EP2366007B1 - Agent de lavage pour lave-vaisselle - Google Patents

Agent de lavage pour lave-vaisselle Download PDF

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Publication number
EP2366007B1
EP2366007B1 EP09795393.9A EP09795393A EP2366007B1 EP 2366007 B1 EP2366007 B1 EP 2366007B1 EP 09795393 A EP09795393 A EP 09795393A EP 2366007 B1 EP2366007 B1 EP 2366007B1
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EP
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Prior art keywords
dishwasher detergent
automatic dishwasher
acid
weight
preferred
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EP09795393.9A
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German (de)
English (en)
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EP2366007A1 (fr
Inventor
Dorota SENDOR-MÜLLER
Johannes Zipfel
Arnd Kessler
Christian Nitsch
Sven Müller
Wolfgang Wick
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • 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 application describes automatic dishwashing detergents, automatic dishwashing processes using these dishwashing detergents.
  • automatic dishwashing detergents In order to obtain spotless dishes, bleaching agents are used in automatic dishwashing detergents. In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwashing detergents generally also contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.
  • bleaches are limited due to incompatibilities with other detergent or cleaning active ingredients, such as enzymes, or because of stability issues in the storage of bleach-containing detergents and cleaners. This is especially true for liquid detergents or cleaning agents.
  • One technical option for improving the cleaning performance of automatic dishwashing detergents is to increase the alkalinity of these detergents. While, on the one hand, with increasing alkalinity, the cleaning performance of automatic dishwashing detergents increases, on the other hand strongly alkaline cleaners also cause damage in the silicate structure of glasses and can cause strong irritation on contact with the skin.
  • alkali metal phosphates Particularly effective builders for increasing the alkalinity have proved to be the alkali metal phosphates, which for this reason form the main constituent of the vast majority of commercially available automatic dishwashing detergents.
  • the registration US 2004/194810 describes a method for cleaning dishes, in which first a basic detergent, then an acidic cleaning composition and then another acidic or basic cleaning composition is applied.
  • dishwashing detergent should be characterized by a good cleaning performance despite freedom from phosphate and bleach, with an improved cleaning performance, for example against bleachable stains, being preferred without at the same time causing increased damage to glass or ceramic surfaces.
  • the bleachable stains include, for example, stains caused by tea or vegetable dyes, for example from vegetables or fruits.
  • the automatic dishwashing compositions according to the invention are preferably low-alkaline.
  • Preferred automatic dishwasher detergents according to the invention are characterized in that the automatic dishwasher detergent has a pH (10% solution, 20 ° C.) between 9 and 11.5, preferably between 9.5 and 11.5, in particular between 10.0 and 11.0.
  • a first essential ingredient of the composition of the invention is the citrate.
  • the term "citrate” also encompasses citric acid as well as its salts, especially theirs Alkali metal salts.
  • Particularly preferred machine dishwasher detergents according to the invention contain citrate, preferably sodium citrate, in amounts of 12 to 50% by weight, preferably 15 to 40% by weight and in particular 15 to 30% by weight, in each case based on the total weight of the automatic dishwashing detergent.
  • Citrate or citric acid has proven to be particularly effective over other builders in combination with the anionic copolymer in terms of tea cleaning.
  • the automatic dishwashing compositions according to the invention may contain, in addition to the citrates, additional builders, in particular carbonates or organic cobuilders.
  • organic co-builders are polycarboxylates / polycarboxylic acids, dextrins and phosphonates. These substance classes are described below,
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
  • NTA nitrilotriacetic acid
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these may be mentioned here.
  • the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the automatic dishwashing compositions of the invention may contain two or more different phosphonates.
  • the proportion by weight of the phosphonates in the total weight of automatic dishwashing agents according to the invention is from 1 to 8% by weight, preferably from 1.2 to 6% by weight and in particular from 1.5 to 4% by weight.
  • polysulfonates contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the polymeric sulfonates in addition to carboxyl-containing monomer and sulfonic acid-containing monomer further comprise at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • a second essential ingredient of the invention is the dicarboxylic acid b).
  • the proportion by weight of the dicarboxylic acid in the total weight of automatic dishwashing detergents according to the invention is preferably 1.0 to 18% by weight, preferably 2.0 to 16% by weight and in particular 4.0 to 12% by weight.
  • dicarboxylic acid includes not only the free acids but also their salts, for example their sodium or potassium salts.
  • the proportion by weight of the free acid when used, the proportion by weight of the free acid must be adjusted, that is to say converted from the proportion by weight of the salt to the proportion by weight of the acid.
  • the group of preferred dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and maleic acid.
  • maleic acid has been proven.
  • Automatic dishwashing detergent characterized in that the automatic dishwashing agent contains dicarboxylic acid b) maleic acid, are therefore preferred according to the invention.
  • succinic acid or “maleic acid” or one of the other acids mentioned includes not only the free acids but also their salts, for example their sodium or potassium salts.
  • the use of the acid salt on the Shut off the proportion by weight of the free acid that is, to convert from the proportion by weight of the salt to the proportion by weight of the acid.
  • the dicarboxylic acid b) can be used in the automatic dishwasher according to the invention, for example as a powder or as an aqueous solution.
  • Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in Table 2 below: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 maleic 1.0 to 18 1.0 to 18 2.0 to 16 4.0 to 12 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100
  • compositions according to the invention may contain further washing or cleaning-active substances, preferably from the group of surfactants, enzymes, organic solvents, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
  • nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants.
  • 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, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 C 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 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.
  • 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.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • 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 with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 -lkohol 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 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.
  • ethoxylated nonionic surfactants consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty carbonate 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 selected 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 mol, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature.
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference.
  • the nonionic surfactant solid at room temperature preferably 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 content of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% Wt .-% and in particular more than 70 wt .-% 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.
  • 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 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.
  • nonionic surfactants of the general formula 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 stand for integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula 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 unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C 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 1 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 C 9-15 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 exhibit in aqueous solution to the required low viscosity and are inventively used with particular preference.
  • R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 in which R 1 and R 2 independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 -alkyl or -alkenyl radical;
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention
  • preferred end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2, in addition to a group R 1 which is linear or branched, saturated or unsaturated , aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where x is from 1 to 90 , preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • 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 with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals By using the above-described nonionic surfactants having a free hydroxyl group on one of the two terminal alkyl radicals, the formation of deposits in machine dishwashing can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
  • 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 ] OR 2 , in which R 1 and R 2 for 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- Is 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 R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 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 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • the proportion by weight of this nonionic surfactant in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5% by weight. and in particular between 1 and 3 wt .-%.
  • the group of nonionic surfactants of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 comprises a number of particularly preferred compounds.
  • R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2) y OR 2 are in which R 3 and R 4 is H, and the subscripts x and y are preferably independently from each other assume values from 1 to 40, preferably from 1 to 15.
  • R 1 -O (CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2) y OR 2 in which the radicals R 1 and R 2 are independently saturated alkyl groups having 4 to 14 Represent carbon atoms and the indices x and y independently of one another assume values of 1 to 15 and in particular of 1 to 12.
  • 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 inventive automatic dishwashing agent in a preferred embodiment is between 0.1 and 15% by weight, preferably between 0.2 and 10% by weight, preferably between 0.5 and 8% by weight. and in particular between 1.0 and 6 wt .-%.
  • Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in Table 34 below: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] citrate 12 to 50 15 to 40 12 to 50 15 to 40 maleic 1.0 to 18 1.0 to 18 2.0 to 16 2.0 to 16 carbonate 5 to 50 10 to 30 5 to 50 10 to 30 phosphonate 1 to 8 1 to 8 1,2 to 6 1,2 to 6 Nonionic surfactant 0.1 to 15 0.1 to 15 0.5 to 8 0.5 to 8 phosphate - - - - bleach - - - - Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100
  • dishwashing agents may contain enzyme (s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Washing or cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • a preferred machine dishwashing detergent according to the invention is characterized in that the dishwashing agent, based on its total weight, enzyme preparation (s) in amounts of 0.1 to 12 wt .-%, preferably from 0.2 to 10 wt .-% and in particular from 0.5 to 8 wt .-% contains.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • the automatic dishwasher detergents according to the invention can be present in the ready-to-use form known to the person skilled in the art, that is to say, for example, in solid or liquid form but also as a combination of solid and liquid supply forms.
  • Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms.
  • the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
  • Inventive agents can be formulated as single-phase or multi-phase products.
  • automatic dishwashing detergents with one, two, three or four phases are 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.
  • the individual phases of multiphase agents may have the same or different states of matter.
  • Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.
  • Particularly preferred in particular two- or multi-phase tablets for example two-layer tablets, in particular two-layer tablets with a trough and a mold body located in the trough.
  • Automatic dishwasher 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 automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • disintegration aids so-called tablet disintegrants
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain.
  • the cellulose used as disintegration aid is preferably not in used finely divided form, but transferred before admixing to be compressed premixes in a coarser form, for example, granulated or compacted.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • Preferred disintegration aids preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • preferred effervescent systems consist of at least two components which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.
  • organic solvents are derived, for example, from the groups of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents in the context of the present application being solvents which are completely water-soluble at room temperature, ie. without miscibility, are miscible.
  • Organic solvents which can be used in the compositions according to the invention preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the given concentration range.
  • the solvents are preferably 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, di ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy trig
  • the organic solvents from the group of the organic amines and / or the alkanolamines have proved to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance of bleachable soiling, in particular on tea stains.
  • Particularly preferred organic amines are the primary and secondary alkylamines, the alkyleneamines and mixtures of these organic amines.
  • the group of preferred primary alkylamines include monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and cyclohexylamine.
  • the group of preferred secondary alkylamines includes in particular dimethylamine.
  • Preferred alkanolamines are in particular the primary, secondary and tertiary alkanolamines and mixtures thereof.
  • Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, diethylethanolamine (2- (diethylamino) ethanol).
  • Particularly preferred secondary alkanolamines are diethanolamine (2,2'-iminodiethanol, DEA, bis (2-hydroxyethyl) amine), N-methyl-diethanolamine, N-ethyl-diethanolamine. Diisopropanolamine and morpholine.
  • Particularly preferred tertiary alkanolamines are triethanolamine and triisopropanolamine.
  • Combination products characterized in that they contain an organic solvent, wherein the organic solvent is an organic amine and / or an alkanolamine, preferably monoethanolamine, are particularly preferred according to the invention.
  • a further subject of this application is a machine dishwashing detergent according to the invention, characterized in that the automatic dishwashing agent, based on its total weight, organic amine and / or an alkanolamine, preferably ethanolamine, in amounts of 0.1 to 15 wt .-%, preferably 0.2 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-% and in particular from 1.0 to 6 wt .-%.
  • these agents preferably contain from 20 to 80% by weight, preferably from 30 to 70% by weight and in particular from 40 to 60% by weight, of water.
  • the metering units of these liquid forms of supply preferably comprise those for a Cleaning cycle necessary amount of washing- or cleaning-active substances.
  • Preferred liquid metering units have a weight between 25 and 60 g, preferably between 30 and 55 g and in particular between 55 and 50 g.
  • the dishwasher detergents according to the invention exhibit their advantageous cleaning and drying properties, in particular also in low-temperature cleaning processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C.
  • agents according to the invention are distinguished from conventional automatic dishwasher detergents by improved tea cleaning.

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Claims (11)

  1. Agent de liquide vaisselle utilisé en lave-vaisselle sans phosphate et sans agent de blanchiment, contenant :
    a) 10 à 60 % en poids en citrate,
    b) 0,5 à 20 % en poids d'acide dicarboxylique,
    caractérisé en ce que l'agent de liquide vaisselle utilisé en lave-vaisselle contient, rapporté à son poids total, 1 à 8 % en poids de phosphonate chélatant.
  2. Agent de liquide vaisselle utilisé en lave-vaisselle selon la revendication 1, caractérisé en ce que l'agent de liquide vaisselle utilisé en lave-vaisselle contient, rapporté à son poids total, contient de 12 à 50 % en poids, de préférence 15 à 40 % en poids et en particulier 15 à 30 % en poids en citrate.
  3. Agent de liquide vaisselle utilisé en lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de liquide vaisselle utilisé en lave-vaisselle selon contient de l'acide maléique en tant qu'acide dicarboxylique b).
  4. Agent de liquide vaisselle utilisé en lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de liquide vaisselle utilisé en lave-vaisselle contient, rapporté à son poids total, de 1,0 à 18 % en poids, de préférence de 2,0 à 16 % en poids et en particulier de 4,0 à 12 % en poids en acide dicarboxylique.
  5. Agent de liquide vaisselle utilisé en lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de liquide vaisselle utilisé en lave-vaisselle contient, rapporté à son poids total, de 2,0 à 20 % en poids, de préférence de 2,5 à 15 % en poids et en particulier de 2,5 à 10 % en poids en copolymère anionique, comprenant
    i) des monomères mono- ou polyinsaturés issus du groupe des acides carboxyliques
    ii) des monomères mono- ou polyinsaturés issus du groupe des acides sulfoniques
    iii) facultativement, d'autres monomères ioniques ou non ioniques.
  6. Agent de liquide vaisselle utilisé en lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de liquide vaisselle utilisé en lave-vaisselle contient, rapporté à son poids total, de préférence de 1,2 à 6 % en poids et en particulier de 1,5 à 4 % en poids de phosphonate.
  7. Agent de liquide vaisselle utilisé en lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de liquide vaisselle contient, rapporté à son poids total, un tensioactif non ionique dans des quantités allant de 0,1 à 15 % en poids, de préférence de 0,2 à 10 % en poids, de manière particulièrement préférée de 0,5 à 8 % en poids et en particulier de 1,0 à 6 % en poids.
  8. Agent de liquide vaisselle utilisé en lave-vaisselle selon l'une des revendications précédentes, caractérisé en ce que l'agent de liquide vaisselle contient un tensioactif A non ionique de la formule générale R1O(AlkO)xM(OAlk)yOR2, dans laquelle
    - R1 et R2 représentent indépendamment l'un de l'autre un radical alkyle ramifié ou non ramifié, saturé ou insaturé, le cas échéant hydroxylé, comportant 4 à 22 atomes de carbone ;
    - Alk représente un radical alkyle ramifié ou non ramifié comportant 2 à 4 atomes de carbone ;
    - x et y représentent indépendamment l'un de l'autre des valeurs comprises entre 1 et 70 ; et
    - M représente un radical alkyle issu du groupe comprenant le CH2, le CHR3, le CR3R4, le CH2CHR3 et le CHR3CHR4, dans lequel R3 et R4 représentent indépendamment l'un de l'autre un radical alkyle ramifié ou non ramifié, saturé ou insaturé, comportant 1 à 18 atomes de carbone.
  9. Agent de liquide vaisselle utilisé en lave-vaisselle sans phosphate et sans agent de blanchiment, contenant :
    a) 12 à 50 % en poids en citrate,
    b) 1,0 à 18 % en poids en acide maléique,
    c) 5 à 50 % en poids en carbonate,
    d) 1 à 8 % en poids en phosphonate chélatant.
  10. Procédé de nettoyage de vaisselle dans un lave-vaisselle, utilisant un agent de liquide vaisselle utilisé en lave-vaisselle selon l'une des revendications précédentes.
  11. Procédé selon la revendication 10, caractérisé en ce que le procédé de nettoyage de la vaisselle est exécuté à une température de matière tinctoriale inférieure à 60 °C.
EP09795393.9A 2008-12-15 2009-12-14 Agent de lavage pour lave-vaisselle Active EP2366007B1 (fr)

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DE102008061859A DE102008061859A1 (de) 2008-12-15 2008-12-15 Maschinelles Geschirrspülmittel
PCT/EP2009/067040 WO2010072603A1 (fr) 2008-12-15 2009-12-14 Agent de lavage pour lave-vaisselle

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US20110237482A1 (en) 2011-09-29
EP2366007A1 (fr) 2011-09-21
DE102008061859A1 (de) 2010-06-17

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