EP2185677B1 - Détergents - Google Patents

Détergents Download PDF

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Publication number
EP2185677B1
EP2185677B1 EP08803452A EP08803452A EP2185677B1 EP 2185677 B1 EP2185677 B1 EP 2185677B1 EP 08803452 A EP08803452 A EP 08803452A EP 08803452 A EP08803452 A EP 08803452A EP 2185677 B1 EP2185677 B1 EP 2185677B1
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Prior art keywords
automatic dishwashing
dishwashing agent
acid
weight
previous
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German (de)
English (en)
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EP2185677A1 (fr
Inventor
Johannes Zipfel
Nadine Warkotsch
Arnd Kessler
Christian Nitsch
Sven Müller
Luca Bellomi
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • 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
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • 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

Definitions

  • the present patent application describes detergents, in particular detergents for the machine cleaning of dishes.
  • This application relates in particular to liquid, low-alkaline and bleach-free automatic dishwashing detergents.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes.
  • a tableware that has been completely cleaned at first glance of food waste is then rated as not having any flaw if, after machine dishwashing, it still has discolorations which are based, for example, on the attachment of vegetable dyes to the dish surface.
  • 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. A limitation of the alkalinity of the automatic dishwashing detergent is therefore desirable from the user's point of view.
  • DE 10133137 discloses liquid aqueous machine dishwashing detergents which may contain copolymer and phosphorate.
  • the dishwashing detergent should, despite its bleach-free properties, have an improved cleaning performance compared with bleachable soiling without, at the same time, increasing damage to glassware. or ceramic surfaces.
  • the bleachable stains include, for example, stains caused by tea or vegetable dyes, for example from vegetables or fruits.
  • Preferred automatic dishwasher detergents according to the invention are therefore characterized in that the automatic dishwasher detergent has a pH (20 ° C.) between 9 and 11.5, preferably between 9.5 and 11.5.
  • Aqueous automatic dishwasher detergents are preferred according to the invention.
  • the water content of these aqueous automatic dishwashing agents is preferably between 10 and 80% by weight, preferably between 20 and 70% by weight and in particular between 30 and 60% by weight.
  • machine dishwashing detergents contain one or more builders.
  • the builders include in particular carbonates, phosphates, organic cobuilders and silicates.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances 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, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • 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.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Particularly preferred machine dishwasher detergents according to the invention contain citrate as one of their essential builders.
  • Machine dishwashing detergents characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention.
  • Citrate or citric acid have proved to be the most effective builders in addition to the phosphates, in combination with phosphonate, in particular 1-hydroxyethane-1,1-diphosphonic acid, and the sulfonic acid-containing copolymers with respect to the cleaning performance, such as the final rinse performance and, in particular, the scale inhibition.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • Automatic dishwashing detergents according to the invention can be prepared as builder crystalline layer-form silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • phosphates In addition to citrates, phosphates have proven to be the most effective builders in terms of cleaning performance. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • phosphates are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as detergents or cleaning agents in the context of the present application
  • preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of 2 to 40 wt .-%, preferably from 2 to 30 wt .-% and in particular from 3 to 25 wt .-%, particularly preferably from 3 to 15 wt .-%, each based on the Weight of washing or cleaning agent.
  • phosphate preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate
  • 2 to 40 wt .-% preferably from 2 to 30 wt .-% and in particular from 3 to 25 wt .-%, particularly preferably from 3 to
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • the content of silicates is less than 10 Wt .-%, preferably below 5 wt .-% and in particular below 2 wt .-% limited.
  • Particularly preferred automatic dishwasher detergents according to the invention are silicate-free.
  • the automatic dishwashing compositions according to the invention may contain the aforementioned builders both in the form of individual substances and in the form of substance mixtures of two, three, four or more builders.
  • the dishwashing detergent contains at least two builders from the group of the phosphates, carbonates and citrates, wherein the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably 2 to 50 wt .-%, preferably 5 to 40 wt .-% and in particular 10 to 30 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following tables: ingredient Recipe 1 Recipe 2 Recipe 3 Recipe 4 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 2 to 40 3 to 15 - - citrate - ** - 5 to 30 7 to 20 carbonate 3 to 20 4 to 15 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5
  • the agents according to the invention may contain alkali metal hydroxides.
  • These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
  • the automatic dishwashing compositions of the invention contain phosphonate (s).
  • the proportion by weight of the phosphonate, based on the total weight of the automatic dishwashing agent, is preferably more than 1.8% by weight, preferably more than 2.2% by weight and in particular more than 2.4% by weight of phosphonate.
  • the phosphonate content is preferably between 2 and 30 wt .-%, preferably between 2 and 20 wt .-%, particularly preferably between 2 and 15 wt .-% and in particular between 2 and 15 wt .-%.
  • the complexing phosphonates include a number of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriamine penta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. 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. Preference is given to using HEDP from the group of phosphonates.
  • 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
  • Liquid automatic dishwashing compositions which contain as phosphonate 1-hydroxyethane-1,1-diphosphonic acid (HEDP) are particularly preferred according to the invention.
  • HEDP phosphonate 1-hydroxyethane-1,1-diphosphonic acid
  • MGDA methylglycinediacetic acid
  • Preferred alternative cleaning agents contain MGDA in amounts above 10 wt .-%, preferably above 15 wt .-%, each based on the total weight of the automatic dishwashing detergent.
  • a third characteristic constituent of inventive dishwasher detergents containing phosphonate are the sulfonic acid-containing copolymers c), which in addition to sulfonic acid-containing monomer (s) comprise at least one unsaturated carboxylic acid.
  • the copolymers c) may have two, three, four or more different monomer units.
  • Preferred liquid automatic dishwasher detergents contain the polymer c) in amounts of 0.2 to 18 wt .-%, preferably 0.5 to 15 wt .-% and in particular 1.0 to 12 wt .-%, each based on the total weight of automatic dishwashing detergent.
  • 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-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salt
  • the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
  • metal ions preferably alkali metal ions and especially sodium ions.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group ii) and from 10 to 50% by weight of monomer from group i), in each case based on the polymer.
  • 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 .
  • Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following tables: ingredient Recipe 21 Recipe 22 Recipe 23 Recipe 24 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 2 to 40 2 to 30 2 to 30 3 to 15 carbonate 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5
  • the copolymers c) comprise, besides carboxyl-containing monomer and monomer containing sulfonic acid groups, 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, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C
  • a weight ratio of the components c) and b) of less than 3: 1 has proven to be advantageous.
  • the weight ratio of components c) and b) denotes the ratio of the weight proportions c) and b) of the total weight of the automatic dishwashing agent to one another.
  • the weight fraction of the phosphonate b) should therefore amount to at least one third of the weight fraction of the anionic polymer c).
  • the weight proportion of the phosphonate is thus at least 3 wt .-% of the total weight of the automatic dishwashing detergent.
  • Liquid automatic dishwashing detergent according to one of the preceding claims, characterized in that the weight ratio of the components c) and b) less than 3: 1, preferably less than 2.5: 1, more preferably less than 2: 1 and in particular between 2: 1 and 1: 5, are preferred according to the invention.
  • preferred dishwashing detergents according to the invention may contain surfactants.
  • surfactants has been found to be particularly advantageous in terms of cleaning performance and drying, the nonionic gave the best results from the group of non-ionic surfactants used with particular preference, anionic surfactants and amphoteric surfactants.
  • Anionic and amphoteric surfactants are preferably used in combination with defoamers or foam inhibitors.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general Formula RO (G) x , in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit with 5 or 6 C-atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • 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.
  • Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C9-11 alcohol containing 7 EO, C 13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical 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 alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Gained alcohol were used.
  • a particularly preferred 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 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol
  • at least 12 mol preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature.
  • nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Also, nonionic surfactants having waxy consistency at room temperature are preferred depending on their purpose.
  • 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% by weight and in particular more than 70% by weight, of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more 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 have the required low viscosity in aqueous solution and can be used according to the invention 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.
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical 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 from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 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.
  • R 1 and R 2 independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 independently of one another is selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 , but preferably is -CH 3
  • 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 ] j OR 2 in which R 1 and R 2 is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical 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 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.
  • 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 automatic dishwashing detergent contains, based on its total weight, nonionic surfactant in amounts of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight. % and in particular from 1.0 to 6 wt .-%.
  • Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following table: ingredient Recipe 29 Recipe 30 Recipe 31 Recipe 32 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 carbonate 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5
  • anionic or amphoteric surfactants preferably in combination with defoamers or foam inhibitors, can also be used in the machine dishwashing process according to the invention.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-16 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products of Shell Oil Company under the name DAN ® , are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable amphoteric surfactants are, for example, betaines or alkylamidoalkylamines.
  • Preferred amphoteric surfactants are the alkylbetaines of the formula A1, the alkylamidobetaines of the formula A2, the sulfobetaines of the formula A3 and the amidosulfobetaines of the formula A4, R 1 -N + (CH 3 ) 2 -CH 2 COO - (A1) R 1 -CO-NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 COO - (A2) R 1 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (A3) R 1 -CO-NH- (CH 2 ) 3 -N + (CH 3 ) 2 -CH 2 CH (OH) CH 2 SO 3 - (A4)
  • R 1 has the same meaning as in formula A.
  • amphoteric surfactants are the carbo-betaines, in particular the carbo-betaines of the formula A1 and A2, most preferably the alkylamido-betaines of the formula A2.
  • betaines and sulfobetaines are the following compounds designated as INCI: almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, caprylic / capramidopropyl betaines, carnitines, cetyl betaines, cocamidoethyl betaines, cocamidopropyl Betaines, cocamidopropyl hydroxysultaines, coco-betaines, coco-hydroxysultaines, coco / oleamidopropyl betaines, coco-sultaines, decyl betaines, dihydroxyethyl oleyl glycinates, dihydroxyethyl soy glycinates, dihydroxyethyl
  • a preferred amphoteric surfactant is cocamidopropyl betaine (cocoamidopropyl betaine).
  • a particularly preferred amphoteric surfactant is caprylic / Capramidopropyl Betaine (CAB), which is available for example under the trade name Tegotens ® B 810 from Th. Goldschmidt AG.
  • alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium laureth 5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodia
  • Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials.
  • preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R 2 SiO) x and are also referred to as silicone oils.
  • dishwashing compositions according to the invention may also contain enzymes. 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 as well as the further developments of the abovementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens . It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • 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.
  • the automatic dishwashing detergent based in each case on its total weight, contains from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight.
  • 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.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-form detergents, solutions of the enzymes, preferably as concentrated as possible, sparingly mixed with water and / or with stabilizers or other 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.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • 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.
  • Some exemplary formulations of preferred automatic dishwashing detergents according to the invention can be found in the following tables: ingredient Recipe 37 Recipe 38 Recipe 39 Recipe 40 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 carbonate 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5
  • Protease preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8
  • Amylase preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 water 10 to 80 20 to 70 30 to 70 30 to 70 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
  • the cleaning performance of automatic dishwashing detergents according to the invention can be improved by the addition of organic solvents.
  • the preferred subject of the present application are therefore automatic dishwashing detergents which, in addition to the other ingredients listed, furthermore contain at least one organic solvent.
  • Preferred liquid automatic dishwashing detergents are characterized in that the dishwashing agent, based on its total weight, organic solvent in amounts of 0.2 to 15 wt .-%, preferably 0.5 to 12 wt .-%, particularly preferably 1.0 to 10 Wt .-% contains.
  • 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, in particular 1,2-propanediol, 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,
  • the organic solvents from the group of the organic amines and / or the alkanolamines have proven to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance of bleachable soilings, in particular of 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.
  • the proportion by weight of alkanolamine in the total weight of preferred automatic dishwashing agent according to the invention is from 0.1 to 10% by weight, preferably from 0.2 to 8% by weight, preferably from 0.4 to 6% by weight and in particular from 1 to 5% by weight. %
  • Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following table: ingredient Recipe 45 Recipe 46 Recipe 47 Recipe 48 [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] [Wt .-%] tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 carbonate 3 to 20 3 to 20 3 to 20 4 to 15 phosphonate > 1.5 > 1.5 > 1.5 > 1.5
  • Amylase preparation 0.1 to 12 0.2 to 10 0.5 to 8 0.5 to 8 alkanolamine 0.1 to 10 0.2 to 8 0.4 to 6 1 to 5 water 10 to 80 20 to 70 30 to 70 30 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add
  • Glass corrosion inhibitors are further preferred ingredients of automatic dishwashing detergents according to the invention. Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • the spectrum of the inventively preferred zinc salts preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or are not soluble, ie have a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l, to those salts which have 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 includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • the glass corrosion inhibitor at least one zinc salt of an inorganic or organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight.
  • the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 5 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • thickening agents are preferably added to these agents.
  • a large group of particularly preferred thickeners are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickening agents from these classes of compounds are widely available commercially and are sold for example under the trade name Acusol ® -810, Acusol ® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ®-GT-282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ® -xg (anionic heteropolysaccharide based on ⁇ -D-glucose, D-mannose, D- glucuronic acid, Schoner GmbH), -XN deuteron ® (non-ionic polysacc
  • thickening agents examples include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, gum ethers, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids , Polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas.
  • the machine dishwashing detergents according to the invention contain the thickener in amounts of between 0.1 and 8% by weight, preferably between 0.2 and 6% by weight and more preferably between 0.4 and 4% by weight. % based on the total weight of the automatic dishwashing detergent
  • the pourability and settling stability of the liquid automatic dishwasher detergents according to the invention can, in addition to the thickeners, also be influenced by the ratio of the potassium and sodium ions in this agent.
  • Machine dishwashing agents according to the invention which have a ratio of potassium to sodium ions above 1: 1, preferably above 2: 1, more preferably above 4: 1 and in particular above 8.1, have proved to be advantageous.
  • the packaging and packaging of agents according to the invention is carried out using the water-soluble or water-insoluble packaging materials known to the person skilled in the art.
  • the packaging means may be one, two or more chamber container.
  • water-insoluble two- or multi-chamber container typically have a total volume of between 100 and 5000 ml, preferably between 200 and 2000 ml.
  • the volume of the individual chambers is preferably between 50 and 2000 ml, preferably between 100 and 1000 ml.
  • Preferred two- or multi-chamber containers have a bottle shape.
  • the automatic dishwashing compositions according to the invention are present in these packaging materials, preferably in the form of separate partial formulations. These sub-formulations do not form a common phase boundary, but rather are located in separate regions of the packaging means and have different compositions from each other.
  • the two-chamber or multi-chamber container preferably has at least one spout, which can be configured, for example, in the form of a common spout for all the means contained in the bottle.
  • the weights given above for the washing and cleaning ingredients and the pH values refer to the automatic dishwashing detergent obtained by combining all the partial formulations.
  • individual sub-formulations contained in the chambers may deviate from the characteristics characterizing the machine dishwashing detergent according to the invention, provided that only the combination of all sub-formulations comprises a machine dishwashing detergent according to the invention having the above-mentioned characterizing and optionally preferred Features.
  • individual sub-formulations may be free of phosphonate or anionic copolymer, provided that the combination of all sub-formulations results in a machine dishwashing detergent which comprises> 1.5% by weight of phosphonate and 0.1 to 20% by weight of anionic copolymer comprising i) unsaturated carboxylic acid (n) and ii) contains sulfonic acid group-containing (s) monomer (s).
  • pH value of the low-alkaline dishwashing detergents according to the invention mentioned above also relate to the pH of the overall composition and not to the pH of any partial formulations.
  • individual partial formulations may have pH values (20 ° C.) below 8 or above 12, provided that the combination of the partial formulations results in a machine dishwashing detergent which has a pH (20 ° C.) between 8 and 12.
  • Machine dishwashing detergent 1 Machine dishwashing detergent 2 ingredient Partial formulation 1 [% by weight] Partial formulation 2 [% by weight] Partial formulation 1 [% by weight] Partial formulation 2 [% by weight] tripolyphosphate 3 to 40 3 to 30 3 to 30 2 to 15 carbonate 0 to 10 3 to 20 - 4 to 15 phosphonate 0 to 4 2 to 6 0 to 4 2 to 6
  • Nonionic surfactant 0.1 to 15 0 to 4 0.5 to 8 - Enzyme preparation 0.1 to 12 - 0.5 to 8 - water 10 to 80 20 to 70 30 to 70 30 to 70 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 Machine
  • the automatic dishwasher detergents according to the invention show their advantageous cleaning properties, in particular also low-temperature cleaning processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that these processes are carried out at temperatures up to a maximum of 55 ° C., preferably up to a maximum of 50 ° C.
  • compositions according to the invention are distinguished from conventional automatic dishwashing agents by an improved cleaning performance on bleachable soiling.
  • An object of the present application is therefore also the use of a machine dishwashing detergent according to the invention for cleaning bleachable stains in automatic dishwashing.
  • soiled dishes were rinsed in a dishwashing machine (Miele G 698) at a water hardness of 21 ° dH and a temperature of 50 ° C. with 33 ml of the automatic dishwashing detergent listed in the table below.

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Claims (14)

  1. Agent pour le lavage mécanique de la vaisselle, liquide, faiblement alcalin et exempt d'agent de blanchiment, possédant une valeur de pH (20 °C) entre 8 et 12, contenant :
    a) de 10 à 60 % en poids de builder ;
    b) de plus de 1,5 % en poids de phosphonate ;
    c) de 0,1 à 20 % en poids, de copolymère anionique, comprenant :
    i) un ou plusieurs acides carboxyliques insaturés ;
    ii) un ou plusieurs monomères contenant un ou plusieurs groupes d'acides sulfoniques.
  2. Agent liquide pour le lavage mécanique de la vaisselle selon la revendication 1, caractérisé en ce que l'agent pour le lavage mécanique de la vaisselle présente une valeur de pH (20 °C) entre 9 et 11,5, de préférence entre 9,5 et 11,5.
  3. Agent liquide pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent pour le lavage de la vaisselle contient au moins deux builder choisies parmi le groupe des phosphates, des carbonates et des citrates, la fraction pondérale de ces builders, rapportée au poids total de l'agent pour le lavage mécanique de la vaisselle s'élève de 2 à 50 % en poids, de préférence de 5 à 40 % en poids et en particulier de 10 à 30 % en poids.
  4. Agent liquide pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent pour le lavage mécanique de la vaisselle contient, rapporté à son poids total, plus de 1,8 % en poids, de préférence plus de 2,2 % en poids et en particulier plus de 2,4 % en poids, de phosphonate.
  5. Agent liquide pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient, à titre de phosphonate b), de l'acide 1-hydroxyéthane-1,1-diphosphonique (HEDP).
  6. Agent liquide pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent pour le lavage mécanique de la vaisselle contient, rapporté à son poids total, 0,2 à 18 % en poids, de préférence 0,5 à 15 % en poids et en particulier 1,0 à 12 % en poids du copolymère anionique c).
  7. Agent liquide pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent pour le lavage mécanique de la vaisselle contient, à titre de polymère anionique c), un copolymère comprenant :
    i) un ou plusieurs acides carboxyliques insaturés ;
    ii) un ou plusieurs monomères contenant un ou plusieurs groupes d'acides sulfoniques ;
    iii) un ou plusieurs autres monomères non ionogènes.
  8. Agent liquide pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que la proportion des constituants c) et b) est inférieure à 2:1, de préférence inférieure à 1,8:1, de manière particulièrement préférée inférieure à 1,5:1 et en particulier s'élève entre 1,5:1 et 1:5.
  9. Agent liquide pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent pour le lavage de la vaisselle contient, rapporté à son poids total, un agent tensioactif non ionique dans des quantités 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.
  10. Agent liquide pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent pour le lavage de la vaisselle contient, rapporté à son poids total, une ou plusieurs enzymes dans des quantités de 0,1 à 12 % en poids, de préférence de 0,2 à 10 % en poids et en particulier de 0,5 à 8 % en poids.
  11. Procédé pour le lavage de la vaisselle dans un lave-vaisselle, en mettant en oeuvre un agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 10.
  12. Procédé selon la revendication 11, caractérisé en ce qu'au cours du processus de lavage, on n'introduit de manière dosée aucun adoucisseur d'eau supplémentaire et aucun agent de rinçage supplémentaire dans l'espace interne du lave-vaisselle.
  13. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que ce procédé est mis en oeuvre à des températures s'élevant au maximum à 55 °C, de préférence au maximum à 50°C.
  14. Utilisation d'un agent de lavage mécanique pour la vaisselle selon l'une quelconque des revendications 1 à 10 pour le nettoyage de saletés blanchissables lors du lavage mécanique de la vaisselle.
EP08803452A 2007-09-10 2008-09-01 Détergents Active EP2185677B1 (fr)

Priority Applications (1)

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PL08803452T PL2185677T3 (pl) 2007-09-10 2008-09-01 Środek czyszczący

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DE102007042907A DE102007042907A1 (de) 2007-09-10 2007-09-10 Reinigungsmittel
PCT/EP2008/061469 WO2009033973A1 (fr) 2007-09-10 2008-09-01 Détergents

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EP2185677A1 EP2185677A1 (fr) 2010-05-19
EP2185677B1 true EP2185677B1 (fr) 2011-06-29

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US (1) US20100222247A1 (fr)
EP (1) EP2185677B1 (fr)
KR (1) KR101520514B1 (fr)
AT (1) ATE514768T1 (fr)
DE (1) DE102007042907A1 (fr)
ES (1) ES2367089T3 (fr)
PL (1) PL2185677T3 (fr)
WO (1) WO2009033973A1 (fr)

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JP5503545B2 (ja) * 2007-11-09 2014-05-28 ザ プロクター アンド ギャンブル カンパニー モノカルボン酸単量体、ジカルボン酸単量体、およびスルホン酸基含有単量体を含む洗浄用組成物
JP5750265B2 (ja) * 2008-03-31 2015-07-15 株式会社日本触媒 スルホン酸基含有マレイン酸系水溶性共重合体水溶液および乾燥して得られる粉体
DE102011079146A1 (de) * 2011-07-14 2013-01-17 Henkel Ag & Co. Kgaa Klarspül- und Geschirrspülmittel
US20150107629A1 (en) * 2013-10-22 2015-04-23 Church & Dwight Co., Inc. Enzyme-containing automatic dishwashing booster/rinse aid composition, kit containing the same and method of using the same
US9969959B2 (en) * 2014-03-07 2018-05-15 Ecolab Usa Inc. Detergent composition that performs both a cleaning and rinsing function
MX2016011249A (es) * 2014-03-07 2016-11-30 Ecolab Usa Inc Composicion de detergente que realiza funciones tanto de limpieza como de enjuague.
US9796947B2 (en) * 2014-03-07 2017-10-24 Ecolab Usa Inc. Detergent composition comprising a polymer that performs both a cleaning and rinsing function
EP3050954A1 (fr) * 2015-02-02 2016-08-03 The Procter and Gamble Company Nouvelle utilisation de polymères sulfonés
US20180216041A1 (en) 2015-07-06 2018-08-02 Ecolab Usa Inc. Stain removal through novel oxidizer and chelant combination
WO2018202383A1 (fr) 2017-05-04 2018-11-08 Unilever N.V. Composition de détergent
CA3081788C (fr) 2017-11-14 2022-08-09 Ecolab Usa Inc. Compositions detergentes caustiques a liberation controlee de matieres solides
EP4007803A1 (fr) 2019-09-27 2022-06-08 Ecolab USA Inc. Détergent et produit de rinçage concentré 2-en-1 pour lave-vaisselle
US20210222091A1 (en) * 2020-01-22 2021-07-22 Dune Sciences, Inc. Self-preserving liquid laundry detergent formulation
EP4428139A1 (fr) 2023-03-08 2024-09-11 Giovanni Bozzetto S.p.A. Derives de phosphonate de polyaminomethylene a faible teneur en phosphore et a proprietes sequestrantes et dispersantes, utilisations et procedes associes pour leur preparation

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DE4321429A1 (de) * 1993-06-28 1995-01-05 Henkel Kgaa Geschirrspülmittel mit biologisch abbaubarer Builderkomponente I
GB2285052A (en) * 1993-12-23 1995-06-28 Procter & Gamble Detergent composition
EP0821722B1 (fr) * 1995-04-17 2000-07-26 The Procter & Gamble Company Preparation et utilisation de particules composites contenant du peroxyde de diacyle
US6225277B1 (en) * 1995-10-09 2001-05-01 The Procter & Gamble Company Hard surface cleaning compositions
AU2001249529A1 (en) * 2000-03-29 2001-10-08 National Starch And Chemical Investment Holding Corporation Polymers that inhibit calcium phosphate and calcium carbonate scale in autodish applications
DE10050622A1 (de) * 2000-07-07 2002-05-02 Henkel Kgaa Klarspülmittel II a
US6521576B1 (en) * 2000-09-08 2003-02-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Polycarboxylic acid containing three-in-one dishwashing composition
DE10133137A1 (de) * 2001-10-30 2003-01-30 Henkel Kgaa Wäßrige"3in1"-Geschirrspülmittel
DE102004044411A1 (de) * 2004-09-14 2006-03-30 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophob modifizierte Polycarboxylate
DE102007006630A1 (de) * 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel

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Publication number Publication date
WO2009033973A1 (fr) 2009-03-19
KR101520514B1 (ko) 2015-05-18
ES2367089T3 (es) 2011-10-28
DE102007042907A1 (de) 2009-03-12
US20100222247A1 (en) 2010-09-02
EP2185677A1 (fr) 2010-05-19
KR20100061669A (ko) 2010-06-08
ATE514768T1 (de) 2011-07-15
PL2185677T3 (pl) 2011-11-30

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