EP1509588B1 - Agents de rin age protegeant le verre contre la corrosion - Google Patents

Agents de rin age protegeant le verre contre la corrosion Download PDF

Info

Publication number
EP1509588B1
EP1509588B1 EP03732487A EP03732487A EP1509588B1 EP 1509588 B1 EP1509588 B1 EP 1509588B1 EP 03732487 A EP03732487 A EP 03732487A EP 03732487 A EP03732487 A EP 03732487A EP 1509588 B1 EP1509588 B1 EP 1509588B1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
rinse aid
acids
ether
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.)
Revoked
Application number
EP03732487A
Other languages
German (de)
English (en)
Other versions
EP1509588A1 (fr
Inventor
Arnd Kessler
Ulrich Pegelow
Ingo Hardacker
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
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=29594298&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1509588(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1509588A1 publication Critical patent/EP1509588A1/fr
Application granted granted Critical
Publication of EP1509588B1 publication Critical patent/EP1509588B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid 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
    • 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
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid 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
    • 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
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to rinse aid for automatic dishwashing for the corrosion protection of glassware during rinsing operations of a dishwasher.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So even a completely cleaned of leftovers dishes is then rated as not flawless if it has after dishwasher washing whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets.
  • rinse aid In order to obtain glossy and spotless dishes, it is therefore successfully used today rinse aid.
  • the addition of rinse aid at the end of the washing program ensures that the water runs as completely as possible from the items to be washed, so that the different surfaces at the end of the washing program are residue-free and flawless gloss.
  • the automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses.
  • the temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection.
  • rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Such rinse aids are in liquid form and are widely described in the art. Your task is primarily to prevent limescale and deposits on the cleaned dishes. In addition to water and low-foaming nonionic surfactants, these rinse aids often also contain hydrotopes, pH regulators such as citric acid or scale-inhibiting polymers.
  • the European patent application EP 0 383 482 (Procter & Gamble) finally describes automatic dishwasher detergents containing insoluble zinc salts, which are distinguished by improved glass corrosion protection.
  • the insoluble zinc salts must have a particle size below 1.7 millimeters to achieve such an effect.
  • Zinc-containing Klarspulstoff be in the Patents US 4,443,270 (Procter & Gamble) and US 4,908,148 (Procter & Gamble).
  • the international patent application WO 00/39259 discloses water-soluble glasses according to DIN ISO 719, which contain at least one glass corrosion-inhibiting active ingredient whose weight fraction of the glass is not more than 85 wt .-% and which is released under the conditions of cleaning and / or rinsing from this glass.
  • the object of the present invention was to provide new rinse aid, which provide at least the same results in terms of performance properties as marketable rinse aid and beyond the other performance benefits, in particular the added benefit of reducing glass corrosion in automatic dishwashing provide.
  • R 2 may optionally be alkoxylated, wherein the alkoxy group is preferably selected from ethoxy, propoxy, butoxy groups and mixtures thereof.
  • the rinse aids of the invention may contain, in addition to the above, one or more other nonionic surfactant (s).
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • 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, especially fatty acid methyl esters.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable Alkypolyglycoside meet the general formula RO (G) z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.
  • 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 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.
  • polyhydroxy fatty acid amides of the following formula wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the following formula in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 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 oxyalkyl radical having from 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [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 then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • 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.
  • rinse aids which contain surfactants of the general formula I as nichionic surfactant (s) in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
  • nichionic surfactant (s) in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1
  • the preferred nonionic surfactants of formula XVII can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the formula I above may vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals.
  • R 1 in formula I 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.
  • Preferred automatic dishwashing agents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
  • nonionic surfactants which have a C 9-15 -alkyl radical 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.
  • the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above Room temperature.
  • preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.
  • Suitable nonionic surfactants in addition to the nonionic surfactants according to the invention 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 high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the 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) surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • ethoxylated nonionic surfactant consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • 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 automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 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 that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • a further preferred machine dishwashing detergent according to the invention contains nonionic surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ], in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 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 for values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are 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 are values 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 may be different.
  • R 1 and R 2 are preferably 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 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 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, with the variation width 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 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 1 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • dishwashing agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are 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, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • R 1 and R 2 are linear or branched
  • Anionic, cationic and / or amphoteric surfactants may also be used in conjunction with the surfactants mentioned, these having only minor importance owing to their foaming behavior in automatic dishwashing, and in most cases only in amounts below 10% by weight, in most cases even below 5% by weight .-%, for example, from 0.01 to 2.5 wt .-%, each based on the agent used.
  • the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.
  • Particularly preferred surfactants can be defined by the formulas C 9-11 (EO) 8 -C (CH 3 ) 2 CH 2 CH 3 , C 11-15 (EO) 15 (PO) 6 -C 12-14 , C 9-11 (EO) 8 (CH 2 ) 4 CH 3 .
  • R 1 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c is between 1 and 30, preferably between 1 and 20
  • the EO and PO groups in the above formula may also be reversed so that surfactants of the general formula R 1 (PO) b (EO) a (BO) c , in the R 1 for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c for values between 1 and 30, preferably between 1 and 20, is also usable with preference.
  • surfactants of the general formula R 1 (PO) b (EO) a (BO) c in the R 1 for a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30, preferably 6 to 20 C atoms, a for values between 2 and 30, b for values between 0 and 30 and c for values between 1 and 30, preferably between 1 and 20, is also usable with preference.
  • Particularly preferred representatives of this group of surfactants can be distinguished by the formulas C 9-11 (PO) 3 (EO) 13 (BO) 15 , C 9-11 (PO) 3 (EO) 13 (BO) 6 , C 9- 11 (PO) 3 (EO) 13 (BO) 3 , C 911 (EO) 13 (BO) 6 , C 9-11 (EO) 13 (BO) 3 , C 9-11 (PO) (EO) 13 ( BO) 3 , C 9-11 (EO) 8 (BO) 3 , C 911 (EO) 8 (BO) 2 , C 12-15 (EO) 7 (BO) 2 , C 9-11 (EO) 8 ( BO) 2 , C 9-11 (EO) 8 (BO).
  • a particularly preferred surfactant of formula C 13-15 (EO) 9-10 (BO) 1-2 is commercially available under the name Plurafac LF ® 221st It is also possible to use a surfactant of the formula C 12-13 (EO) 10 (BO) 2 .
  • rinse aids which contain the nonionic surfactant (s) in amounts of from 1.5 to 30% by weight, preferably from 2.5 to 25 wt .-%, particularly preferably from 5 to 22.5 wt .-%, and in particular from 7.5 to 20 wt .-%, each based on the rinse aid.
  • the rinse aids according to the invention contain at least one agent which is capable of providing corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher, from the group of the compounds of zinc.
  • Rinsing agents which are particularly preferred according to the invention are characterized in that the agent (s) effective for the corrosion protection, from the group of zinc salts of at least one monomeric and / or polymeric organic acid from the group of unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms, the resin acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids derived from the oxo acids, the amino acids and / or the polymeric carboxylic acids.
  • the agent (s) effective for the corrosion protection from the group of zinc salts of at least one monomeric and / or polymeric organic acid from the group of unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, the saturated and uns
  • Preferred agents capable of providing corrosion protection for glassware during dishwashing and / or rinsing operations of a dishwashing machine are compounds containing zinc in oxidized form, ie zinc compounds in which zinc is cationic.
  • both soluble and poorly soluble or insoluble zinc compounds can be present in the compositions according to the invention, it being necessary to stabilize poorly or non-soluble compounds in a suitable manner against settling (for example via the parameters particle size of the particles and viscosity of the composition).
  • Preferred compositions according to the invention contain one or more Zinc salt (s) of at least one monomeric and / or polymeric organic acid.
  • the acids concerned preferably originate from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acid, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms and / or resin acids.
  • the zinc salts of monomeric and / or polymeric organic acids are branched from the groups of unbranched saturated or unsaturated monocarboxylic acids saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.
  • the acids mentioned below are again preferred in the context of the present invention:
  • benzoic acid 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (Trimesionklare).
  • sugar acids galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.
  • hydroxy acids From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-dihydroxybutanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2 Hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
  • oxo acids 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
  • polymeric carboxylic acids polyacrylic acid, polymethacrylic acid, alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methylmethacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers.
  • inventively preferred zinc salts of organic acids preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts having a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature).
  • the first group of zinc salts include, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate, zinc tosylate (p-toluenesulfonic acid Zn salt) and zinc gluconate:
  • the rinse aids according to the invention contain at least one zinc salt, but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate , Zinc lactate and / or zinc citrate.
  • zinc ricinoleate, zinc abietate and zinc oxalate are also preferably used.
  • Preferred rinse aids according to the invention comprise the antacorrosion agent (s) in amounts of from 0.2 to 15% by weight, preferably from 0.5 to 12% by weight, more preferably from 1.0 to 10 wt .-% and in particular from 1.5 to 9 wt .-% in each case based on the rinse aid.
  • the rinse aids according to the invention contain water or an aqueous solution of other active ingredients and / or auxiliaries ad 100%. Depending on the amount and type of substances used, it may also be necessary to use water-miscible solvents.
  • water-miscible solvents The most important ingredients which, besides water and nonionic surfactants as well as glass corrosion inhibitors, can be contained in the agents according to the invention are described below.
  • Acidifying agents can be added to the rinse aids according to the invention in order to lower the pH of the liquor in the final rinse cycle.
  • inorganic acids and organic acids, provided that they are compatible with the other ingredients.
  • solid mono-, oligo- and polycarboxylic acids are used.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).
  • Rinse aid which additionally contains one or more acid-caking agents, preferably mono-, oligo- and polycarboxylic acids, particularly preferably tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and in particular citric acid in amounts of from 0.5 to 10% by weight , preferably from 1 to 7.5 wt .-%, particularly preferably from 2 to 5 wt .-% and in particular from 2.5 to 4 wt .-%, each based on the rinse aid, contain, are preferred embodiments of the present invention ,
  • the agents according to the invention may also contain salts of the abovementioned acids as buffer substances.
  • Preferred here are the alkali metal salts, and among these, the sodium salts are particularly preferred.
  • Particularly preferred according to the invention is the use of tri-sodium citrate.
  • Non-aqueous solvents which can be used in the compositions according to the invention are derived, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated.
  • the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents, so that preferred rinse aids are characterized in that they non
  • the rinse aids of the present invention may further contain hydrotropes.
  • hydrotropes The addition of such substances causes a poorly soluble substance in the presence of the hydrotrope, which is itself no solvent, becomes water-soluble.
  • Substances which cause such solubility improvement are termed hydrotropes or hydrotropes.
  • Typical hydrotropes eg in the preparation of liquid washing or detergents, are xylene and cumene sulfonate.
  • Other substances for example urea or N-methylacetamide, increase the solubility by a structure-breaking effect, in which the water structure in the vicinity of the hydrophobic group of a sparingly soluble substance is degraded.
  • preferred rinse aids contain solubilizers, preferably aromatic sulfonates of the formula in amounts of 0.5 to 10 wt .-%, preferably from 1 to 7.5 wt .-%, particularly preferably from 2 to 5 wt .-% and in particular from 2.5 to 4 wt .-%, in each case based on the rinse aid, wherein each of R 1, R 2, R 3, R 4, R 5 is independently selected from H or a C 1-5 alkyl or alkenyl group and X is a cation.
  • Preferred substituents R 1 , R 2 , R 3 , R 4 , R 5 are independently selected from H or a methyl, ethyl, n- propyl, iso- propyl, n- butyl, iso- butyl, tert -Butyl, n- pentyl, iso- pentyl or neo- pentyl.
  • at least three of said radicals R 1 to R 5 are hydrogen atoms, with aromatic sulfonates being preferred in which three or four substituents on the aromatic ring are hydrogen atoms.
  • the remaining or the remaining two radicals can take any position to the sulfonate group and each other.
  • the radical R 3 is an alkyl radical
  • R 1 , R 2 , R 4 , and R 5 are H ( para- substitution).
  • aromatic sulfonates in the context of the present invention are toluene, cumene or xylene sulfonate.
  • the para-isomer is preferred in the context of the present invention.
  • the para-isopropylbenzenesulfonate is also the preferred compound in the case of the cumene sulfonates.
  • xylene is usually used industrially as a mixture of isomers
  • the industrially available xylenesulfonate is also a mixture of several compounds resulting from the sulfonation of ortho, meta and para- xylene result.
  • X in the general formula given above represents a cation, for example an alkali metal cation such as sodium or potassium.
  • X may also represent the equivalent charge portion of a more cost cation, such as Mg 2+ / 2 or Al 3+ / 3, wherein the said cations, sodium is preferred.
  • the rinse aids according to the invention may preferably additionally comprise one or more substances from the groups of the soil-release polymers, the dyes and the fragrances.
  • soil release compounds which prevent the re-soiling of surfaces and / or facilitate the removal of soil after a single application.
  • the soil release compounds which can be used according to the invention include all compounds known from the prior art.
  • Particularly suitable are cationic polymers, in particular polymers with imino groups, cationic cellulose derivatives or cationic homo- and / or copolymers with quaternized ammonium alkyl methacrylate groups as monomer units.
  • the cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides with quaternary side groups as soil release compounds.
  • monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; qua
  • the rinse aids In order to improve the aesthetic impression of the rinse aids according to the invention, they can be dyed with suitable dyes.
  • Dyes which are preferred in the context of the present invention and whose selection does not present any difficulty to a person skilled in the art have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity towards dishes in order not to stain them.
  • Preferred for use in the rinse aids according to the invention are all colorants which can be oxidatively destroyed and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
  • One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a commercial product ® for example as Basacid Green 970 from BASF, Ludwigshafen, is, as well as mixtures thereof with suitable. blue dyes.
  • Pigmosol ® come ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl Red 545 FL (CI 45170), Sandolan® ® rhodamine EB400 (CI 45100), Basacid® ® Yellow 094 (CI 47005) Sicovit ® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), pigment Blue 15 (CI 74160), Supranol Blue ® GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan Yellow ® N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.
  • the colorant When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the surfaces to be treated, and in particular for plastics. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the rinse aid detergents varies. For highly soluble colorants, such as the Basacid Green ® above or also above Sandolan Blue ®, dye concentrations in the range of a few 10 -2 to 10 -3 wt .-% are typically chosen.
  • the appropriate concentration of the colorant in rinse aids is typically a few 10 -3 to 10 -4 wt .-%.
  • Fragrances are added to the compositions within the scope of the present invention in order to improve the aesthetics of the products and to provide the consumer, in addition to the performance of the product, with a visually and sensory "typical and unmistakable" product.
  • fragrance compounds for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear Alkanals with 8-18 C-atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones eg the Jonone, ⁇ -isomethylionone and methyl-cedrylketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool , Phenylethylalkohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • Uncleaned glasses were rinsed in a continuous dishwashing machine in a 65 ° C program with pre-rinse with a commercial machine dishwashing detergent at a water hardness of 0-1 ° dH. In the cleaning a liquid load dirt was metered.
  • Example V1 and E1 in each case about 19 g of a commercially available machine dishwashing detergent were metered in for each cleaning cycle.
  • Comparative Example C1 3 ml of a commercial rinse aid were additionally added to the rinse cycle, while in Example E1 according to the invention, 3 ml of a rinse aid with a zinc acetate content of 5% by weight were metered into the rinse cycle in addition to the machine dishwashing detergent.
  • the rinse was repeated 50/100/200 times under the conditions described above. The overall appearance of the items to be washed was assessed on the basis of the rating scale below.
  • the table shows that the use of a zinc-containing rinse aid according to the invention, glass corrosion phenomena in automatic dishwashing can be significantly reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Surface Treatment Of Glass (AREA)
  • Laminated Bodies (AREA)

Claims (8)

  1. Agent de rinçage pour le lavage mécanique de la vaisselle, contenant
    a) à concurrence de 0,1 à 35 % en poids un ou plusieurs agents tensioactifs non ioniques répondant à la formule générale

            R1O[CH2CH(R3)O]xR2,

    dans laquelle R1 représente un radical d'hydrocarbure aliphatique ou aromatique, saturé ou insaturé, linéaire ou ramifié, contenant de 1 à 30 atomes de carbone, R2 représente un radical d'hydrocarbure aliphatique, saturé ou insaturé, linéaire ou ramifié, contenant de 1 à 30 atomes de carbone, qui est substitué avec 1, 2, 3, 4 ou 5 groupes hydroxyle et, de manière facultative, avec d'autres groupes éther, R3 représente un atome d'hydrogène ou un groupe méthyle, un groupe éthyle, un groupe n-propyle, un groupe iso-propyle, un groupe n-butyle, un groupe iso-butyle ou un groupe tert-butyle, et x peut prendre des valeurs entre 1 et 40,
    b) à concurrence de 0,1 à 10 % en poids, au moins un agent du groupe des composés du zinc, qui est en mesure de procurer une protection contre la corrosion pour des articles en verre dans des processus de lavage et/ou de rinçage d'un lave-vaisselle,
    c) de l'eau ou une solution aqueuse de substances actives et/ou de substances auxiliaires supplémentaires que l'on ajoute pour obtenir 100 %, avec cette mesure que l'agent de rinçage contient un ou plusieurs agents tensioactifs non ioniques à concurrence de 0,1 à 35 % en poids.
  2. Agents de rinçage selon la revendication 1, caractérisés en ce qu'ils contiennent lesdits un ou plusieurs agents tensioactifs non ioniques dans des quantités de 1,5 à 30 % en poids, de préférence de 2,5 à 25 % en poids, de manière particulièrement préférée de 5 à 22,5 % en poids, et en particulier de 7,5 à 20 % en poids, chaque fois rapportés à l'agent de rinçage.
  3. Agents de rinçage selon l'une quelconque des revendications 1 ou 2, caractérisés en ce que l'agent, respectivement les agents manifestant une activité de protection contre la corrosion provient, respectivement proviennent du groupe des sels de magnésium et/ou de zinc d'au moins un acide organique monomère et/ou polymère du groupe des acides monocarboxyliques non ramifiés, saturés ou insaturés, des acides monocarboxyliques ramifiés, saturés ou insaturés, des acides dicarboxyliques saturés et insaturés, des acides gras non ramifiés ou ramifiés, insaturés ou saturés, une ou plusieurs fois hydroxylés contenant au moins 8 atomes de carbone, des acides résiniques, des acides monocarboxyliques, dicarboxyliques et tricarboxyliques aromatiques, des acides sacchariques, des hydroxyacides, des oxoacides, des aminoacides et/ou des acides carboxyliques polymères.
  4. Agents de rinçage selon l'une quelconque des revendications 1 à 3, caractérisés en ce qu'ils contiennent l'agent, respectivement les agents manifestant une activité de protection contre la corrosion, dans des quantités de 0,2 à 15 % en poids, de préférence de 0,5 à 12 % en poids, de manière particulièrement préférée de 1,0 à 10 % en poids, et en particulier de 1,5 à 9 % en poids, chaque fois rapportés à l'agent de rinçage.
  5. Agents de rinçage selon l'une quelconque des revendications 1 à 4, caractérisés en ce qu'ils contiennent en outre un ou plusieurs acidifiants, de préférence des acides monocarboxyliques, oligocarboxyliques et polycarboxyliques, de manière particulièrement préférée, de l'acide tartrique, de l'acide succinique, de l'acide malonique, de l'acide adipique, de l'acide maléique, de l'acide fumarique, de l'acide oxalique, et de l'acide polyacrylique et, en particulier, de l'acide citrique dans des quantités de 0,5 à 10 % en poids, de préférence de 1 à 7,5 % en poids, de manière particulièrement préférée de 2 à 5 % en poids, et en particulier de 2,5 à 4 % en poids, chaque fois rapportés à l'agent de rinçage.
  6. Agents de rinçage selon l'une quelconque des revendications 1 à 5, caractérisés en ce qu'ils contiennent un ou plusieurs solvants non aqueux, de préférence de l'éthanol, du n-propanol, du i-propanol, du 1-butanol, du 2-butanol, du glycol, du propanediol, du butanediol, du glycérol, du diglycol, du propyldiglycol, du butyldiglycol, de l'hexylèneglycol, de l'éther méthylique d'éthylèneglycol, de l'éther éthylique d'éthylèneglycol, de l'éther propylique d'éthylèneglycol, de l'éther mono-n-butylique d'éthylèneglycol, de l'éther méthylique de diéthylèneglycol, de l'éther éthylique de diéthylèneglycol, de l'éther méthylique, éthylique ou propylique de propylèneglycol, de l'éther méthylique ou éthylique de dipropylèneglycol, du méthoxy-, de l'éthoxy- ou du butoxy-triglycol, du 1-butoxyéthoxy-2-propanol, du 3-méthyl-3-méthoxybutanol, de l'éther t-butylique de propylèneglycol, ainsi que des mélanges de ces solvants.
  7. Agents de rinçage selon l'une quelconque des revendications 1 à 6, caractérisés en ce qu'ils contiennent des dissolvants, de préférence des sulfonates aromatiques répondant à la formule
    Figure imgb0007
     dans des quantités de 0,5 à 10 % en poids, de préférence de 1 à 7,5 % en poids, de manière particulièrement préférée de 2 à 5 % en poids, et en particulier de 2,5 à 4 % en poids, chaque fois rapportés à l'agent de choisi, indépendamment l'un de l'autre, parmi un atome d'hydrogène ou un radical alkyle ou alcényle en C1-C5 et X représente un cation.
  8. Agent de rinçage selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il contient en outre une ou plusieurs substances choisies parmi les groupes des polymères « soil-release », des colorants et des parfums.
EP03732487A 2002-06-06 2003-05-28 Agents de rin age protegeant le verre contre la corrosion Revoked EP1509588B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10225114A DE10225114A1 (de) 2002-06-06 2002-06-06 Klarspülmittel mit Glaskorrosionsschutz
DE10225114 2002-06-06
PCT/EP2003/005593 WO2003104367A1 (fr) 2002-06-06 2003-05-28 Agents de rinçage protegeant le verre contre la corrosion

Publications (2)

Publication Number Publication Date
EP1509588A1 EP1509588A1 (fr) 2005-03-02
EP1509588B1 true EP1509588B1 (fr) 2008-06-11

Family

ID=29594298

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03732487A Revoked EP1509588B1 (fr) 2002-06-06 2003-05-28 Agents de rin age protegeant le verre contre la corrosion

Country Status (6)

Country Link
EP (1) EP1509588B1 (fr)
AT (1) ATE398166T1 (fr)
AU (1) AU2003238419A1 (fr)
DE (2) DE10225114A1 (fr)
ES (1) ES2306874T3 (fr)
WO (1) WO2003104367A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017083988A1 (fr) * 2015-11-22 2017-05-26 Jempak Corporation Produits détergents monodose, compositions de rinçage et procédés

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040176264A1 (en) † 2002-12-30 2004-09-09 The Procter & Gamble Company Rinse aid composition containing water-soluble metal salt for use in automatic dishwashing for glassware corrosion protection
US20040180807A1 (en) † 2002-12-30 2004-09-16 The Procter & Gamble Company Rinse aid composition containing water-soluble metal salt for use in automatic dishwashing for metal corrosion and rust formation protection
EP1571198A1 (fr) * 2004-03-02 2005-09-07 Dalli-Werke GmbH & Co. KG. Composés au manganèse liés à des polymères dans des compositions détergentes
US8431517B2 (en) * 2004-09-28 2013-04-30 The Procter & Gamble Company Surface corrosion protection detergent compositions containing polyvalent metal compounds and high levels of low foaming, nonionic surfactants
US20060069001A1 (en) * 2004-09-28 2006-03-30 The Procter & Gamble Company Methods of protecting glassware surfaces from corrosion using detergent compositions containing polyvalent metal compounds and high levels of low foaming, nonionic surfactants
DE102019200702A1 (de) * 2019-01-21 2020-07-23 Henkel Ag & Co. Kgaa Mehrkomponentiges Reinigungssystem
DE102019219881A1 (de) * 2019-12-17 2021-06-17 Henkel Ag & Co. Kgaa Klarspülmittel für automatische Geschirrspülmaschinen
DE102019219861A1 (de) * 2019-12-17 2021-06-17 Henkel Ag & Co. Kgaa Nichtionisches Tensid zur Verbesserung der Klarspülleistung beim automatischen Geschirrspülen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3267272D1 (en) * 1981-07-17 1985-12-12 Procter & Gamble Rinse aid composition
US4908148A (en) * 1989-02-13 1990-03-13 The Procter & Gamble Company Rinse additive compositions providing glassware protection comprising insoluble zinc compounds
US6448210B1 (en) * 1999-03-19 2002-09-10 Johnsondiversey, Inc. Liquid automatic dishwashing composition with glassware protection
DE10032612A1 (de) * 2000-07-07 2002-02-14 Henkel Kgaa Klarspülmittel II
DE10060533A1 (de) * 2000-12-06 2002-06-20 Henkel Kgaa Maschinelle Geschirrspülmittel und Klarspüler mit Geruchsabsorber

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017083988A1 (fr) * 2015-11-22 2017-05-26 Jempak Corporation Produits détergents monodose, compositions de rinçage et procédés

Also Published As

Publication number Publication date
WO2003104367A1 (fr) 2003-12-18
DE10225114A1 (de) 2003-12-24
ATE398166T1 (de) 2008-07-15
AU2003238419A1 (en) 2003-12-22
EP1509588A1 (fr) 2005-03-02
DE50309978D1 (de) 2008-07-24
ES2306874T3 (es) 2008-11-16

Similar Documents

Publication Publication Date Title
EP1863894B1 (fr) Utilisation des acetales dans des detergents et nettoyants
DE102005027605A1 (de) Geschirrspülmittelformulierungen enthaltend Oligoester
KR102467665B1 (ko) 액체 세정제
US20190055496A1 (en) Method of cleaning household surfaces
EP1509588B1 (fr) Agents de rin age protegeant le verre contre la corrosion
EP3015540B1 (fr) Nettoyants de surfaces dures comprenant des tensioactifs non ioniques alcoxylés éthoxylés
EP1664257B1 (fr) Detergents pour lave-vaisselle contenant un melange polymere special
EP3478812B1 (fr) Utilisation de detergent sous forme de bloc pour netttoyer la zone des w.c.
WO2006128543A1 (fr) Compose tensioactif
EP1409625B1 (fr) Detergents pour lave-vaisselle comportant des tensioactifs a coefficients de diffusion determines
EP2109663B1 (fr) Agent de nettoyage pour surfaces en verre
EP3116984B1 (fr) Mélange de tensioactifs amélioré ayant un degré d'éthoxylation optimisé
EP1409624B1 (fr) Detergents pour lave-vaisselle comportant des tensioactifs a tension superficielle dynamique basse
EP1904613B1 (fr) Produits de nettoyage et d'entretien presentant une emulsibilite amelioree
US9957467B2 (en) Hard surface cleaners comprising ethoxylated alkoxylated nonionic surfactants
DE10140535B4 (de) Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz
EP1987119B1 (fr) Agent de lavage ou de nettoyage
DE102014212622A1 (de) Reinigungsmittel umfassend Hydroxamsäure und/oder deren Salze
EP1664256B1 (fr) Compostions detergentes pour lave-vaisselle conprenant des polym res speciaux
DE102007039654A1 (de) Reinigungsmittel für Glasoberflächen
DE102015221442A1 (de) Tensidmischung enthaltend Aminoxid zur Verbesserung der Klarspülleistung
WO2005017083A1 (fr) Produit nettoyant pour le traitement en douceur de surfaces contenant du carbonate, sensibles aux acides
WO2000073409A1 (fr) Detergent solides a base de tensioactifs

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041104

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KESSLER, ARND

Inventor name: PEGELOW, ULRICH

Inventor name: HARDACKER, INGO

17Q First examination report despatched

Effective date: 20051102

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 50309978

Country of ref document: DE

Date of ref document: 20080724

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

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

Ref country code: FI

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

Effective date: 20080611

Ref country code: SI

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

Effective date: 20080611

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2306874

Country of ref document: ES

Kind code of ref document: T3

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

Ref country code: NL

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

Effective date: 20080611

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

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

Effective date: 20080911

Ref country code: PT

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

Effective date: 20081111

Ref country code: CZ

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

Effective date: 20080611

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: RO

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

Effective date: 20080611

Ref country code: SK

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

Effective date: 20080611

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: DALLI-WERKE WAESCHE-UND KOERPERPFLEGE GMBH & CO KG

Effective date: 20090306

Opponent name: PROCTER & GAMBLE, INC.

Effective date: 20090310

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

Ref country code: IE

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

Effective date: 20080611

Ref country code: DK

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

Effective date: 20080611

Ref country code: EE

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

Effective date: 20080611

Ref country code: BG

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

Effective date: 20080911

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: DALLI-WERKE WAESCHE-UND KOERPERPFLEGE GMBH & CO KG

Effective date: 20090306

Opponent name: UNILEVER N.V.

Effective date: 20090311

Opponent name: PROCTER & GAMBLE, INC.

Effective date: 20090310

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20090531

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

Ref country code: MC

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

Effective date: 20090531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: LI

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

Effective date: 20090531

Ref country code: CH

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

Effective date: 20090531

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

Ref country code: BE

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

Effective date: 20090531

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

APBM Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOSNREFNO

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

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

Ref country code: GR

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

Effective date: 20080912

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: DALLI-WERKE WAESCHE-UND KOERPERPFLEGE GMBH & CO KG

Effective date: 20090306

Opponent name: PROCTER & GAMBLE, INC.

Effective date: 20090310

Opponent name: UNILEVER N.V.

Effective date: 20090311

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

Ref country code: HU

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

Effective date: 20081212

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

Ref country code: CY

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

Effective date: 20080611

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

Ref country code: ES

Payment date: 20120607

Year of fee payment: 10

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

Ref country code: AT

Payment date: 20120426

Year of fee payment: 10

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: DALLI-WERKE WAESCHE-UND KOERPERPFLEGE GMBH & CO KG

Effective date: 20090306

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

Ref country code: GB

Payment date: 20130522

Year of fee payment: 11

Ref country code: DE

Payment date: 20130522

Year of fee payment: 11

Ref country code: LU

Payment date: 20130529

Year of fee payment: 11

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

Ref country code: TR

Payment date: 20130422

Year of fee payment: 11

Ref country code: FR

Payment date: 20130531

Year of fee payment: 11

Ref country code: IT

Payment date: 20130518

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 50309978

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 50309978

Country of ref document: DE

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20130911

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20130911

REG Reference to a national code

Ref country code: DE

Ref legal event code: R107

Ref document number: 50309978

Country of ref document: DE

Effective date: 20140206

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 398166

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140528