a bag or a casting mold.
  • Inventive agents can be formulated as single-phase or multi-phase products.
  • Machine 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 dosing unit with two or more phases, are particularly preferred.
  • Two-phase or multi-phase tablets for example two-layer tablets, in particular two-layer tablets with a trough and a shaped body located in the trough, are particularly preferred.
  • Detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering 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 form are selected with particular preference so that a metering of the prefabricated units is ensured 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, in a preferred embodiment have a water-soluble sheath.
  • the object underlying the present invention is achieved by a method for cleaning objects with glass surface, in which bringing a previously described cleaning agent with the glass surface in contact and the surface is processed in a known manner.
  • the cleaning is done with a cleaning machine, especially a dishwasher.
  • the contact is usually carried out in the presence of water.
  • the washing liquor forming from cleaning agent and water preferably has a pH which is in the range from 7.5 to 12, in particular from 8 to 11, particularly preferably from 9.5 to 10.5. In these pH ranges, corrosion of the glass surfaces usually occurs. Without being bound by any theory, the alkaline cleaning liquor causes the glass swells. Complexing agents contained in the cleaning agent can then attack the glass structure. PDADMAC prevents or at least significantly reduces this attack of the complexing agents on the swollen glass structure.
  • the method according to the invention is preferably a machine cleaning method;
  • the glass objects or objects to be cleaned are given with a glass surface, for example in a commercial dishwasher and cleaned at the given programs.
  • the cleaning agent according to the invention can also be used in a manual cleaning of dishes and objects with glass surfaces.
  • the temperature at which the purification is carried out is in particular in the range from 5 to 90 Ā° C, especially from 20 Ā° C to 80 Ā° C, particularly preferably from 40 Ā° C to 60 Ā° C. At these temperatures, a good cleaning can be done. Stains from the surfaces can be easily removed. In terms of environmentally friendly cleaning, however, lower temperatures, especially those which are in the range of 40 Ā° C to 60 Ā° C, are preferred.
  • the cleaning agent according to the invention makes it possible by the combination of complexing agents, in particular MGDA, citric acid or HEDP in combination with a polymer, namely PDADMAC, to replace phosphates in cleaning agents.
  • complexing agents in particular MGDA, citric acid or HEDP
  • a polymer namely PDADMAC
  • PDADMAC makes it possible to reduce or even substantially avoid glass corrosion, especially at alkaline pH values.
  • the object underlying the present invention is therefore achieved by the use of PDADMAC in a cleaning agent, in particular in a phosphate-free cleaning agent, especially for machine cleaning of objects with a glass surface, to reduce glass corrosion, especially at alkaline pH values ,
  • a phosphate-free detergent of the following composition was prepared:
  • MGDA methylglycinediacetic acid
  • TAED tetraacetylethylenediamine
  • PVP polyvinylpyrrolidone
  • This detergent was a phosphate-free detergent for machine dishwashing. Indicated are both the weight% and the active amount in g / job (g per cleaning cycle).
  • a solid detergent was prepared which was in the form of a table weighing 17 g to 20 g, especially 17 g.
  • the detergent was dissolved in tap water at a concentration of 6 g / l.
  • 0.6 g / L of PDADMAC or 0.06 g / L of PDADMAC was added.
  • a proportion of 0.6 g / l corresponded to 10 wt .-% 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 (QCM) was used.
  • the measuring principle of a QCM works by means of the determination of the oscillation frequency of a quartz crystal. As soon as a substance adsorbs or desorbs from the sensor on this quartz crystal, which represents the sensor, this causes a change in the resonance frequency. This frequency change can be detected and converted into a mass change.
  • a sensor crystal was used, which was coated with a soda-lime glass. This coated sensor was over-rinsed with a phosphate-free detergent having the above composition.
  • a glass-coated sensor with a cleaning agent according to the invention comprising 10% by weight and 1% by weight, respectively, of PDADMAC was rinsed over. The process of overflowing the sensor was carried out at 60 Ā° C in a QCM Q-Sense (Stockholm, Sweden). The cleaning agents removed the glass coating from the sensor after a certain period of time (mass removal). This mass removal from the sensor corresponds to the severity of the glass corrosion.
  • the beginning of the mass removal measured from the moment when the sensor is flushed 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 determination of the time t, from which a mass removal took place, corresponds to the period from the beginning of the overflushing of the sensor with the detergent up to the moment in which a significant mass removal was recognizable. The information is given here in minutes. Mass removal was determined relative to the original mass value. The indication is therefore here in%. Rinsing with a detergent that did not contain a PDADMAC caused a loss of mass of the sensor of more than 50% of the glass layer after less than 30 minutes. PDADMAC was able to delay the occurrence of mass loss three times later. The mass loss was initially about 50% here. Both in the comparative example and in the detergent according to the invention, which had 1% by weight of PDADMAC, a limit value developed. Further glass removal did not take place here.
  • a second inventive detergent which had 10 wt .-% PDADMAC, tested.
  • the first loss of mass occurred only after a 4 to 6 times as long as without PDADMAC.
  • a maximum value was reached. This was again about 10 to 20% less than in the inventive detergent containing 1 wt .-% PDADMAC.
  • a cleaning agent according to the invention which comprises PDADMAC therefore makes it possible to significantly reduce glass corrosion. This occurs on the one hand much later and ensures a lower loss of mass over time. The glass corrosion thus occurs only after a larger number of rinsing cycles. In addition, the severity of the glass corrosion is reduced compared to cleaning agents known in the prior art.

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Abstract

The invention relates to a cleaning agent which allows corrosion of glass to be reduced or even prevented especially in machine-operated cleaning processes. The cleaning agent is especially a dish soap for cleaning dishes in a dishwasher, said dish soap containing polydiallyldimethylammonium chloride (PDADMAC). The invention further relates to a method for cleaning objects having a glass surface using the disclosed cleaning agent.

Description

ā€žReinigungsmittel umfassend einen Glaskorrosionsinhibitor" "Detergent comprising a glass corrosion inhibitor"
Die vorliegende Erfindung betrifft ein Reinigungsmittel, mit welchem insbesondere beim maschinellen Reinigen Glaskorrosion verringert oder sogar vermieden werden kann. Bei dem Reinigungsmittel handelt es sich insbesondere um ein GeschirrspĆ¼lmittel zur maschinellen Reinigung von Geschirr. Weiterhin betrifft die vorliegende Erfindung ein Verfahren zum Reinigen von GegenstƤnden mit GlasoberflƤche unter Verwendung des erfindungsgemƤƟen Reinigungsmittels. The present invention relates to a cleaning agent with which glass corrosion can be reduced or even avoided, in particular during machine cleaning. The cleaning agent is in particular a dishwashing detergent for machine cleaning of dishes. Furthermore, the present invention relates to a method for cleaning objects with glass surface using the cleaning agent according to the invention.
Die Aufgabe von Reinigungsmitteln ist Ć¼blicherweise die Reinigung von verschmutzen OberflƤchen. Dabei sollen sie einerseits hartnƤckige Anschmutzungen entfernen. Andererseits sollen die gereinigten OberflƤchen jedoch nicht angegriffen werden. Insbesondere bei GegenstƤnden, welche eine OberflƤche aus Glas aufweisen, ist hƤufig problematisch, dass das Glas angegriffen wird, so dass es zur Glaskorrosion kommt. Insbesondere beim maschinellen Reinigen von Geschirr mit konventionellen GeschirrspĆ¼lmitteln ist Glaskorrosion ein hƤufig auftretendes Problem. Ɯblicherweise weist die Waschflotte, bei der Geschirr mit konventionellen GeschirrspĆ¼lmitteln gereinigt wird, einen pH-Wert von 8,0 oder mehr auf. Viele marktĆ¼bliche Glasarten werden hier angegriffen und zeigen dadurch im Laufe vieler SpĆ¼lzyklen TrĆ¼bungserscheinungen, welche als Glaskorrosion bezeichnet werden. The task of cleaning agents is usually the cleaning of dirty surfaces. They should on the one hand remove stubborn stains. On the other hand, however, 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. Especially when machine washing dishes with conventional dishwashing detergents, glass corrosion is a common problem. Usually, the wash liquor used to clean dishes with conventional dishwashing detergents has a pH of 8.0 or more. Many commercially available types of glass are attacked here and thus show in the course of many rinse cycles turbidity phenomena, which are referred to as glass corrosion.
Im Sinne einer umweltfreundlichen Reinigung ist es wĆ¼nschenswert, dass Reinigungsmittel und insbesondere GeschirrspĆ¼lmittel einen geringen Phosphatgehalt aufweisen oder sogar vollstƤndig ohne Phosphate auskommen. Notwendige Ersatzstoffe hierfĆ¼r sind Komplexbildner, welche jedoch die zu reinigende GlasoberflƤchen angreifen. In terms of environmentally friendly cleaning, it is desirable that detergents 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.
Die Aufgabe der vorliegenden Erfindung besteht nun in der Bereitstellung eines Reinigungsmittels, insbesondere eines GeschirrspĆ¼lmittels zur Reinigung von GegenstƤnden mit GlasoberflƤchen, wobei die insbesondere durch Komplexbildner verursachte Glaskorrosion vermindert oder wenigstens verringert werden soll. Dabei soll die Reinigungsleistung des Produktes im Hinblick auf die Entfernung von Anschmutzungen nicht nachteilig beeinflusst werden. The object of the present invention is now to provide a cleaning agent, in particular a dishwashing detergent for cleaning articles with glass surfaces, wherein the particular caused by complexing glass corrosion is to be reduced or at least reduced. The cleaning performance of the product should not be adversely affected with regard to the removal of stains.
Ɯberraschenderweise wurde gefunden, dass Polydiallyldimethylammoniumchlorid (PDADMAC) die Glaskorrosion, die durch Reinigungsmittel verursacht wird, deutlich verringert. Die der vorliegenden Erfindung zugrundeliegende Aufgabe wird daher gelƶst durch ein Reinigungsmittel umfassend wenigstens ein Tensid, einen oder mehrere Komplexbildner und PDADMAC. Das erfindungsgemƤƟe Reinigungsmittel umfasst vorzugweise PDADMAC in einem Anteil von 0,01 bis 50 Gew.-%, insbesondere von 0,01 bis 30 Gew.-%, bevorzugt von 0,01 bis 12 Gew.-%, insbesondere bevorzugt von 0,01 bis 1 Gew.-%. Ein Anteil von weniger als 0,01 Gew.-% von PDADMAC in einem Reinigungsmittel fĆ¼hrt zu keiner deutlich erkennbaren Verringerung der Glaskorrosion. Ein Anteil von 1 Gew.-% kann gut in Reinigungsmitteln eingearbeitet werden. Gleichzeitig wird hierdurch eine deutliche Verringerung der Glaskorrosion erreicht. Ein Anteil von 50 Gew.-% kann auch in ein Reinigungsmittel eingearbeitet werden, ohne dass dessen Reinigungsleistung nachteilig beeintrƤchtigt wird. Ein darĆ¼ber hinaus gehender Anteil fĆ¼hrt jedoch zu keiner weiteren Verbesserung im Hinblick auf die Glaskorrosion. Surprisingly, it has been found that polydiallyldimethylammonium chloride (PDADMAC) significantly reduces the glass corrosion caused by detergents. The object underlying the present invention is therefore achieved by a cleaning agent comprising at least one surfactant, one or more complexing agents and PDADMAC. The cleaning agent according to the invention preferably comprises PDADMAC in a proportion of 0.01 to 50 wt .-%, in particular from 0.01 to 30 wt .-%, preferably from 0.01 to 12 wt .-%, particularly preferably from 0.01 to 1% by weight. A proportion of less than 0.01% by weight of PDADMAC in a detergent does not result in any appreciable reduction in glass corrosion. A proportion of 1 wt .-% can be well incorporated in cleaning agents. At the same time thereby a significant reduction of the glass corrosion is achieved. A proportion of 50 wt .-% can also be incorporated into a cleaning agent, without its cleaning performance is adversely affected. However, a further amount does not lead to any further improvement with respect to the glass corrosion.
Das erfindungsgemƤƟe Reinigungsmittel umfasst wenigstens ein Tensid. Dies bedeutet, dass das Reinigungsmittel ein Tensid oder mehrere Tenside umfassen kann. Das wenigstens eine Tensid ist dabei vorzugsweise ausgewƤhlt aus der Gruppe, die nichtionische Tenside, kationische Tenside, anionische Tenside, zwitterionische Tenside sowie deren Mischungen umfasst. ErfindungsgemƤƟ kann das Reinigungsmittel daher vorzugsweise ein oder mehrere nichtionische Tenside umfassen. Es ist jedoch auch mƶglich, dass es ein nichtionisches Tensid zusammen beispielsweise mit einem anionischen Tensid umfasst. Andere Kombinationen der Tenside sind erfindungsgemƤƟ mit umfasst. The cleaning agent according to the invention comprises at least one surfactant. This means that the cleaning agent may 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. Therefore, according to the invention, the cleaning agent may preferably comprise one or more nonionic surfactants. However, it is also possible that it comprises a nonionic surfactant together with, for example, an anionic surfactant. Other combinations of the surfactants are included according to the invention.
In einer bevorzugten AusfĆ¼hrungsform enthƤlt das erfindungsgemƤƟe Reinigungsmittel mindestens ein nichtionisches Tensid. Als nichtionische Tenside (Niotensid) kƶnnen alle dem Fachmann bekannten nichtionischen Tenside eingesetzt werden. Als nichtionische Tenside eignen sich beispielsweise Alkylglykoside der allgemeinen Formel RO(G)x in der R einem primƤren geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen entspricht und G das Symbol ist, das fĆ¼r eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise fĆ¼r Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1 ,2 bis 1 ,4. In a preferred embodiment, the cleaning agent according to the invention contains at least one nonionic surfactant. As nonionic surfactants (nonionic surfactant) it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte FettsƤurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette. Another class of preferred nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N- dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid , und der FettsƤurealkanolamide kƶnnen geeignet sein. Die Menge dieser nichtionischen Tenside betrƤgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die HƤlfte davon. Weitere geeignete Tenside sind PolyhydroxyfettsƤureamide der folgenden Formel, 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 may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof. Further suitable surfactants are polyhydroxy fatty acid amides of the following formula
R-CO-Nā€” [Z] R-CO-N- [Z]
in der R fĆ¼r einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R fĆ¼r Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] fĆ¼r einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den PolyhydroxyfettsƤureamiden handelt es sich um bekannte Stoffe, die Ć¼blicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer FettsƤure, einem FettsƤurealkylester oder einem FettsƤurechlorid erhalten werden kƶnnen. R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 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.
Zur Gruppe der PolyhydroxyfettsƤureamide gehƶren auch Verbindungen der folgenden Formel The group of polyhydroxy fatty acid amides also includes compounds of the following formula
R1-0ā€” R2 R1-0 R2
I Ā I
R-CO-N-[Z] Ā R-CO-N- [Z]
in der R fĆ¼r einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R fĆ¼r einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R2 fĆ¼r einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei Ci-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] fĆ¼r einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein Ci-4-alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives thereof residue.
[Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N- Alkoxy- oder N-Aryloxy-substituierten Verbindungen kƶnnen durch Umsetzung mit FettsƤuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewĆ¼nschten PolyhydroxyfettsƤureamide Ć¼berfĆ¼hrt werden. [Z] is preferably obtained by reductive amination of a reduced sugar, for example 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 catalyst.
Als bevorzugte Tenside werden schwachschƤumende nichtionische Tenside eingesetzt. Mit besonderem Vorzug enthalten die erfindungsgemƤƟen Reinigungsmittel, insbesondere Reinigungsmittel fĆ¼r das maschinelle GeschirrspĆ¼len, nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole. Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primƤre Alkohole mit vorzugsweise 8 bis 18 C- Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie Ć¼blicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum Beispielaus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 Mol EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehƶren beispielsweise Ci 2-i4-Alkohole mit 3 EO oder 4 EO, Csn-Alkohol mit 7 EO, Ci s-i s-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, Ci2-i 8-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus Ci2-i4-Alkohol mit 3 EO und Ci 2-i s-Alkohol mit 5 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die fĆ¼r ein spezielles Produkt einer ganzen oder einer gebrochenen Zahl entsprechen kƶnnen. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow rƤnge ethoxylates, NRE). ZusƤtzlich zu diesen nichtionischen Tensiden kƶnnen auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfĆ¼r sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, the cleaning agents according to the invention, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. As nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in in which the alcohol radical can be linear 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. In particular, however, preferred are alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C 12-14-alcohols with 3 EO or 4 EO, Csn-alcohol with 7 EO, cis-s 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 Ci2-i4-alcohol with 3 EO and Ci 2-i s-alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
Mit besonderem Vorzug werden daher ethoxylierte Niotenside, die aus C6-2o-Monohydroxy- alkanolen oder C6-2o-Alkylphenolen oder Ci 6-2o-Fettalkoholen und mehr als 12 Mol, vorzugsweise mehr als 15 Mol und insbesondere mehr als 20 Mol Ethylenoxid pro Mol Alkohol gewonnen wurden, eingesetzt. Ein besonders bevorzugtes Niotensid wird aus einem geradkettigen Fettalkohol mit 16 bis 20 Kohlenstoffatomen (Ci 6-2o-Alkohol), vorzugsweise einem Cis-Alkohol und mindestens 12 Mol, vorzugsweise mindestens 15 Mol und insbesondere mindestens 20 Mol Ethylenoxid gewonnen. Hierunter sind die sogenannten ā€žnarrow rƤnge ethoxylates" besonders bevorzugt. Particular preference is therefore given to ethoxylated nonionic surfactants which are prepared from C 6-2o-monohydroxyalkanols or C 6-2o-alkylphenols or C 6-2o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 6-2o-alcohol), preferably a cis-alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow ranks ethoxylates" are particularly preferred.
Insbesondere bevorzugt sind nichtionische Tenside, die einen Schmelzpunkt oberhalb Raumtemperatur aufweisen. Nichtionische(s) Tensid(e) mit einem Schmelzpunkt oberhalb von 20Ā°C, vorzugsweise oberhalb von 25Ā°C, besonders bevorzugt zwischen 25 und 60Ā°C und insbesondere zwischen 26,6 und 43,3Ā°C, ist/sind besonders bevorzugt. Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 Ā° C, preferably above 25 Ā° C, more preferably between 25 and 60 Ā° C and especially between 26.6 and 43.3 Ā° C, is / are particularly preferred ,
Geeignete nichtionische Tenside, die Schmelz- beziehungsweise Erweichungspunkte im genannten Temperaturbereich aufweisen, sind beispielsweise schwachschƤumende nichtionische Tenside, die bei Raumtemperatur fest oder hochviskos sein kƶnnen. Werden Niotenside eingesetzt, die bei Raumtemperatur hochviskos sind, so ist bevorzugt, dass diese eine ViskositƤt oberhalb von 20 PaĀ«s, vorzugsweise oberhalb von 35 PaĀ«s und insbesondere oberhalb 40 PaĀ«s aufweisen. Auch Niotenside, die bei Raumtemperatur wachsartige Konsistenz besitzen, sind bevorzugt. Niotenside aus der Gruppe der alkoxylierten Alkohole, besonders bevorzugt aus der Gruppe der gemischt alkoxylierten Alkohole und insbesondere aus der Gruppe der EO-AO-EO-Niotenside, werden ebenfalls mit besonderem Vorzug eingesetzt. Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that these s, preferably above 35 Pa Ā«s and in particular above 40 PaĀ« s have a viscosity above 20 Pa. " Nonionic surfactants which have waxy consistency at room temperature are also preferred. Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also used with particular preference.
Das bei Raumtemperatur feste Niotensid besitzt vorzugsweise Propylenoxideinheiten (PO) im MolekĆ¼l. Vorzugsweise machen solche PO-Einheiten bis zu 25 Gew.-% , besonders bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids aus. Besonders bevorzugte nichtionische Tenside sind ethoxylierte Monohydroxyalkanole oder Alkylphenole, die zusƤtzlich Polyoxyethylen-Polyoxypropylen Blockcopolymereinheiten aufweisen. Der Alkohol- beziehungsweise Alkylphenolteil solcher NiotensidmolekĆ¼le macht dabei vorzugsweise mehr als 30 Gew.-%, besonders bevorzugt mehr als 50 Gew.-% und insbesondere mehr als 70 Gew.-% der gesamten Molmasse solcher Niotenside aus. Bevorzugte Mittel sind dadurch gekennzeichnet, dass sie ethoxylierte und propoxylierte Niotenside enthalten, bei denen die Propylenoxideinheiten im MolekĆ¼l bis zu 25 Gew.-%, bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids ausmachen. The nonionic surfactant solid at room temperature preferably has propylene oxide units (PO) in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight, of the total molecular weight 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 up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
Bevorzugt einzusetzende Tenside stammen aus den Gruppen der alkoxylierten Niotenside, insbesondere der ethoxylierten primƤren Alkohole und Mischungen dieser Tenside mit strukturell komplizierter aufgebauten Tensiden wiePreferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as
Polyoxypropylen/Polyoxyethylen/Polyoxypropylen ((PO/EO/PO)-Tenside). Solche (PO/EO/PO)-Niotenside zeichnen sich darĆ¼ber hinaus durch gute Schaumkontrolle aus. Polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
Weitere besonders bevorzugt einzusetzende Niotenside mit Schmelzpunkten oberhalb Raumtemperatur enthalten 40 bis 70% einesFurther particularly preferably used nonionic surfactants with melting points above room temperature contain 40 to 70% of a
Polyoxypropylen/Polyoxyethylen/Polyoxypropylen-Blockpolymerblends, der 75 Gew.-% eines umgekehrten Block-Copolymers von Polyoxyethylen und Polyoxypropylen mit 17 Mol Ethylenoxid und 44 Mol Propylenoxid und 25 Gew.-% eines Block-Copolymers von Polyoxyethylen und Polyoxypropylen, initiiert mit Trimethylolpropan und enthaltend 24 Mol Ethylenoxid und 99 Mol Propylenoxid pro Mol Trimethylolpropan, enthƤlt. Polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blends comprising 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
Als besonders bevorzugte Niotenside haben sich im Rahmen der vorliegenden Erfindung schwachschƤumende Niotenside erwiesen, welche alternierende Ethylenoxid- und Alkylenoxideinheiten aufweisen. Unter diesen sind wiederum Tenside mit EO-AO-EO-AO- Blƶcken bevorzugt, wobei jeweils eine bis zehn EO- beziehungsweise AO-Gruppen aneinander gebunden sind, bevor ein Block aus den jeweils anderen Gruppen folgt. Hier sind nichtionische Tenside der allgemeinen Formel Ri-0-(C H2-CIn the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula Ri-O- (CH 2 -C
bevorzugt, in der R fĆ¼r einen geradkettigen oder verzweigten, gesƤttigten oder einbeziehungsweise mehrfach ungesƤttigten C6-24-Alkyl- oderā€” Alkenylrest steht; jede Gruppe R2 beziehungsweise R3 unabhƤngig voneinander ausgewƤhlt ist aus -Chta, -CH2CH3, -CH2CH2-CH3, CH(CH3)2 und die Indizes w, x, y, z unabhƤngig voneinander fĆ¼r ganze Zahlen von 1 bis 6 stehen. in which R 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 -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
Die bevorzugten Niotenside der vorstehenden Formel lassen sich durch bekannte Methoden aus den entsprechenden Alkoholen R -OH und Ethylen- beziehungsweise Alkylenoxid herstellen. Der Rest R in der vorstehenden Formel kann je nach Herkunft des Alkohols variieren. Werden native Quellen genutzt, weist der Rest R eine gerade Anzahl von Kohlenstoffatomen auf und ist in der Regel unverzweigt, wobei die linearen Reste aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, zum Beispielaus Kokos-, Palm-, Talgfett- oder Oleylalkohol, bevorzugt sind. Aus synthetischen Quellen zugƤngliche Alkohole sind beispielsweise die Guerbetalkohole oder in 2-Stellung methylverzweigte beziehungsweise lineare und methylverzweigte Reste im Gemisch, so wie sie Ć¼blicherweise in Oxoalkoholresten vorliegen. UnabhƤngig von der Art des zur Herstellung der in den Mitteln enthaltenen Niotenside eingesetzten Alkohols sind Niotenside bevorzugt, bei denen R in der vorstehenden Formel fĆ¼r einen Alkylrest mit 6 bis 24, vorzugsweise 8 bis 20, besonders bevorzugt 9 bis 15 und insbesondere 9 bis 1 1 Kohlenstoffatomen steht. The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R -OH and ethylene or alkylene oxide. The radical R in the above formula may vary depending on the origin of the alcohol. When native sources are used, the group R has an even number of carbon atoms and is usually unbranched, the linear groups being selected from alcohols of native origin containing from 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol , are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.
Als Alkylenoxideinheit, die alternierend zur Ethylenoxideinheit in den bevorzugten Niotensiden enthalten ist, kommt neben Propylenoxid insbesondere Butylenoxid in Betracht. Aber auch weitere Alkylenoxide, bei denen R2 beziehungsweise R3 unabhƤngig voneinander ausgewƤhlt sind aus -CH2CH2-CH3 beziehungsweise -CH(CH3)2 sind geeignet. Bevorzugt werden Niotenside der vorstehenden Formel eingesetzt, bei denen R2 beziehungsweise R3 fĆ¼r einen Rest -CH3, w und x unabhƤngig voneinander fĆ¼r Werte von 3 oder 4 und y und z unabhƤngig voneinander fĆ¼r Werte von 1 oder 2 stehen. As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3) 2 are suitable. Preference is given to using nonionic surfactants of the above formula in which R 2 or R 3 is a radical -CH 3, w and x are independently of one another values of 3 or 4 and y and z are independently of one another values of 1 or 2.
Zusammenfassend sind insbesondere nichtionische Tenside bevorzugt, die einen C9-is-Alkylrest mit 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten, gefolgt von 1 bis 4 Ethylenoxideinheiten, gefolgt von 1 bis 4 Propylenoxideinheiten aufweisen. Diese Tenside weisen in wƤssriger Lƶsung die erforderliche niedrige ViskositƤt auf und sind erfindungsgemƤƟ mit besonderem Vorzug einsetzbar. In summary, particularly preferred are nonionic surfactants having a C9-alkyl group having 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 according to the invention with particular preference.
Tenside der allgemeinen Formel Surfactants of the general formula
R -CH(OH)CH20-(AO)w-(A'0)x-(A"0)y-(A'"0)z-R2, in der R und R2 unabhƤngig voneinander fĆ¼r einen geradkettigen oder verzweigten, gesƤttigten oder ein-beziehungsweise mehrfach ungesƤttigten C2-4o-Alkyl- oder -Alkenylrest steht; A, Ī‘', A" und A'" unabhƤngig voneinander fĆ¼r einen Rest aus der Gruppe -CH2CH2, -CH2CH2-CH2, -CH2- CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-, -CH2-CH(CH2-CH3) steht; und w, x, y und z fĆ¼r Werte zwischen 0,5 und 90 stehen, wobei x, y und/oder z auch 0 sein kƶnnen, sind erfindungsgemƤƟ besonders bevorzugt. R is -CH (OH) CH 2 O- (AO) w- (A'0) x- (A "0) y - (A '" 0) z R 2 , in which R and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-4 -alkyl or -alkenyl radical; A, Ī‘ ', A "and A'" independently of one another are radicals 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 are values between 0.5 and 90, where x, y and / or z can also be 0, are particularly preferred according to the invention.
Ganz besonders bevorzugt sind hierbei nichtionische Tenside der allgemeinen Formel R 0[CH2CH(CH3)0]x[CH2CH20]y[CH2CH(CH3)0]zCH2CH(OH)R2, in der R fĆ¼r einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22, insbesondere 6 bis 18, Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26, insbesondere 4 bis 20, Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x und z fĆ¼r Werte zwischen 0 und 40 und y fĆ¼r einen Wert von mindestens 15, vorzugsweise von 15 bis 120, besonders bevorzugt von 20 bis 80, steht. Very particular preference is given here to nonionic surfactants of the general formula R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] zCH 2 CH (OH) R 2 , where R is a linear or branched aliphatic radical Hydrocarbon radical having 4 to 22, in particular 6 to 18, carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26, in particular 4 to 20, carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y is a value of at least 15, preferably from 15 to 120, particularly preferably from 20 to 80.
In einer bevorzugten AusfĆ¼hrungsform enthƤlt das Reinigungsmittel, bezogen auf sein Gesamtgewicht, nichtionisches Tensid der allgemeinen FormelIn a preferred embodiment, the detergent contains, based on its total weight, nonionic surfactant of the general formula
RO[CH2CH(CH3)0]x[CH2CH20]y[CH2CH(CH3)0]zCH2CH(OH)R2 in Mengen von 0,1 bis 15 Gew.- %, vorzugsweise von 0,2 bis 10 Gew.-%, besonders bevorzugt von 0,5 bis 8 Gew.-% und insbesondere von 1 ,0 bis 6 Gew.-%. RO [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 of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight. -%, particularly preferably from 0.5 to 8 wt .-% and in particular from 1, 0 to 6 wt .-%.
Bevorzugt sind insbesondere solche endgruppenverschlossene poly(oxyalkylierten) Niotenside gemƤƟ der Formel R 0[CH2CH20]yCH2CH(OH)R2, in der R fĆ¼r einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22, insbesondere mit 6 bis 16, Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26, insbesondere mit 4 bis 20, Kohlenstoffatomen oder Mischungen hieraus bezeichnet und y fĆ¼r einen Wert zwischen 15 und 120 vorzugsweise 20 bis 100, insbesondere 20 bis 80 steht. Zur Gruppe dieser nichtionischen Tenside zƤhlen beispielsweise Hydroxymischether der allgemeinen Formel C6-22-CH(OH)CH20(EO)2o-i 2o-C2-26, zum Beispiel die C8-12 Fettalkohol- (EO)22-2-hydroxydecylether und die C4-22 Fettalkohol-(EO)4o-8o-2-hydroxyalkylether. Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants according to the formula R 0 [CH 2 CH 2 O] yCH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22, in particular 6 to 16, carbon atoms or mixtures thereof R 2 is a linear or branched hydrocarbon radical having 2 to 26, in particular having 4 to 20, carbon atoms or mixtures thereof and y is a value between 15 and 120 preferably 20 to 100, in particular 20 to 80 stands. The group of these nonionic surfactants include, for example, hydroxy mixed ethers of the general formula C6-22-CH (OH) CH20 (EO) 2o-i 2o-C2-26, for example the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o-8o-2-hydroxyalkyl ether.
Ein erfindungsgemƤƟ bevorzugtes maschinelles GeschirrspĆ¼lmittel ist insbesondere dadurch gekennzeichnet, dass als schwachschƤumendes nichtionisches Tensid ein Tensid der allgemeinen Formel R CH(OH)CH20-(CH2CH20)2o-i2o- R2 eingesetzt wird, wobei R und R2 unabhƤngig voneinander fĆ¼r einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 2 bis 20, insbesondere 4 bis 16, Kohlenstoffatomen stehen. Bevorzugt sind weiterhin Tenside der Formel R 0[CH2CH(CH3)0]X[CH2CH20]YCH2CH(OH)R2, in der R fĆ¼r einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet und x fĆ¼r Werte zwischen 0,5 und 4, vorzugsweise 0,5 bis 1 ,5, und y fĆ¼r einen Wert von mindestens 15 steht. A machine dishwashing detergent preferred according to the invention is characterized in particular by using as low-foaming nonionic surfactant a surfactant of the general formula R CH (OH) CH 2 O- (CH 2 CH 2 O) 2o-i 2 -R 2 , where R and R 2 are independently of one another linear or branched aliphatic hydrocarbon radical having 2 to 20, in particular 4 to 16, carbon atoms. Also preferred are surfactants of the formula R 0 [CH 2 CH (CH 3 ) O] X [CH 2 CH 2 O] YCH 2 CH (OH) R 2 , in which R is a linear or branched aliphatic hydrocarbon radical having 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 represents values between 0.5 and 4, preferably 0.5 to 1.5, and y represents a value of at least 15.
Erfind ungsgemƤƟ sind weiterhin auch Tenside der allgemeinen Formel In accordance with the invention are also surfactants of the general formula
R 0[CH2CH(CH3)0]x[CH2CH20]yCH2CH(OH)R2 bevorzugt, in der R fĆ¼r einen linearen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 4 bis 22 Kohlenstoffatomen oder Mischungen hieraus steht, R2 einen linearen oder verzweigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen oder Mischungen hieraus bezeichnet u nd x fĆ¼r einen Wert zwischen 1 und 40 und y fĆ¼r einen Wert zwischen 15 und 40 steht, wobei die Alkyleneinheiten [CH2CH(CH3)0] und [CH2CH2O] randomisiert, das heiƟt in Form einer statistischen , zufƤlligen Verteilung vorliegen. R 0 [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] yCH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R 2 is a linear or branched one Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units randomized [CH 2 CH (CH 3) O] and [CH 2 CH 2 O], that is in Form a random statistical distribution.
Zur Gruppe der bevorzugten endgruppenverschlossenen poly(oxyalkylierten) Niotenside zƤhlen auch Niotenside der Formel The group of preferred end-capped poly (oxyalkylated) nonionic surfactants also includes nonionic surfactants of the formula
RO[CH2CH20]x[CH2CH(R3)0]yCH2CH(OH)R2, in der R und R2 unabhƤngig voneinander fĆ¼r einen linearen oder verzweigten, gesƤttigten oder ein- beziehungsweise mehrfach ungesƤttigten Kohlenwasserstoffrest mit 2 bis 26 Kohlenstoffatomen steht, R3 unabhƤngig voneinander ausgewƤhlt ist aus ā€” CH3, -CH2CH3, - CH2CH2-CH3, -CH(CH3)2, vorzugsweise jedoch fĆ¼r ā€” CH3 steht, und x und y unabhƤngig voneinander fĆ¼r Werte zwischen 1 und 32 stehen, wobei Niotenside mit R3 = ā€” CH3 und Werten fĆ¼r x von 15 bis 32 und y von 0,5 und 1 ,5 ganz besonders bevorzugt sind . RO [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2 , in which R and R 2 independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms , R 3 is independently selected from - CH3, -CH2CH3, - CH2CH2-CH3, -CH (CH3) 2, but preferably is - CH3, and x and y are independently values between 1 and 32, wherein nonionic surfactants with R 3 = - CH 3 and values for x of 15 to 32 and y of 0.5 and 1.5, are very particularly preferred.
Weitere bevorzugt einsetzbare Niotenside sind die endgruppenverschlossenen poly(oxyalkylierten) Niotenside der Formel Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
R 0[CH2CH(R3)0]x[CH2]kCH(OH)[CH2]jOR2 , in der R und R2 fĆ¼r lineare oder verzweigte , gesƤttigte oder ungesƤttigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 1 bis 30 Kohlenstoffatomen stehen , R3 fĆ¼r H oder einen Methyl-, Ethyl-, n-Propyl-, iso-Propyl, n-Butyl-, 2-Butyl- oder 2-Methyl-2-Butylrest steht, x fĆ¼r Werte zwischen 1 und 30, k und j fĆ¼r Werte zwischen 1 und 12, vorzugsweise zwischen 1 u nd 5 stehen. Wenn der Wert x 2 ist, kann jedes R3 in der obenstehenden Formel R 0[CH2CH(R3)0]x[CH2]kCH(OH)[CH2]jOR2 unterschied lich sein. R und R2 sind vorzugsweise lineare oder verzweigte, gesƤttigte oder ungesƤttigte, aliphatische oder aromatische Kohlenwasserstoffreste mit 6 bis 22 Kohlenstoffatomen, wobei Reste mit 8 bis 18 C-Atomen besonders bevorzugt sind. FĆ¼r den Rest R3 sind H, -Ch oder -CH2CH3 besonders bevorzugt. Besonders bevorzugte Werte fĆ¼r x liegen im Bereich von 1 bis 20, insbesondere von 6 bis 15. R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] kCH (OH) [CH 2 ] jOR 2 in which R and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 Carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is between 1 and 30 , k and j are values between 1 and 12, preferably between 1 and 5. When the value x is 2, each R 3 in the above formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] kCH (OH) [CH 2 ] jOR 2 may be different. R and R 2 are preferred linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R 3 , H, -Ch 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.
Wie vorstehend beschrieben, kann jedes R3 in der obenstehenden Formel unterschiedlich sein, falls x 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht x beispielsweise fĆ¼r 3, kann der Rest R3 ausgewƤhlt werden, um Ethylenoxid- (R3 = H) oder Propylenoxid- (R3 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefĆ¼gt sein kƶnnen, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 fĆ¼r x ist hierbei beispielhaft gewƤhlt worden und kann durchaus grĆ¶ĆŸer sein, wobei die Variationsbreite mit steigenden x- Werten zunimmt und beispielsweise eine groƟe Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)-Gruppen einschlieƟt, oder umgekehrt. As described above, each R 3 in the above formula may be different if x is 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R 3 can be selected to form ethylene oxide (R 3 = H) or propylene oxide (R 3 = CH 3 ) units which may be joined in any order, for example (EO) (PO ) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) (PO ) (PO). The value 3 for x has been selected here by way of example and may well be greater, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
Besonders bevorzugte endgruppenverschlossene poly(oxyalkylierte) Alkohole der obenstehenden Formel weisen Werte von k = 1 und j = 1 auf, so dass sich die vorstehende Formel zu R 0[CH2CH(R3)0]x(CH2CH(OH)CH2OR2 vereinfacht. In der letztgenannten Formel sind R\ R2 und R3 wie oben definiert und x steht fĆ¼r Zahlen von 1 bis 30, vorzugsweise von 1 bis 20 und insbesondere von 6 bis 18. Besonders bevorzugt sind Tenside, bei denen die Reste R und R2 9 bis 14 C-Atome aufweisen, R3 fĆ¼r H steht und x Werte von 6 bis 15 annimmt. Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula becomes R 0 [CH 2 CH (R 3 ) O] x (CH 2 CH (OH) CH 2 OR 2. In this formula, R \ R 2 and R 3 are as defined above and x represents 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 and R 2 have 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
Weitere bevorzugt eingesetzte nichtionische Tenside sind nichtionische Tenside der allgemeinen Formel R 0(AlkO)xM(OAIk)yOR2, wobei Further preferably used nonionic surfactants are nonionic surfactants of the general formula R 0 (AlkO) xM (OAlk) y OR 2 , where
R und R2 unabhƤngig voneinander fĆ¼r einen verzweigten oder unverzwe igten, gesƤttigten oder ungesƤttigten, gegebenenfalls hydroxylierten Alkylrest mit 4 bis 22 Kohlenstoffatomen stehen; R and R 2 independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms;
Alk fĆ¼r einen verzweigten oder unverzweigten Alkylrest mit 2 bis 4 Kohlenstoffatomen steht; x und y unabhƤngig voneinander fĆ¼r Werte zwischen 1 und 70 stehen; und Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and
M fĆ¼r einen Alkylrest aus der Gruppe CH2, CHR3, CR3R4, CH2CHR3 und CHR3CHR4 steht, wobei R3 und R4 unabhƤngig voneinander fĆ¼r einen verzweigten oder unverzwe igten, gesƤttigten oder ungesƤttigten Alkylrest mit 1 bis 18 Kohlenstoffatomen stehen. M is an alkyl radical from the group CH 2, CHR 3, CR 3 R 4, CH 2 CHR 3 and CHR 3 CHR 4, wherein R 3 and R 4 independently represent a branched or unverzwe temperate, saturated or unsaturated alkyl radical having 1 to 18 Carbon atoms.
Bevorzugt sind hierbei nichtionische Tenside der allgemeinen Formel Nonionic surfactants of the general formula are preferred here
R -CH(OH)CH2-0(CH2CH20)xCH2CHR(OCH2CH2)y-CH2CH(OH)-R2, wobei R, R und R2 unabhƤngig voneinander fĆ¼r einen Alkylrest oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen; x und y unabhƤngig voneinander fĆ¼r Werte zwischen 1 und 40 stehen Bevorzugt sind hierbei insbesondere Verbindungen der allgemeinen Formel R is -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 and R 2 are independently an alkyl or alkenyl radical of 6 to 22 carbon atoms; x and y independently represent values between 1 and 40 Particular preference is given here to compounds of the general formula
R -CH(OH)CH2-0(CH2CH20)xCH2CHR(OCH2CH2)yO-CH2CH(OH)-R2, in denen R fĆ¼r einen linearen, gesƤttigten Alkylrest mit 8 bis 16 Kohlenstoffatomen, vorzugsweise 10 bis 14 Kohlenstoffatomen steht und n und m unabhƤngig voneinander Werte von 20 bis 30 aufweisen. Entsprechende Verbindungen kƶnnen beispielsweise durch Umsetzung von Alkyldiolen HO-CHR-CH2-OH mit Ethylenoxid erhalten werden, wobei im Anschluss eine Umsetzung mit einem Alkylepoxid zum Verschluss der freien OH-Funktionen unter Ausbildung eines Dihydroxyethers erfolgt. R is -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 wherein R is a linear saturated alkyl radical of 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms; n and m independently of one another have values of 20 to 30. Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.
In einer weiteren bevorzugten AusfĆ¼hrungsform ist das nichtionische Tensid ausgewƤhlt aus nichtionischen Tensiden der allgemeinen Formel In a further preferred embodiment, the nonionic surfactant is selected from nonionic surfactants of the general formula
R -0(CH2CH20)xCR3R4(OCH2CH2)yO-R2, in der R und R2 unabhƤngig voneinander fĆ¼r einen Alkylrest oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen; R -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y O -R 2 , in which R and R 2 independently represent an alkyl or alkenyl radical having 4 to 22 carbon atoms;
R3 und R4 unabhƤngig voneinander fĆ¼r H oder fĆ¼r einen Alkylrest oder Alkenylrest mit 1 bis 18 Kohlenstoffatomen und R 3 and R 4 independently of one another are H or an alkyl radical or alkenyl radical having 1 to 18 carbon atoms and
x und y unabhƤngig voneinander fĆ¼r Werte zwischen 1 und 40 stehen. Bevorzugt sind hierbei insbesondere Verbindungen der allgemeinen Formel R -0(CH2CH20)xCR3R4(OCH2CH2)yO-R2, in der R3 und R4 fĆ¼r H stehen und die Indices x und y unabhƤngig voneinander Werte von 1 bis 40, vorzugsweise von 1 bis 15 annehmen. x and y independently represent values between 1 and 40. Compounds of the general formula R -O (CH 2 CH 2 O) xCR 3 R 4 (OCH 2 CH 2 ) yO-R 2 in which R 3 and R 4 are H and the indices x and y independently of one another have values from 1 to 2 are preferred 40, preferably from 1 to 15 accept.
Besonders bevorzugt sind insbesondere Verbindungen der allgemeinen Formel R -0(CH2CH20)xCR3R4(OCH2CH2)yO-R2, in der die Reste R und R2 unabhƤngig voneinander gesƤttigte Alkylreste mit 4 bis 14 Kohlenstoffatome darstellen und die Indices x und y unabhƤngig voneinander Werte von 1 bis 15 und insbesondere von 1 bis 12 annehmen. Particular preference is given in particular to compounds of the general formula R -O (CH 2 CH 2 O) xCR 3 R 4 (OCH 2 CH 2 ) yO-R 2 in which the radicals R and R 2 independently of one another represent 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.
Weiterhin bevorzugt sind solche Verbindungen der allgemeinen Formel R -0(CH2CH20)xCR3R4(OCH2CH2)yO-R2, in der einer der Reste R und R2 verzweigt ist. Further preferred are those compounds of the general formula R -O (CH 2 CH 2 O) xCR 3 R 4 (OCH 2 CH 2 ) yO-R 2 , in which one of the radicals R and R 2 is branched.
Ganz besonders bevorzugt sind Verbindungen der allgemeinen Formel R -0(CH2CH20)xCR3R4(OCH2CH2)yO-R2, in der die Indices x und y unabhƤngig voneinander Werte von 8 bis 12 annehmen. Very particular preference is given to compounds of the general formula R -O (CH 2 CH 2 O) xCR 3 R 4 (OCH 2 CH 2 ) yO-R 2 , in which the indices x and y independently of one another assume values of 8 to 12.
Die angegebenen C-KettenlƤngen sowie Ethoxylierungsgrade beziehungsweise Alkoxylierungsgrade der vorgenannten Niotenside stellen statistische Mittelwerte dar, die fĆ¼r ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kƶnnen. Aufgrund der Herste II verfahren bestehen Handelsprodukte der genannten Formeln zumeist nicht aus einem individuellen Vertreter, sondern aus Gemischen, wodurch sich sowohl fĆ¼r die C-KettenlƤngen als auch fĆ¼r die Ethoxylierungsgrade beziehungsweise Alkoxylierungsgrade Mittelwerte und daraus folgend gebrochene Zahlen ergeben kƶnnen. The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical average values which, for a specific product, may be an integer or a fractional number. Due to the methods II trade products of the formulas mentioned are usually not from an individual representative, but from mixtures, which may result in both the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation averages and resulting broken numbers.
SelbstverstƤndlich kƶnnen die vorgenannten nichtionischen Tenside nicht nur als Einzelsubstanzen, sondern auch als Tensidgemische aus zwei, drei, vier oder mehr Tensiden eingesetzt werden. Als Tensidgemische werden dabei nicht Mischungen nichtionischer Tenside bezeichnet, die in ihrer Gesamtheit unter eine der oben genannten allgemeinen Formeln fallen, sondern vielmehr solche Mischungen, die zwei, drei, vier oder mehr nichtionische Tenside enthalten, die durch unterschiedliche der vorgenannten allgemeinen Formeln beschrieben werden kƶnnen. Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
Insbesondere bevorzugt sind solche nichtionische Tenside, die einen Schmelzpunkt oberhalb Raumtemperatur aufweisen. Nichtionische(s) Tensid(e) mit einem Schmelzpunkt oberhalb von 20Ā°C, vorzugsweise oberhalb von 25Ā°C, besonders bevorzugt zwischen 25Ā°C und 60Ā°C und insbesondere zwischen 26,6Ā°C und 43,3Ā°C, ist/sind besonders bevorzugt. Particular preference is given to those nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 Ā° C, preferably above 25 Ā° C, more preferably between 25 Ā° C and 60 Ā° C and especially between 26.6 Ā° C and 43.3 Ā° C. / are particularly preferred.
Der Gewichtsanteil des nichtionischen Tensids am Gesamtgewicht des erfindungsgemƤƟen Reinigungsmittels betrƤgt in einer bevorzugten AusfĆ¼hrungsform von 0, 1 bis 20 Gew.-%, besonders bevorzugt von 0,5 bis 15 Gew.-%, insbesondere von 2,5 bis 10 Gew.-%. The proportion by weight of the nonionic surfactant in the total weight of the cleaning agent according to the invention in a preferred embodiment is from 0.1 to 20% by weight, more preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight. ,
Bevorzugte Reinigungsmittel sind weiterhin dadurch gekennzeichnet, dass sie weniger als 1 ,0 Gew.-% und insbesondere kein anionisches Tensid enthalten, da der Zusatz anionischer Tenside sich im Hinblick auf die Tabletten(phasen)eigenschaften, insbesondere deren HƤrte, FriabilitƤt und NachhƤrteverhalten als nachteilig erwiesen hat. ErfindungsgemƤƟ liegt das Reinigungsmittel bevorzugt in Form eines Formkƶrpers, insbesondere einer Tablette vor. Preferred cleaning agents are further characterized in that they contain less than 1, 0 wt .-% and in particular no anionic surfactant, since the addition of anionic surfactants with respect to the tablet (phase) properties, in particular their hardness, friability and Post-hardening has proved to be disadvantageous. According to the invention, the cleaning agent is preferably in the form of a shaped body, in particular a tablet.
Das erfindungsgemƤƟe Reinigungsmittel umfasst weiterhin einen oder mehrere Komplexbildner. Die Komplexbildner haben insbesondere die Aufgabe der Komplexierung von Ca- und Mg-Ionen aus dem SpĆ¼lwasser. Diese Aufgabe wird von Phosphaten erfĆ¼llt. Da Phosphate zur Entrophierung der GewƤsser beitragen, werden diese durch Komplexbildner ersetzt. Geeignete Komplexbildner sind dem Fachmann bekannt. Beispielsweise kƶnnen Silikate, Aluminiumsilikate (insbesondere Zeolithe), Salze organischer Di- und PolycarbonsƤuren, Phosphonate oder lonentauscher als Komplexbildner eingesetzt werden. Vorzugsweise ist der Komplexbildner wasserlƶslich. The cleaning agent according to the invention furthermore 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 fulfilled by phosphates. Since phosphates contribute to the deoxidation of waters, they are replaced by complexing agents. Suitable complexing agents are known to the person skilled in the art. For example, silicates, aluminum silicates (in particular zeolites), salts of organic di- and polycarboxylic acids, phosphonates or ion exchangers can be used as complexing agents. Preferably, the complexing agent is water-soluble.
Organische Komplexbildner, welche in dem erfindungsgemƤƟen Reinigungsmittel vorhanden sein kƶnnen, sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren PolycarbonsƤuren, wobei unter PolycarbonsƤuren solche CarbonsƤuren verstanden werden, die mehr als eine SƤurefunktion tragen. Beispielsweise sind dies CitronensƤure, AdipinsƤure, BernsteinsƤure, GlutarsƤure, ƄpfelsƤure, WeinsƤure, MaleinsƤure, FumarsƤure, ZuckersƤuren, AminocarbonsƤuren, NitrilotriessigsƤure (NTA), MethylglycindiessigsƤure (MGDA) und deren Abkƶmmlinge sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der PolycarbonsƤuren wie CitronensƤure, AdipinsƤure, BernsteinsƤure, GlutarsƤure, WeinsƤure, ZuckersƤuren und Mischungen aus diesen. Besonders bevorzugte erfindungsgemƤƟe Reinigungsmittel, insbesondere maschinelle GeschirrspĆ¼lmittel enthalten als eines ihrer wesentlichen Komplexbildner ein oder mehrere Salze der CitronensƤure, also Citrate. Organic complexing agents which may 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 meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. Particularly preferred cleaning agents according to the invention, in particular automatic dishwashing agents, contain as one of their essential complexing agents one or more salts of citric acid, ie citrates.
Citrate kƶnnen in Kombination mit Carbonaten und/oder Hydroxycarbonaten eingesetzt werden. Besonders bevorzugte Reinigungsmittel sind dadurch gekennzeichnet, dass das GeschirrspĆ¼lmittel neben Citrat mindestens einen weiteren phosphorfreien Komplexbildner enthƤlt, wobei der weitere phosphorfreie Komplexbildner vorzugsweise ausgewƤhlt ist aus MethylglycindiessigsƤure (MGDA), GlutaminsƤurediacetat (GLDA), AsparaginsƤurediacetat (ASDA), Hydroxyethyliminodiacetat (HEIDA), Iminodisuccinat (IDS) und Ethylendiamindisuccinat (EDDS), besonders bevorzugt aus MGDA und GLDA, wobei der Gewichtsanteil der Komplexbildner, bezogen auf das Gesamtgewicht des Reinigungsmittels, bevorzugt 5 bis 80 Gew.-%, vorzugsweise 15 bis 75 Gew.-% und insbesondere 30 bis 70 Gew.-% betrƤgt. Die Kombination von mindestens drei GerĆ¼ststoffen aus der oben genannten Gruppe hat sich fĆ¼r die Reinigungs- und KlarspĆ¼lleistung erfindungsgemƤƟer Reinigungsmittel, insbesondere maschineller GeschirrspĆ¼lmittel als vorteilhaft erwiesen. Citrates can be used in combination with carbonates and / or hydroxycarbonates. Particularly preferred cleaning agents are characterized in that the dishwashing detergent contains, in addition to citrate, at least one further phosphorus-free complexing agent, wherein the further phosphorus-free complexing agent is preferably selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic diacetic acid (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate ( IDS) and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA and GLDA, wherein the weight fraction of the complexing agent, based on the total weight of the cleaning agent, preferably 5 to 80 wt .-%, preferably 15 to 75 wt .-% and in particular 30 to 70 Wt .-% is. The combination of at least three builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular automatic dishwashing detergents.
ErfindungsgemƤƟe Mittel kƶnnen weiterhin Phosphonat(e) als Komplexbildner enthalten. ErfindungsgemƤƟ einsetzbare Phosphonate sind vorzugsweise ausgewƤhlt aus AminotrimethylenphosphonsƤure (ATMP); Ethylendiamintetra(methylenphosphonsƤure) (EDTMP); Diethylentriaminpen-ta(methylenphosphonsƤure) (DTPMP); 1 -Hydroxyethan-1 , 1 - diphosphonsƤure (HEDP); 2-Phosphonobutan-1 ,2,4-tricarbonsƤure (PBTC); Hexamethylendiamintetra(methylenphosphonsƤure) (HDTMP) undCompositions according to the invention can furthermore contain phosphonate (s) as complexing agent. Phosphonates which can be used according to the invention are preferably selected from aminotrimethylenephosphonic acid (ATMP); Ethylenediaminetetra (methylenephosphonic acid) (EDTMP); Diethylene triamine penta (methylenephosphonic acid) (DTPMP); 1-hydroxyethane-1, 1-diphosphonic acid (HEDP); 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC); Hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and
Nitrilotri(methylenphosphonsƤure) (NTMP), wobei mit besonderem Vorzug 1 -Hydroxyethan- 1 , 1 -diphosphonsƤure (HEDP) und Diethylentriaminpenta(methylenphosphonsƤure) (DTPMP) eingesetzt werden. Phosphonat(e) werden in erfindungsgemƤƟen Mitteln vorzugsweise in Mengen von 0,5 bis 20 Gew.-%, insbesondere von 0,5 bis 10 Gew.-% und vor allem von 0,5 bis 8 Gew.-% eingesetzt. Nitrilotri (methylenephosphonic acid) (NTMP), with particular preference to use 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Phosphonate (s) are preferably used in inventive compositions in amounts of 0.5 to 20 wt .-%, in particular from 0.5 to 10 wt .-% and especially from 0.5 to 8 wt .-%.
Insbesondere ist der Komplexbildner ausgewƤhlt aus der Gruppe, die CitronensƤure und deren Salze, MethylglycidinessigsƤure (MGDA), 1-Hydroxyethan-(1 , 1-diphosphonsƤure) (HEDP) sowie deren Mischungen umfasst. Diese Komplexbildner sind besonders bevorzugt wenn es sich bei einem Reinigungsmittel um ein solches handelt, welches frei von Phosphaten ist. Ein solches Reinigungsmittel ist erfindungsgemƤƟ bevorzugt. Diese Komplexbildner sind in der Lage, das in phosphatfreien Reinigungsmitteln fehlende Phosphat in seiner Wirkung zu ersetzen und somit zu einer guten Reinigungsleistung beizutragen. Die durch die Komplexbildner verursachte Glaskorrosion kann durch das erfindungsgemƤƟ beigefĆ¼gt PDADMAC deutlich verringert oder sogar vermieden werden. In particular, the complexing agent is selected from the group comprising citric acid and its salts, methyl glycidylacetic acid (MGDA), 1-hydroxyethane- (1, 1-diphosphonic acid) (HEDP) and mixtures thereof. These complexing agents are particularly preferred when a cleaning agent is one which is free of 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 detergents in its effect 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 present invention attached PDADMAC.
ErfindungsgemƤƟ umfasst das Reinigungsmittel vorzugsweise weiterhin einen oder mehrere Korrosionsinhibitoren. Korrosionsinhibitoren dienen dem Schutze des SpĆ¼lgutes oder der Maschine, wobei im Bereich des maschinellen GeschirrspĆ¼lens besonders Silberschutzmittel eine besondere Bedeutung haben. Einsetzbar sind die bekannten Substanzen des Standes der Technik. Allgemein kƶnnen vor allem Silberschutzmittel ausgewƤhlt aus der Gruppe der Triazole, der Benzotriazole, der Bisbenzotriazole, der Aminotriazole, der Alkylaminotriazole und der Ɯbergangsmetallsalze oder -komplexe eingesetzt werden. Besonders bevorzugt zu verwenden sind Benzotriazol und/oder Alkylaminotriazol. Als Beispiele der erfindungsgemƤƟ bevorzugt einzusetzenden 3-Amino-5-alkyl-1 ,2,4-triazole kƶnnen genannt werden: Propyl-, -Butyl-, -Pentyl-, - Heptyl-, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-sƤu-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-triazol. In GeschirrspĆ¼lmitteln werden die Alkyl-amino-1 ,2,4-triazole beziehungsweise ihre physiologisch vertrƤglichen Salze in einer Konzentration von 0,001 bis 10 Gew.%, vorzugsweise 0,0025 bis 2 Gew.%, besonders bevorzugt 0,01 bis 0,04 Gew.-% eingesetzt. Bevorzugte SƤuren fĆ¼r die Salzbildung sind SalzsƤure, SchwefelsƤure, PhosphorsƤure, KohlensƤure, schweflige SƤure, organische CarbonsƤuren wie Essig-, Glykol-, Citronen-, BernsteinsƤure. Ganz besonders wirksam sind 5-Pentyl-, 5-Heptyl-, 5- Nonyl-, 5-Undecyl-, 5-lsononyl-, 5-Versatic-10-sƤurealky1-3-amino-1 ,2,4-triazole sowie Mischungen dieser Substanzen. Man findet in Reinigerformulierungen darĆ¼ber hinaus hƤufig aktivchlorhaltige Mittel, die das Korrodieren der SilberoberflƤche deutlich vermindern kƶnnen. In chlorfreien Reinigern werden besonders Sauerstoff- und Stickstoffhaltige organische redoxaktive Verbindungen, wie zwei- und dreiwertige Phenole, beispielsweise Hydrochinon, Brenzkatechin, Hydroxyhydrochinon, GallussƤure, Phloroglucin, Pyrogallol beziehungsweise Derivate dieser Verbindungsklassen eingesetzt. Auch satz- und komplexartige anorganische Verbindungen, wie Salze der Metalle Mn, Ti, Zr, Hf, V, Co und Ce finden hƤufig Verwendung. Bevorzugt sind hierbei die Ɯbergangsmetallsalze, die ausgewƤhlt sind aus der Gruppe der Mangan- und/oder Cobaltsalze und/oder -komplexe, besonders bevorzugt der Cobalt(amin)-Komplexe, der Cobalt(acetat)- Komplexe, der Cobalt-(Carbonyl)-Komplexe, der Chloride des Cobalts oder Mangans und des Mangansulfats. Ebenfalls kƶnnen Zinkverbindungen zur Verhinderung der Korrosion am SpĆ¼lgut eingesetzt werden. According to the invention, the cleaning agent preferably further comprises one or more corrosion inhibitors. Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. Examples of the 3-amino-5-alkyl-1, 2,4-triazoles preferably used according to the invention may be: propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl -, undecyl, - dodecyl, - isononyl, - versatic-10-sƤu-realkyl, - phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - (4-methoxyphenyl) -, - (2-, 3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-fury1) -, - (5-oxo-2-pyrrolidinyl) -1, 3-amino-1, 2,4-triazole. In dishwashing agents, the alkylamino-1, 2,4-triazoles or their physiologically tolerable salts in a concentration of 0.001 to 10 wt.%, Preferably 0.0025 to 2 wt.%, Particularly preferably 0.01 to 0.04 % By weight used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-acid alkyl 1-3-amino-1, 2,4-triazoles and mixtures of these substances. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds are used. Also, compound and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.
Anstelle von oder zusƤtzlich zu den vorstehend beschriebenen Silberschutzmitteln, beispielsweise den Benzotriazolen, kƶnnen redoxaktive Substanzen eingesetzt werden. Diese Substanzen sind vorzugsweise anorganische redoxaktive Substanzen aus der Gruppe der Mangan-, Titian-, Zirkonium-, Hafnium-, Vanadium-, Cobalt- und Cer-Salze und/oder -Komplexe, wobei die Metalle vorzugsweise in einer der Oxidationsstufen II, 1 1 1 , IV, V oder VI vorliegen. Instead of or in addition to the silver protectants described above, for example the benzotriazoles, 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, wherein the metals preferably in one of the oxidation states II, 1 1 1, IV, V or VI.
Die verwendeten Metallsalze beziehungsweise Metallkomplexe sollen zumindest teilweise in Wasser lƶslich sein. Die zur Salzbildung geeigneten Gegenionen umfassen alle Ć¼blichen ein-, zwei-, oder dreifach negativ geladenen anorganischen Anionen, beispielsweise Oxid, Sulfat, Nitrat, Fluorid, aber auch organische Anionen wie beispielsweise Stearat. Metallkomplexe im Sinne der Erfindung sind Verbindungen, die aus einem Zentralatom und einem oder mehreren Liganden sowie gegebenenfalls zusƤtzlich einem oder mehreren der o.g. Anionen bestehen. Das Zentralatom ist eines der o.g. Metalle in einer der o.g. Oxidationsstufen. Die Liganden sind neutrale MolekĆ¼le oder Anionen, die ein-oder mehrzƤhnig sind; der Begriff "Liganden" im Sinne der Erfindung ist beispielsweise in "Rƶmpp Chemie Lexikon, Georg Thieme Verlag Stuttgart/New York, 9. Auflage, 1990, Seite 2507" nƤher erlƤutert. ErgƤnzen sich in einem Metallkomplex die Ladung des Zentralatoms und die Ladung des/der Liganden nicht auf Null, so sorgt, je nachdem, ob ein kationischer oder ein anionischer LadungsĆ¼berschuss vorliegt, entweder eines oder mehrere der o.g. Anionen oder ein oder mehrere Kationen, beispielsweise Natrium-, Kalium-, Ammoniumionen, fĆ¼r den Ladungsausgleich. Geeignete Komplexbildner sind beispielsweise Citrat, Acetylacetonat oder 1 -Hydroxyethan-1 ,1-diphosphonat. The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as, for example, stearate. Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the above-mentioned. Anions exist. The central atom is one of the o.g. 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 explained in more detail, for example, in "Rƶmpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507". If, in a metal complex, the charge of the central atom and the charge of the ligand (s) do not complete to zero, then, depending on whether there is a cationic or an anionic charge surplus, either one or more of the above mentioned obeys. Anions or one or more cations, such as sodium, potassium, ammonium ions, for the charge balance. Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.
Die in der Chemie gelƤufige Definition fĆ¼r "Oxidationsstufe" ist beispielsweise in "Rƶmpp Chemie Lexikon, Georg Thieme Verlag Stuttgart/New York, 9. Auflage, 1991 , Seite 3168" wiedergegeben. Besonders bevorzugte Metallsalze und/oder Metallkomplexe sind ausgewƤhlt aus der Gruppe MnSC , Mn (ll)-citrat, Mn(1 1 )-stearat, Mn(ll)-acetylacetonat, Mn(1 1 )[1 -Hydroxyethan-1 ,1- diphosphonat], V2O5, V2O4, V02, TiOSC , K2TiF6, K2ZrF6, C0SO4, Co(N03)2, Ce(N03)3, sowie deren Gemische, so dass die Metallsalze und/oder Metallkomplexe ausgewƤhlt aus der Gruppe MnSCU Mn(ll)-citrat, Mn(ll)-stearat, Mn(ll)-acetylacetonat, Mn(1 1 )41-Hydroxyethan-1 ,1-di-phosphonat], V2O5, V2O4, VO2, T1OSO4, K2TiF6, K2ZrF6, C0SO4. Co(N03)2, Ce(N03)3 mit besonderem Vorzug eingesetzt werden. The definition of "oxidation state" which is common in chemistry is reproduced, for example, in "Rƶmpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168". Particularly preferred metal salts and / or metal complexes are selected from the group MnSC, Mn (II) citrate, Mn (1 1) stearate, Mn (II) acetylacetonate, Mn (1 1) [1-hydroxyethane-1, 1- diphosphonate], V2O5, V2O4, V0 2 , TiOSC, K 2 TiF 6 , K 2 ZrF 6 , C0SO 4, Co (NO 3 ) 2, Ce (NO 3 ) 3, and mixtures thereof, such that the metal salts and / or metal complexes selected from the group MnSCU Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (1 1) 41-hydroxyethane-1, 1-di-phosphonate], V2O5, V2O4, VO2, T1OSO4, K 2 TiF 6, K 2 ZrF 6, C0SO4. Co (NO 3 ) 2, Ce (NO 3 ) 3 can be used with particular preference.
Bei diesen Metallsalzen beziehungsweise Metallkomplexen handelt es sich im Allgemeinen um handelsĆ¼bliche Substanzen, die zum Zwecke des Silberkorrosions-Schutzes ohne vorherige Reinigung in den Wasch- oder Reinigungsmitteln eingesetzt werden kƶnnen. So ist beispielsweise das aus der SCh-Herstellung (Kontaktverfahren) bekannte Gemisch aus fĆ¼nf- und vierwertigem Vanadium (V2O5, VO2, V2O4) geeignet, ebenso wie das durch VerdĆ¼nnen einer Ti(S04)2-Lƶsung entstehende Titanylsulfat, TiOSC . These metal salts or metal complexes are generally commercially available substances which can be used for the purpose of silver corrosion protection without prior purification in detergents or cleaners. For example, the mixture of pentavalent and tetravalent vanadium (V2O5, VO2, V2O4) known from SCh production (contact method) is suitable, as well as the titanyl sulfate, TiOSC, formed by diluting a Ti (SO4) 2 solution.
Die anorganischen redoxaktiven Substanzen, insbesondere Metallsalze beziehungsweise Metallkomplexe sind vorzugsweise gecoatet, dass heiƟt vollstƤndig mit einem wasserdichten, bei den Reinigungstemperaturen aber leichtlƶslichen Material Ć¼berzogen, um ihre vorzeitige Zersetzung oder Oxidation bei der Lagerung zu verhindern. Bevorzugte Coatingmaterialien, die nach bekannten Verfahren, etwa Schmelzcoatingverfahren nach Sandwik aus der Lebensmittelindustrie, aufgebracht werden, sind Paraffine, Mikrowachse, Wachse natĆ¼rlichen Ursprungs wie Carnaubawachs, Candellilawachs, Bienenwachs, hƶherschmelzende Alkohole wie beispielsweise Hexadecanol, Seifen oder FettsƤuren. Dabei wird das bei Raumtemperatur feste Coatingmaterial in geschmolzenem Zustand auf das zu coatende Material aufgebracht, beispielsweise indem feinteiliges zu coatendes Material in kontinuierlichem Strom durch eine ebenfalls kontinuierlich erzeugte SprĆ¼hnebelzone des geschmolzenen Coatingmaterials geschleudert wird. Der Schmelzpunkt muss so gewƤhlt sein, dass sich das Coatingmaterial wƤhrend der Silberbehandlung leicht lƶst beziehungsweise schnell aufschmilzt. Der Schmelzpunkt sollte idealerweise im Bereich zwischen 45Ā°C und 65Ā°C und bevorzugt im Bereich 50Ā°C bis 60Ā°C liegen. The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, that is to say completely coated with a water-tight material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids. In this case, the coating material which is solid at room temperature is applied in the molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a likewise continuously produced spray zone of the molten coating material. The melting point must be selected so that the coating material dissolves easily during the silver treatment or melts quickly. The melting point should ideally be in the range between 45 Ā° C and 65 Ā° C and preferably in the range 50 Ā° C to 60 Ā° C.
Vorzugsweise sind in der vorliegenden Erfindung Korrosionsinhibitoren in einem Anteil von 0,05 bis 1 Gew.-%, insbesondere von 0, 1 bis 0,3 Gew.-% enthalten. Vorzugsweise handelt es sich bei dem Korrosionsinhibitor um Zinkacetat. In the present invention, corrosion inhibitors are preferably contained in an amount of 0.05 to 1% by weight, in particular of 0.1 to 0.3% by weight. Preferably, the corrosion inhibitor is zinc acetate.
Neben den bisher genannten Komponenten kƶnnen die erfindungsgemƤƟen Mittel weitere Inhaltsstoffe enthalten. Hierzu zƤhlen beispielsweise weitere Tenside, Additive zur Verbesserung des Ablauf- und Trocknungsverhaltens, zur Einstellung der ViskositƤt, zur Stabilisierung sowie weitere in HandgeschirrspĆ¼lmitteln Ć¼bliche Hilfs- und Zusatzstoffe, etwa UV-Stabilisatoren, ParfĆ¼m, Perlglanzmittel, Farbstoffe, Korrosionsinhibitoren, Konservierungsmittel, organische Salze, Desinfektionsmittel, Enzyme, pH-Stellmittel sowie HautgefĆ¼hl-verbessernde oder pflegende Additive. In addition to the components mentioned so far, the compositions according to the invention may contain further ingredients. These include, for example, other surfactants, additives for improving the drainage and drying behavior, for adjusting the viscosity, for stabilization and other auxiliary substances and additives customary in hand dishwashing detergents, for example UV stabilizers, perfume, Pearlescing agents, dyes, corrosion inhibitors, preservatives, organic salts, disinfectants, enzymes, pH adjusters, and skin feel enhancing or conditioning additives.
Als Additive geeignete Polymere sind insbesondere MaleinsƤure-AcrylsƤure-Copolymer-Na-Salz (beispielsweise SokalanĀ® CP 5 der Firma BASF, Ludwigshafen (Deutschland)), modifiziertes PolyacrylsƤure-Na-Salz (beispielsweise SokalanĀ® CP 10 der Firma BASF, Ludwigshafen (Deutschland)), modifiziertes Polycarboxylat-Na-Salz (beispielsweise SokalanĀ® HP 25 der Firma BASF, Ludwigshafen (Deutschland)), Polyalkylenoxid, modifiziertes Heptamethyltrisiloxan (beispielsweise SilwetĀ® L-77 der Firma BASF, Ludwigshafen (Deutschland)), Polyalkylenoxid, modifiziertes Heptamethyltrisiloxan (beispielsweise SilwetĀ® L-7608 der Firma BASF, Ludwigshafen (Deutschland)) sowie Polyethersiloxane (Copolymere von Polymethylsiloxanen mit Ethylenoxid- /Propylenoxidsegmenten (Polyetherblƶcken)), vorzugsweise wasserlƶsliche lineare Polyethersiloxane mit terminalen Polyetherblƶcken wie TegoprenĀ® 5840, TegoprenĀ® 5843, TegoprenĀ® 5847, TegoprenĀ® 5851 , TegoprenĀ® 5863 oder TegoprenĀ® 5878 der Firma Evonik, Essen (Deutschland). Als Additive geeignete Buildersubstanzen sind insbesondere PolyasparaginsƤure- Na-Salz, Ethylendiamintriacetatkokosalkylacetamid (beispielsweise RewopolĀ® CHT 12 der Firma Evonik, Essen (Deutschland)), MethylglycindiessigsƤure-Tri-Na-Salz und AcetophosphonsƤure. Mischungen mit tensidischen oder polymeren Additiven zeigen im Falle von TegoprenĀ® 5843 und TegoprenĀ® 5863 Synergismen. Der Einsatz der Tegopren-Typen 5843 und 5863 ist jedoch bei der Anwendung auf harte OberflƤchen aus Glas, insbesondere Glasgeschirr, weniger bevorzugt, da diese Silikontenside auf Glas aufziehen kƶnnen. In einer besonderen AusfĆ¼hrungsform der Erfindung wird auf die genannten Additive verzichtet. Polymers suitable as additives maleic acid-acrylic acid copolymer Na salt are, in particular (for example Sokalan Ā® CP 5 from the company BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na-salt (for example Sokalan Ā® CP 10 from BASF, Ludwigshafen (Germany )), modified polycarboxylate-Na-salt (for example Sokalan Ā® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide-modified heptamethyltrisiloxane (such as Silwet Ā® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide-modified heptamethyltrisiloxane (For example, Silwet Ā® L-7608 BASF, Ludwigshafen (Germany)) and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide / propylene oxide (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren Ā® 5840, Tegopren Ā® 5843, Tegopren Ā® 5847, TegoprenĀ® Ā® 5851, TegoprenĀ® Ā® 5863 or TegoprenĀ® Ā® 5878 the company Evon ik, Essen (Germany). As additives suitable builders are especially polyaspartic acid Na salt, Ethylendiamintriacetatkokosalkylacetamid (eg RewopolĀ® Ā® CHT 12 from Evonik, Essen (Germany)), methylglycine-trisodium salt and acetophosphonic. Blends with surfactant or polymeric additives exhibit synergism 5863 in the case of Tegopren 5843 and Tegopren Ā® Ā®. However, the use of Tegopren grades 5843 and 5863 is less preferred when applied to hard surfaces of glass, especially glassware, since these can apply silicone surfactants to glass. In a particular embodiment of the invention, the additives mentioned are dispensed with.
Ein bevorzugtes Reinigungsmittel, insbesondere GeschirrspĆ¼lmittel, umfasst weiterhin ein Bleichmittel, insbesondere ein Sauerstoffbleichmittel sowie gegebenenfalls einen Bleichaktivator und/oder Bleichkatalysator. Als bevorzugtes Belichmittel enthalten erfindungsgemƤƟe Reinigungsmittel ein Sauerstoffbleichmittel aus der Gruppe Natriumpercarbonat, Natriumperborattetrahydrat und Natriumperboratmonohydrat. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder PersƤuren, wie Perbenzoate, Peroxophthalate, DiperazelainsƤure, PhthaloiminopersƤure oder DiperdodecandisƤure. Weiterhin kƶnnen auch Bleichmittel aus der Gruppe der organischen Bleichmittel eingesetzt werden. Typische organische Bleichmittel sind die Diacylperoxide, wie zum Beispiel Dibenzoylperoxid . Weitere typische organische Bleichmittel sind die PeroxysƤuren, wobei als Beispiele besonders die AlkylperoxysƤuren und die ArylperoxysƤuren genannt werden. Wegen seiner guten Bleichleistung wird das Natriumpercarbonat besonders bevorzugt. Ein besonders bevorzugtes Sauerstoffbleichmittel ist Natriumpercarbonat. Als Bleichaktivatoren kƶnnen Verbindungen, die unter Perhydrolysebedingungen aliphatische PeroxocarbonsƤuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte PerbenzoesƤure ergeben, eingesetzt werden. Geeignet sind Substanzen, die 0- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt werden mehrfach acylierte Alkylendiamine, wobei sich Tetraacetylethylendiamin (TAED) als besonders geeignet erwiesen hat. A preferred cleaning agent, in particular dishwashing agent, further comprises a bleaching agent, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst. Preferred cleaning agents according to the invention include an oxygen bleaching agent from the group of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Because of its good bleaching performance, sodium percarbonate is particularly preferred. A particularly preferred oxygen bleach is sodium percarbonate. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
Bei den Bleichkatalysatoren handelt es sich um bleichverstƤrkende Ɯbergangsmetallsalze beziehungsweise Ɯbergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo- Salenkomplexe oder - carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu- Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe- Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar. Mit besonderem Vorzug werden Komplexe des Mangans in der Oxidationsstufe I I, II I, IV oder IV eingesetzt, die vorzugsweise einen oder mehrere makrocyclische(n) Ligand(en) mit den Donorfunktionen N, NR, PR, O und/oder S enthalten. Vorzugsweise werden Liganden eingesetzt, die Stickstoff-Donorfunktionen aufweisen. Dabei ist es besonders bevorzugt, Bleichkatalysator(en) in den erfindungsgemƤƟen Mitteln einzusetzen, welche als makromolekularen Liganden 1 ,4,7-Trimethyl-1 ,4,7-triazacyclononan (Me-TACN), 1 ,4,7-Triazacyclononan (TACN), 1 ,5,9-Trimethyl-1 ,5,9-triazacyclododecan (Me- TACD), 2-Methyl-1 -1 , 4, 7-trimethyl-1 ,4,7-triazacyclononan (Me/Me-TACN) und/oder 2-Methyl- 1 ,4,7-triazacyclononan (Me/TACN) enthalten. Geeignete Mangankomplexe sind beispielsweise [ĪœĪ·Ī™ Īœ2(Ī¼-0)Ī¹(Ī¼-ĪŸĪ‘Ļ‹)2(Ī¤Ī‘Ī°Ī)2](Ī°Ī™Īø4)2, [MnmMnlv(Ī¼-0)2(Ī¼-OAc)1(TACN)2](BPh4)2, [ĪœĪ·'Ī½ 4(Ī¼- 0)6(TACN)4](CI04)4, [ĪœĪ·Īœ Ī™2(Ī¼-0)Ī¹(Ī¼-ĪŸĪ‘Ļ‹)2(ĪœĪ²-Ī¤Ī‘Ī°Ī)2](Ī° Ī™Īø4)2, [ĪœĪ·Īœ'ĪœĪ·'Ī½(Ī¼-0)Ī¹(Ī¼-ĪŸĪ‘ (ĪœĪ²- The bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt 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 ammine complexes can also be used as bleach catalysts. It is particularly preferred to use complexes of manganese in the oxidation state II, II I, IV or IV, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (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). Suitable manganese complexes are, for example, [ĪœĪ· Ī™ Īœ 2 (Ī¼-0) Ī¹ (Ī¼-ĪŸĪ‘Ļ‹) 2 (Ī¤Ī‘Ī°Ī) 2 ] (Ī°Ī™Īø4) 2, [Mn m Mn lv (Ī¼-0) 2 (Ī¼-OAc) 1 (TACN ) 2] (BPh4) 2, [ĪœĪ· ' Ī½ 4 (Ī¼- 0) 6 (TACN) 4 ] (CI0 4 ) 4, [ĪœĪ· Īœ Ī™ 2 (Ī¼-0) Ī¹ (Ī¼-ĪŸĪ‘Ļ‹) 2 (ĪœĪ²- Ī¤Ī‘Ī°Ī) 2 ] (Ī° Ī™Īø4) 2, [ĪœĪ· Īœ 'ĪœĪ·' Ī½ (Ī¼-0) Ī¹ (Ī¼-ĪŸĪ‘ (ĪœĪ²-
OAc = OC(0)CH3). OAc = OC (0) CH3).
Daneben kƶnnen noch ein oder mehrere weitere Ć¼bliche Hilfs- und Zusatzstoffe, insbesondere UV- Stabilisatoren, ParfĆ¼m, Perlglanzmittel (INCI Opacifying Agents; beispielsweise Glykoldistearat, beispielsweise CutinaĀ® AGS der Fa. Cognis, beziehungsweise dieses enthaltende Mischungen, beispielsweise die EuperlaneĀ® der Fa. Cognis), Farbstoffe, Korrosionsinhibitoren, Konservierungsmittel (beispielsweise das technische auch als Bronopol bezeichnete 2-Brom-2- nitropropan-1 ,3-diol (CAS 52-51-7), das beispielsweise als MyacideĀ® BT oder als Boots Bronopol BT von der Firma Boots gewerblich erhƤltlich ist), Desinfektionsmittel, pH-Stellmittel sowie HautgefĆ¼hl- verbessernde oder pflegende Additive (beispielsweise dermatologisch wirksame Substanzen wie Vitamin A, Vitamin B2, Vitamin B12, Vitamin C, Vitamin E, D-Panthenol, Sericerin, Collagen-Partial- Hydrolysat, verschiedene pflanzliche Protein-Partial-Hydrolysate, Proteinhydrolysat-FettsƤure- Kondensate, Liposome, Cholesterin, pflanzliche und tierische Ɩle wie beispielsweise Lecithin, Sojaƶl, usw., Pflanzenextrakte wie beispielsweise Aloe Vera, Azulen, Hamamelisextrakte, Algenextrakte, usw., Allantoin, A.H.A.-Komplexe), in Mengen von Ć¼blicherweise nicht mehr als 5 Gew.-% enthalten sein. In addition, possible to use one or more further customary auxiliaries and additives, in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina Ā® AGS from Cognis, or mixtures comprising, for example, the Euperlane Ā® from.. Cognis), dyes, corrosion inhibitors, preservatives (for example, the technical referred to as Bronopol 2-bromo-2-nitropropane-1, 3-diol (CAS 52-51-7), for example, as Myacide Ā® BT or Boots Bronopol BT of the company Boots is commercially available), disinfectants, pH adjusters and skin feel-improving or nourishing additives (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 hydrolysates, protein hydrolyzate fatty acid condensates, liposomes, cholesterol, vegetable and animal oils such as lecithin, soya oil, etc., plant extracts such as aloe vera, azulene, witch hazel extracts, Algae extracts, etc., allantoin, AHA complexes) in amounts of usually not more than 5% by weight.
Stoffe, die auch als Inhaltsstoffe von kosmetischen Mitteln dienen, werden gegebenenfalls gemƤƟ der International Nomenclature Cosmetic Ingredient (INCI) Nomenklatur bezeichnet. Chemische Verbindungen tragen eine INCI Bezeichnung in englischer Sprache. Die INCI Bezeichnung sind dem "International Cosmetic Ingredient Dictionary and Handbook, 7th Edition (1997)" zu entnehmen, das von The Cosmetic, Toiletry and Fragrance Association (CTFA), Washington D.C. (USA) herausgegeben wird. Die Angabe CAS bedeutet, dass es sich bei der nachfolgenden Zahlenfolge um eine Bezeichnung des Chemical Abstracts Service handelt. Substances which also serve as ingredients of cosmetic products are optionally designated according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English. The INCI name can be found in the International Cosmetic Ingredient Dictionary and Handbook, 7th Edition (1997), published by The Cosmetic, Toiletry and Fragrance Association (CTFA), Washington D.C. (USA) is issued. The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.
Beim Einsatz von BenzoesƤure, SalicylsƤure oder MilchsƤure als pH-Regulatoren und/oder Puffer- Substanzen kƶnnen diese Verbindungen die antibakterielle Wirkung des Silbers und/oder der Silberverbindung unterstĆ¼tzen beziehungsweise verstƤrken. When using benzoic acid, salicylic acid or lactic acid as pH regulators and / or buffer substances, these compounds can support or enhance the antibacterial effect of the silver and / or the silver compound.
Das erfindungsgemƤƟe Reinigungsmittel wird vorzugsweise zum manuellen und/oder maschinellen Reinigen von GegenstƤnden mit GlasoberflƤchen eingesetzt. Insbesondere wird es zum maschinellen Reinigen von GegenstƤnden mit GlasoberflƤchen verwendet. GegenstƤnde mit GlasoberflƤchen im Sinne der vorliegenden Erfindung sind alle GegenstƤnde, welche eine OberflƤche aufweisen, die Glas umfasst. Dies schlieƟt solche GegenstƤnde mit ein, die vollstƤndig aus Glas bestehen. Beispielsweise handelt es sich hierbei um (Trink)GlƤser, Tƶpfe oder SchĆ¼sseln aus Glas oder dekorative GlasgegenstƤnde. Dabei kƶnnen die GlƤser eine Farbe infƤrbung aufweisen oder auf andere Art dekorativ bearbeitet sein. Die GlƤser kƶnnen jedoch auch ohne jegliche farbige Dekorationen sein. The cleaning agent according to the invention is preferably used for manual and / or mechanical cleaning of objects with glass surfaces. In particular, it is used for machine cleaning of articles with glass surfaces. Articles with glass surfaces in the sense of the present invention are all objects which have a surface comprising glass. This includes such items that are made entirely of glass. For example, these are (drinking) glasses, pots or bowls made of glass or decorative glass objects. In this case, the glasses may have a color infƤrbierung or otherwise processed decorative. However, the glasses can be without any colored decorations.
Glas im Sinne der vorliegenden Erfindung sind alle Arten von GlƤsern, wie beispielsweise Kalknatronglas, Borsilikatglas oder Bleiglas. Vorzugsweise handelt es sich bei den GlƤsern um KalknatronglƤser. Glass in the context of the present invention are all types of glasses, such as soda lime glass, borosilicate glass or lead glass. Preferably, the glasses are soda-lime glasses.
Als maschinelle GeschirrspĆ¼lmittel werden nach MaƟgabe dieser Anmeldung Zusammensetzungen bezeichnet, die zur Reinigung verschmutzten Geschirrs in einem maschinellen GeschirrspĆ¼lverfahren eingesetzt werden kƶnnen. Damit unterscheiden sich die erfindungsgemƤƟen maschinellen GeschirrspĆ¼lmittel beispielsweise von den maschinellen KlarspĆ¼lmitteln, die stets in Kombination mit maschinellen GeschirrspĆ¼lmitteln eingesetzt werden und keine eigene Reinigungswirkung entfalten. Automatic dishwashing detergents, according to this application, are compositions which can be used to clean soiled dishes in a dishwasher automatic dishwashing process. Thus, the automatic dishwasher detergents according to the invention differ, for example, from the machine rinse aid agents, which are always used in combination with automatic dishwashing detergents and do not develop their own cleaning action.
Die erfindungsgemƤƟen Reinigungsmittel, insbesondere maschinelle GeschirrspĆ¼lmittel liegen vorzugsweise in Form eines Formkƶrpers, insbesondere eines Kompaktats, vor allem einer Tablette, vor. Sie kƶnnen jedoch auch in Kombination mit anderen Angebotsformen, insbesondere in Kombination mit festen Angebotsformen wie Pulver, Granulaten oder Extrudaten oder in Kombination mit flĆ¼ssigen Angebotsformen auf Basis von Wasser und/oder organischen Lƶsungsmitteln vorliegen. Bei dem Formkƶrper kann es sich beispielsweise auch um ein Granulat handeln, das in einem Beutel oder einer GieƟform enthalten ist. The cleaning agents according to the invention, in particular automatic dishwasher detergents, are preferably in the form of a shaped body, in particular a compactate, in particular a tablet. However, they can also be used in combination with other forms of offer, in particular in combination with solid forms such as powders, granules or extrudates or in combination with liquid formulations based on water and / or organic solvents. The shaped body may, for example, also be a granulate which is contained in a bag or a casting mold.
ErfindungsgemƤƟe Mittel kƶnnen als einphasige oder mehrphasige Produkte konfektioniert werden. Bevorzugt sind insbesondere maschinelle GeschirrspĆ¼lmittel mit einer, zwei, drei oder vier Phasen. Maschinelle GeschirrspĆ¼lmittel, dadurch gekennzeichnet, dass sie in Form einer vorgefertigten Dosiereinheit mit zwei oder mehr Phasen vorliegen, sind besonders bevorzugt. Besonders bevorzugt sind insbesondere zwei- oder mehrphasige Tabletten, beispielsweise Zweischichttabletten, insbesondere Zweischichttabletten mit Mulde und einem in der Mulde befindlichen Formkƶrper. Inventive agents can be formulated as single-phase or multi-phase products. Machine 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 dosing unit with two or more phases, are particularly preferred. Two-phase or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets with a trough and a shaped body located in the trough, are particularly preferred.
ErfindungsgemƤƟe Reinigungsmittel werden vorzugsweise zu Dosiereinheiten vorkonfektioniert. Diese Dosiereinheiten umfassen vorzugsweise die fĆ¼r einen Reinigungsgang notwendige Menge an wasch- oder reinigungsaktiven Substanzen. Bevorzugte Dosiereinheiten weisen ein Gewicht zwischen 12 und 30 g, bevorzugt zwischen 14 und 26 g und insbesondere zwischen 15 und 22 g auf. Detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
Das Volumen der vorgenannten Dosiereinheiten sowie deren Raumform sind mit besonderem Vorzug so gewƤhlt, dass eine Dosierbarkeit der vorkonfektionierten Einheiten Ć¼ber die Dosierkammer einer GeschirrspĆ¼lmaschine gewƤhrleistet ist. Das Volumen der Dosiereinheit betrƤgt daher bevorzugt zwischen 10 und 35 ml, vorzugsweise zwischen 12 und 30 ml und insbesondere zwischen 15 und 25 ml. The volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured 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.
Die erfindungsgemƤƟen Reinigungsmittel, insbesondere die vorgefertigten Dosiereinheiten, weisen in einer bevorzugten AusfĆ¼hrungsform eine wasserlƶsliche UmhĆ¼llung auf. The cleaning agents according to the invention, in particular the prefabricated metering units, in a preferred embodiment have a water-soluble sheath.
In einer weiteren AusfĆ¼hrungsform wird die der vorliegenden Erfindung zugrundeliegende Aufgabe gelƶst durch ein Verfahren zum Reinigen von GegenstƤnden mit GlasoberflƤche, in welchem man ein zuvor beschriebenes Reinigungsmittel mit der GlasoberflƤche in Kontakt bringt und die OberflƤche in bekannter Weise bearbeitet wird. Insbesondere erfolgt die Reinigung mit einer Reinigungsmaschine, besonders einer GeschirrspĆ¼lmaschine. In a further embodiment, the object underlying the present invention is achieved by a method for cleaning objects with glass surface, in which bringing a previously described cleaning agent with the glass surface in contact and the surface is processed in a known manner. In particular, the cleaning is done with a cleaning machine, especially a dishwasher.
Das Kontaktbringen erfolgt Ć¼blicherweise in Anwesenheit von Wasser. Die sich aus Reinigungsmittel und Wasser bildende Waschflotte hat vorzugsweise einen pH-Wert, der im Bereich von 7,5 bis 12, insbesondere von 8 bis 1 1 , besonders bevorzugt von 9,5 bis 10,5 liegt. In diesen pH-Wert Bereichen tritt Ć¼blicherweise eine Korrosion der GlasoberflƤchen auf. Ohne an jegliche Theorie gebunden zu sein, fĆ¼hrt die alkalische Reinigungsflotte dazu, dass das Glas aufquillt. Komplexbildner, welche im Reinigungsmittel enthalten sind, kƶnnen dann die Glasstruktur angreifen. Durch PDADMAC wird dieser Angriff der Komplexbildner auf die aufgequollene Glasstruktur verhindert oder wenigstens deutlich reduziert. The contact is usually carried out in the presence of water. The washing liquor forming from cleaning agent and water preferably has a pH which is in the range from 7.5 to 12, in particular from 8 to 11, particularly preferably from 9.5 to 10.5. In these pH ranges, corrosion of the glass surfaces usually occurs. Without being bound by any theory, the alkaline cleaning liquor causes the glass swells. Complexing agents contained in the cleaning agent can then attack the glass structure. PDADMAC prevents or at least significantly reduces this attack of the complexing agents on the swollen glass structure.
Das erfindungsgemƤƟe Verfahren ist vorzugsweise ein maschinelles Reinigungsverfahren; hierzu werden die zu reinigenden GlasgegenstƤnde beziehungsweise GegenstƤnde mit einer GlasoberflƤche beispielsweise in eine handelsĆ¼blichen GeschirrspĆ¼lmaschine gegeben und bei den vorgegebenen Programmen gereinigt. Das erfindungsgemƤƟe Reinigungsmittel kann jedoch auch bei einem manuellen Reinigen von Geschirr und GegenstƤnden mit GlasoberflƤchen eingesetzt werden. Die Temperatur, bei der die Reinigung durchgefĆ¼hrt wird, liegt insbesondere im Bereich von 5 bis 90 Ā°C, besonders von 20 Ā°C bis 80 Ā°C, besonders bevorzugt von 40 Ā°C bis 60 Ā°C. Bei diesen Temperaturen kann eine gute Reinigung erfolgen. Anschmutzungen von den OberflƤchen kƶnnen gut entfernt werden. Im Sinne einer umweltfreundlichen Reinigung sind jedoch geringere Temperaturen, insbesondere solche, welche im Bereich von 40 Ā°C bis 60 Ā°C liegen, bevorzugt. The method according to the invention is preferably a machine cleaning method; For this purpose, the glass objects or objects to be cleaned are given with a glass surface, for example in a commercial dishwasher and cleaned at the given programs. However, the cleaning agent according to the invention can also be used in a manual cleaning of dishes and objects with glass surfaces. The temperature at which the purification is carried out is in particular in the range from 5 to 90 Ā° C, especially from 20 Ā° C to 80 Ā° C, particularly preferably from 40 Ā° C to 60 Ā° C. At these temperatures, a good cleaning can be done. Stains from the surfaces can be easily removed. In terms of environmentally friendly cleaning, however, lower temperatures, especially those which are in the range of 40 Ā° C to 60 Ā° C, are preferred.
Das erfindungsgemƤƟe Reinigungsmittel ermƶglicht durch die Kombination von Komplexbildnern, wie insbesondere MGDA, ZitronensƤure oder HEDP in Kombination mit einem Polymer, nƤmlich PDADMAC, Phosphate in Reinigungsmitteln zu ersetzen. Dies ermƶglicht zum einen eine umweltfreundliche Reinigung. Zum anderen kƶnnen gesetzliche Vorgaben, welche ab 2017 Phosphat-freie Reinigungsmittel fordern, hierdurch entsprochen werden. Zudem ermƶglicht PDADMAC die, insbesondere bei alkalischen pH-Werten auftretende Glaskorrosion zu verringern oder sogar im Wesentlichen zu vermeiden. The cleaning agent according to the invention makes it possible by the combination of complexing agents, in particular MGDA, citric acid or HEDP in combination with a polymer, namely PDADMAC, to replace phosphates in cleaning agents. This allows for an environmentally friendly cleaning. On the other hand, legal requirements, which demand phosphate-free cleaning agents from 2017, can be met in this way. In addition, PDADMAC makes it possible to reduce or even substantially avoid glass corrosion, especially at alkaline pH values.
In einer weiteren AusfĆ¼hrungsfĆ¼hrungsform wird die der vorliegenden Erfindung zugrundeliegende Aufgabe daher gelƶst durch die Verwendung von PDADMAC in einem Reinigungsmittel, insbesondere in einem Phosphat-freien Reinigungsmittel, besonders zur maschinellen Reinigung von GegenstƤnden mit GlasoberflƤche, zur Verringerung der Glaskorrosion, insbesondere bei alkalischen pH-Werten. In a further embodiment, the object underlying the present invention is therefore achieved by the use of PDADMAC in a cleaning agent, in particular in a phosphate-free cleaning agent, especially for machine cleaning of objects with a glass surface, to reduce glass corrosion, especially at alkaline pH values ,
AusfĆ¼hrungsbeispiel: Embodiment:
Es wurde ein Phosphat-freies Reinigungsmittel der folgenden Zusammensetzung hergestellt: A phosphate-free detergent of the following composition was prepared:
HEDP: 1 -Hydroxyethan-1 , 1 -diphosphonsƤure Ā HEDP: 1-Hydroxyethane-1, 1-diphosphonic acid
MGDA: MethylglycindiessigsƤure MGDA: methylglycinediacetic acid
TAED: Tetraacetylethylendiamin TAED: tetraacetylethylenediamine
PVP: Polyvinylpyrrolidon PVP: polyvinylpyrrolidone
Bei diesem Reinigungsmittel handelte es sich um ein Phosphat-freies Reinigungsmittel fĆ¼r die maschinelle Reinigung von Geschirr. Angegeben sind sowohl die Gew.-% als auch die aktive Menge in g/job (g pro Reinigungsdurchgang). Hergestellt wurde ein festes Reinigungsmittel, welches in Form einer Tabelle mit einem Gewicht von 17 g bis 20 g, insbesondere von 17g, vorlag. This detergent was a phosphate-free detergent for machine dishwashing. Indicated are both the weight% and the active amount in g / job (g per cleaning cycle). A solid detergent was prepared which was in the form of a table weighing 17 g to 20 g, especially 17 g.
Das Reinigungsmittel wurde mit einer Konzentration von 6 g/l in Leitungswasser gelƶst. ZusƤtzlich wurden 0,6 g/l PDADMAC beziehungsweise 0,06 g/l PDADMAC zugegeben. Das PDADMAC wurde von Sigma Aldrich als wƤssrige Lƶsung (20 Gew.-%) erhalten (MW = 400.000 bis 500.000). Ein Anteil von 0,6 g/l entsprach 10 Gew.-% des GeschirrspĆ¼lmittels. Die Zugabe von 0,6 g/l PDADMAC entsprach 1 Gew.-% des GeschirrspĆ¼lmittels. The detergent was dissolved in tap water at a concentration of 6 g / l. In addition, 0.6 g / L of PDADMAC or 0.06 g / L of PDADMAC was added. The PDADMAC was obtained from Sigma Aldrich as an aqueous solution (20% by weight) (MW = 400,000 to 500,000). A proportion of 0.6 g / l corresponded to 10 wt .-% of the dishwashing detergent. The addition of 0.6 g / l PDADMAC corresponded to 1% by weight of the dishwashing detergent.
Zur Bestimmung, inwiefern eine Glaskorrosion erfolgt, wurde eine Quarz-Crystal-Mikrowaage (QCM) benutzt. Das Messprinzip einer QCM funktioniert mittels der Bestimmung der Schwingungsfrequenz eines Quarzkristalls. Sobald eine Substanz an diesem Quarzkristall, der den Sensor darstellt, adsorbiert beziehungsweise vom Sensor desorbiert, verursacht dies eine Ƅnderung in der Resonanzfrequenz. Diese FrequenzƤnderung kann detektiert und in eine MasseƤnderung umgerechnet werden. To determine the extent of glass corrosion, a quartz crystal microbalance (QCM) was used. The measuring principle of a QCM works by means of the determination of the oscillation frequency of a quartz crystal. As soon as a substance adsorbs or desorbs from the sensor on this quartz crystal, which represents the sensor, this causes a change in the resonance frequency. This frequency change can be detected and converted into a mass change.
HƤufig beschrieben ist die MasseƤnderung durch Anlagerung von Materialien auf der OberflƤche des Quarzkristalls. Bekannt ist jedoch auch der Einsatz von QCM zum Nachweis der EffektivitƤt von Tensiden zur Entfernung von Anschmutzungen auf OberflƤchen. Unterschiedliche Anwendungsmƶglichkeiten sind detailliert auf der Homepage der Firma Biolin Scientific (Stockholm, Schweden) (http://www.biolinscientific.com/q-sense/applications) ausgefĆ¼hrt. Mittels QCM kƶnnen somit auch SpĆ¼lzyklen in einer SpĆ¼lmaschine simuliert werden. Dies hat gegenĆ¼ber der DurchfĆ¼hrung in einer SpĆ¼lmaschine den Vorteil, dass innerhalb kurzer Zeit mehrere Zyklen simuliert werden kƶnnen, so dass bereits nach kurzer Zeit belastbare Ergebnisse erhalten werden kƶnnen. Frequently described is the mass change due to deposition of materials on the surface of the quartz crystal. However, the use of QCM to demonstrate the effectiveness of surfactants to remove stains on surfaces is also known. Different applications are detailed on the homepage of Biolin Scientific (Stockholm, Sweden) (http://www.biolinscientific.com/q-sense/applications). It is thus also possible to simulate rinsing cycles in a dishwasher by means of QCM. This has the advantage over the implementation in a dishwasher the advantage that several cycles can be simulated within a short time, so that after a short time reliable results can be obtained.
Zur Bestimmung der AusprƤgung der Glaskorrosion wurde ein Sensorkristall verwendet, der mit einem Kalknatronglas beschichtet wurde. Dieser beschichtete Sensor wurde mit einem Phosphatfreien Reinigungsmittel, welches die oben angegebene Zusammensetzung aufwies, Ć¼berspĆ¼lt. Ebenso wurde ein Glas-beschichteter Sensor mit einem erfindungsgemƤƟen Reinigungsmittel, welches 10 Gew.-% beziehungsweise 1 Gew.-% PDADMAC umfasste, Ć¼berspĆ¼lt. Der Vorgang des Ɯberstrƶmens des Sensors erfolgte bei 60 Ā°C in einer QCM der Firma Q-Sense (Stockholm, Schweden). Durch die Reinigungsmittel wurde nach einem gewissen Zeitraum die Glasbeschichtung vom Sensor abgetragen (Masseabtrag). Dieser Masseabtrag vom Sensor entspricht der AusprƤgung der Glaskorrosion. Der Beginn des Masseabtrags, gemessen ab dem Moment der ƜberspĆ¼lung des Sensors mit dem Reinigungsmittel, sowie die Menge des Masseabtrags stellen dabei die Parameter dar, mit welchen sich die IntensitƤt der Glaskorrosion bestimmen lƤsst. Je spƤter der Masseabtrag beginnt und/oder je geringer der Masseabtrag, desto geringer werden GlƤser durch das Reinigungsmittel angegriffen. Ā To determine the extent of the glass corrosion, a sensor crystal was used, which was coated with a soda-lime glass. This coated sensor was over-rinsed with a phosphate-free detergent having the above composition. Likewise, a glass-coated sensor with a cleaning agent according to the invention comprising 10% by weight and 1% by weight, respectively, of PDADMAC was rinsed over. The process of overflowing the sensor was carried out at 60 Ā° C in a QCM Q-Sense (Stockholm, Sweden). The cleaning agents removed the glass coating from the sensor after a certain period of time (mass removal). This mass removal from the sensor corresponds to the severity of the glass corrosion. The beginning of the mass removal, measured from the moment when the sensor is flushed 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 mass removal begins and / or the lower the mass removal, the lower the glasses are attacked by the cleaning agent.
Die Bestimmung des Zeitpunkts t, ab welchem ein Masseabtrag erfolgte, entspricht dem Zeitraum, ab dem Beginn der ƜberspĆ¼lung des Sensors mit dem Reinigungsmittel bis zu dem Moment, in dem ein deutlicher Masseabtrag erkennbar war. Die Angabe erfolgt hier in Minuten. Der Masseabtrag wurde relativ zum ursprĆ¼nglichen Massewert bestimmt. Die Angabe erfolgt daher hier in %. Das ƜberspĆ¼len mit einem Reinigungsmittel, welches kein PDADMAC enthielt, sorgte bereits nach weniger als 30 min fĆ¼r einen Masseverlust des Sensors von mehr als 50 % der Glasschicht. Durch PDADMAC konnte das Auftreten des Masseverlusts auf einen dreifach spƤteren Zeitpunkt hinausgezƶgert werden. Der Masseverlust betrug anfƤnglich auch hier etwa 50 %. Sowohl bei dem Vergleichsbeispiel als auch bei dem erfindungsgemƤƟen Reinigungsmittel, welches 1 Gew.-% PDADMAC aufwies, entwickelte sich ein Grenzwert. Weiterer Glasabtrag erfolgte hier nicht. Dieser Grenzwert lag jedoch beim Reinigungsmittel ohne PDADMAC unterhalb des Grenzwertes des erfindungsgemƤƟen Reinigungsmittels mit PDADMAC. Ohne PDADMAC wurden am Ende, also im Bereich des Grenzwertes, etwa 10 % mehr Glas vom Sensor abgetragen als mit dem erfindungsgemƤƟen Reinigungsmittel. The determination of the time t, from which a mass removal took place, corresponds to the period from the beginning of the overflushing of the sensor with the detergent up to the moment in which a significant mass removal was recognizable. The information is given here in minutes. Mass removal was determined relative to the original mass value. The indication is therefore here in%. Rinsing with a detergent that did not contain a PDADMAC caused a loss of mass of the sensor of more than 50% of the glass layer after less than 30 minutes. PDADMAC was able to delay the occurrence of mass loss three times later. The mass loss was initially about 50% here. Both in the comparative example and in the detergent according to the invention, which had 1% by weight of PDADMAC, a limit value developed. Further glass removal did not take place here. However, this limit was below the limit value of the detergent according to the invention with PDADMAC in the detergent without PDADMAC. Without PDADMAC, about 10% more glass was removed from the sensor at the end, ie in the range of the limit value, than with the cleaning agent according to the invention.
Weiterhin wurde ein zweites erfindungsgemƤƟes Reinigungsmittel, welches 10 Gew.-% PDADMAC aufwies, getestet. Hier erfolgte der erste Masseverlust erst nach einem 4 bis 6 Mal so langem Zeitraum wie ohne PDADMAC. Das heiƟt der initiale Glasverlust trat erst nach sehr langer Zeit auf. Auch hier erfolgte dann ein Masseverlust von etwa 50 %. Dies bedeutet, dass etwa 50 % der Glasschicht, welche sich auf dem Sensor befand abgetragen wurde. Auch hier wurde nach einem gewissen Materialabtrag ein maximaler Wert erreicht. Dieser betrug nochmals etwa 10 bis 20 % weniger als bei dem erfindungsgemƤƟen Reinigungsmittel, welches 1 Gew.-% PDADMAC enthielt. Furthermore, a second inventive detergent, which had 10 wt .-% PDADMAC, tested. Here, the first loss of mass occurred only after a 4 to 6 times as long as without PDADMAC. This means that the initial loss of glass occurred only after a very long time. Again, then there was a loss of mass of about 50%. This means that about 50% of the glass layer that was on the sensor was removed. Again, after a certain material removal a maximum value was reached. This was again about 10 to 20% less than in the inventive detergent containing 1 wt .-% PDADMAC.
Ein erfindungsgemƤƟes Reinigungsmittel, welches PDADMAC aufweist, ermƶglicht daher eine deutliche Verringerung der Glaskorrosion. Diese tritt zum einen deutlich spƤter auf und sorgt fĆ¼r einen geringeren Masseverlust Ć¼ber die Zeit. Die Glaskorrosion tritt somit erst nach einer grĆ¶ĆŸeren Anzahl an SpĆ¼lzyklen auf. Zudem ist die AusprƤgung der Glaskorrosion gegenĆ¼ber im Stand der Technik bekannten Reinigungsmitteln verringert. A cleaning agent according to the invention which comprises PDADMAC therefore makes it possible to significantly reduce glass corrosion. This occurs on the one hand much later and ensures a lower loss of mass over time. The glass corrosion thus occurs only after a larger number of rinsing cycles. In addition, the severity of the glass corrosion is reduced compared to cleaning agents known in the prior art.

Claims

PatentansprĆ¼che: claims:
1. Reinigungsmittel umfassend wenigstens ein Tensid, einen oder mehrere Komplexbildner und PDADMAC. A cleaning agent comprising at least one surfactant, one or more complexing agents and PDADMAC.
2. Reinigungsmittel nach Anspruch 1 , dadurch gekennzeichnet, dass es PDADMAC in einem Anteil von 0,01 bis 50 Gew.-%, insbesondere von 0,01 bis 30 Gew.-% besonders von 0,01 bis 1 Gew.-% umfasst. 2. Cleaning agent according to claim 1, characterized in that it comprises PDADMAC in a proportion of 0.01 to 50 wt .-%, in particular from 0.01 to 30 wt .-%, especially from 0.01 to 1 wt .-% ,
3. Reinigungsmittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der Komplexbildner ausgewƤhlt ist aus der Gruppe, die CitronensƤure und deren Salze, MGDA, HEDP sowie deren Mischungen umfasst. 3. Cleaning agent according to claim 1 or 2, characterized in that the complexing agent is selected from the group comprising citric acid and its salts, MGDA, HEDP and mixtures thereof.
4. Reinigungsmittel nach einem der AnsprĆ¼che 1 bis 3, weiterhin umfassend einen Korrosionsinhibitor. 4. Cleaning agent according to one of claims 1 to 3, further comprising a corrosion inhibitor.
5. Reinigungsmittel nach Anspruch 4, dadurch gekennzeichnet, dass der Korrosionsinhibitor Zinkacetat umfasst. 5. Cleaning agent according to claim 4, characterized in that the corrosion inhibitor comprises zinc acetate.
6. Reinigungsmittel nach einem der AnsprĆ¼che 1 bis 5, dadurch gekennzeichnet, dass es frei von Phosphaten ist. 6. Cleaning agent according to one of claims 1 to 5, characterized in that it is free of phosphates.
7. Verwendung eines Reinigungsmittels nach einem der AnsprĆ¼che 1 bis 6 zum manuellen und/oder maschinellen Reinigen von GegenstƤnden mit GlasoberflƤchen, insbesondere zum maschinellen Reinigen von GegenstƤnden mit GlasoberflƤchen. 7. Use of a cleaning agent according to one of claims 1 to 6 for manual and / or machine cleaning of objects with glass surfaces, in particular for machine cleaning of objects with glass surfaces.
8. Verfahren zum Reinigen von GegenstƤnden mit GlasoberflƤche wobei man ein Reinigungsmittel nach einem der AnsprĆ¼che 1 bis 6 mit der GlasoberflƤche in Kontakt bringt. 8. A method of cleaning articles with a glass surface, wherein a detergent according to any one of claims 1 to 6 brings into contact with the glass surface.
9. Verfahren nach Anspruch 8 oder 9, dadurch gekennzeichnet, dass die Temperatur, bei der die Reinigung durchgefĆ¼hrt wird, im Bereich von 5 Ā°C bis 90 Ā°C, insbesondere von 20 Ā°C bis 80 Ā°C, besonders von 40 Ā°C bis 60 Ā°C liegt. 9. The method according to claim 8 or 9, characterized in that the temperature at which the cleaning is carried out in the range of 5 Ā° C to 90 Ā° C, in particular from 20 Ā° C to 80 Ā° C, especially from 40 Ā° C to 60 Ā° C is.
10. Verwendung von PDADMAC in einem Reinigungsmittel, insbesondere in einem Reinigungsmittel zur maschinellen Reinigung von GlasoberflƤchen, zur Verringerung der Glaskorrosion. 10. Use of PDADMAC in a detergent, especially in a detergent for machine cleaning of glass surfaces, to reduce glass corrosion.
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