EP2480647A1 - Détergent pour lave-vaisselle - Google Patents

Détergent pour lave-vaisselle

Info

Publication number
EP2480647A1
EP2480647A1 EP10749666A EP10749666A EP2480647A1 EP 2480647 A1 EP2480647 A1 EP 2480647A1 EP 10749666 A EP10749666 A EP 10749666A EP 10749666 A EP10749666 A EP 10749666A EP 2480647 A1 EP2480647 A1 EP 2480647A1
Authority
EP
European Patent Office
Prior art keywords
acid
dishwashing detergent
detergent according
total weight
machine dishwashing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10749666A
Other languages
German (de)
English (en)
Inventor
Dorota SENDOR-MÜLLER
Johannes Zipfel
Arnd Kessler
Christian Nitsch
Thorsten Bastigkeit
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2480647A1 publication Critical patent/EP2480647A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • 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
    • 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
    • C11D3/3796—Amphoteric polymers or zwitterionic polymers

Definitions

  • the present application describes automatic dishwasher detergents
  • bleaching agents are used in automatic dishwashing detergents. To activate these bleaches and to achieve an improved bleaching effect when cleaned at temperatures of 60 ° C and below, contain mechanical
  • Dishwashing detergent generally also bleach activators or bleach catalysts, in particular, the bleach catalysts have proven to be particularly effective.
  • bleaching agents are due to incompatibilities with other washing or cleaning active ingredients, such as enzymes, or due to
  • a technical possibility to improve the cleaning performance of automatic dishwashing detergents, in particular bleach-free automatic dishwasher detergents, is to increase the alkalinity of these detergents.
  • the cleaning as for the rinse aid success is to increase the alkalinity of these detergents.
  • the essential ingredient in this regard is the automatic dishwashing agent intended for the private consumer, therefore builders.
  • these builders increase the alkalinity of the cleaning liquor, whereby fats and oils are emulsified and saponified with increasing alkalinity, and on the other hand reduce the water hardness of the cleaning liquor by complexing the calcium ions contained in the aqueous liquor.
  • the alkali metal phosphates have proven, for this reason the
  • phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents
  • their use is from the standpoint of Environmental protection, however, is not without its problems, since a substantial part of the phosphate enters the water via household wastewater and plays a critical role in overfertilisation, especially in stagnant water (lakes, barrages).
  • eutrophication the use of pentasodium triphosphate in laundry detergents in a number of countries, eg USA, Canada, Italy, Sweden, Norway, has been considerably reduced by law and regulations. completely prohibited in Switzerland. In Germany, detergents since 1984 may contain no more than 20% of this builder.
  • nitrilotriacetic acid especially sodium aluminosilicates (zeolites) are used as phosphate substitutes or substitutes in textile detergents.
  • these substances are not suitable for use in automatic dishwashing detergents for various reasons.
  • alkali metal phosphates in automatic dishwashing detergents therefore, a number of substitutes are discussed in the literature, of which the citrates are particularly noteworthy.
  • Phosphate-free automatic dishwashing detergents which, in addition to a citrate, furthermore contain carbonates, bleaches and enzymes, are described, for example, in European patents EP 662 1 17 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).
  • MGDA methylglycine diacetic acid
  • Machine dishwashing detergents containing MGDA are described, for example, in European patent EP 906 407 B1 (Reckitt Benckiser) or in European patent application EP 1 1 13 070 A2 (Reckitt Benckiser).
  • a first subject of the present application is a phosphate-free machine
  • Dishwashing detergent containing:
  • Amphoteric polymers in the sense of the present application furthermore have, in addition to a positively charged group in the polymer chain, also negatively charged groups or
  • These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • amphoteric polymers contain as monomer unit a compound of the general formula
  • R and R 4 independently of one another are H or a linear or branched one
  • R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3.
  • X represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • Preferred radicals R and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • amphoteric polymers which have a cationic monomer unit of the above general formula in which R and R 4 are H, R 2 and R 3 are methyl and x and y are each 1.
  • R and R 4 are H
  • R 2 and R 3 are methyl
  • x and y are each 1.
  • amphoteric polymers contain a monomer unit of the general formula
  • R1 HC C R2-C (0) -NH- (CH2) -N + R3R4R5
  • R, R 2 , R 3 , R 4 and R 5 independently of one another, denote a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 - CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 - CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H and x is an integer between 1 and 6.
  • amphoteric polymers which have a cationic monomer unit of the above general formula in which R is H and R 2 , R 3 , R 4 and R 5 are methyl and x is 3.
  • H 2 C C (C H 3 ) -C (O) -NH- (C H 2 ) X -N + (CH 3 ) 3
  • amphoteric polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived for example from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated
  • Phosphonates the linear or branched, saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates.
  • Monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred usable amphoteric polymers are from the group of
  • Alkylacrylamide / acrylic acid copolymers the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the
  • Carboxylic acids and optionally other ionic or nonionic monomers are optionally other ionic or nonionic monomers.
  • amphoteric polymers are selected from the group of:
  • Ammonium salts the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyltrialkylammonium chloride and dimethyl (diallyl) ammonium chloride.
  • amphoteric polymers are selected from the group of methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) on
  • amphoteric polymers from the group of:
  • Machine dishwashing agent is preferably 0.05 to 10 wt .-%, preferably 0.05 to 7 wt .-% and in particular 0.05 to 5 wt .-%.
  • Dishwashing agent ethylenediamine disuccinic acid (EDDS), preferred machine
  • Dishwashing detergents are characterized in that the automatic dishwashing agent, based on its total weight, contains 3.0 to 35 wt .-%, preferably 4.0 to 30 wt .-% and in particular 8.0 to 25 wt .-% ethylenediamine disuccinic acid. Machinery
  • Dishwashing compositions containing ethylenediamine disuccinic acid as a complexing agent are described, for example, in International Patent Application WO 2006/029806 A1 (BASF).
  • ethylenediamine disuccinic acid includes not only the free acids but also their salts, for example their sodium or potassium salts
  • the weight fraction of ethylenediamine disuccinic acid used according to the invention is to be adjusted to the weight fraction of the free acid, that is, to be converted from the proportion by weight of the salt to the proportion by weight of the acid.
  • Preferred automatic dishwasher detergents according to the invention are of low alkalinity and have a pH (10% solution, 20 ° C.) of between 9 and 11.5, preferably between 9.5 and 11.5.
  • the automatic dishwashing agents according to the invention preferably contain further
  • a first group of useful builders are the inorganic builders, in particular the carbonates and silicates.
  • Dishwashing detergent characterized in that the automatic dishwashing agent based on its total weight, 2.0 to 50 wt .-% (hydrogen) carbonate, preferably 4.0 to 45 wt .-% (hydrogen) carbonate and in particular 8.0 to 40 wt .-% (hydrogen) carbonate, are preferred in the invention.
  • the group of preferred silicates includes crystalline layered silicates as well as amorphous silicates.
  • automatic dishwasher detergents according to the invention preferably contain no zeolites.
  • crystalline layered silicates of general formula NaMSi be x 0 2x + i ⁇ y H 2 0 used wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, particularly preferred values x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the cleaning agents according to the invention preferably contain a proportion by weight of the crystalline layered silicate of the formula
  • Preferred automatic dishwasher detergents therefore comprise less than 8.0% by weight of silicate, particularly preferably less than 6.0% by weight of silicate and in particular less than 4.0% by weight of silicate, ie for example between 0.1 and 4, 0 wt .-% silicate.
  • 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.
  • a particularly preferred ingredient of the invention is the citrate.
  • the term "citrate” also encompasses citric acid and its salts, in particular their alkali metal salts,
  • Particularly preferred automatic dishwashing agents according to the invention contain citrate, preferably sodium citrate, in amounts of 12 to 50% by weight, preferably 15 to 40% by weight in particular 15 to 30 wt .-%, each based on the total weight of the automatic dishwashing detergent.
  • 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, as well as mixtures of these.
  • NTA nitrilotriacetic acid
  • the free acids typically also have the property of a
  • Acid component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • succinic acid and thus also serve to set a lower and milder pH of detergents or cleaners.
  • Glutaric acid Glutaric acid, adipic acid, gluconic acid and any mixtures of these.
  • the complex-forming phosphonates include, in addition to the 1-hydroxyethane-1, 1-diphosphonic acid a number of different compounds such as
  • Diethylenetriaminepenta methylenephosphonic acid
  • DTPMP Diethylenetriaminepenta
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, wherein the disodium salt neutral and the
  • Tetrasodium salt alkaline reacts.
  • 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 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 dishwasher detergents which contain, as phosphonates, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylene triamine penta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylene triamine penta
  • Dishwashing detergents contain two or more different phosphonates.
  • the proportion by weight of the phosphonates in the total weight of automatic dishwashing detergents according to the invention is preferably 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, oc-chloroacrylic acid, oc-cyanoacrylic acid, crotonic acid, oc-phenyl-acrylic acid, maleic acid,
  • 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-methylbenzylamine.
  • 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.
  • 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 detergents are characterized in that the copolymers Molar masses of 2000 to 200,000 gmol 1 , preferably from 4000 to 25,000 gmol 1 and in particular from 5000 to 15,000 gmol "1 have.
  • polymeric sulfonates in addition
  • Carboxyl-containing monomer and sulfonic acid-containing monomer further 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 preferably monomers of the general formula
  • R (R 2 ) C C (R 3 ) -XR 4 used, in which R to R 3 are independently -H, -CH 3 or -C 2 H 5 , X is an optional spacer group selected is from -CH 2 -, -C (0) 0- and -C (0) -NH-, and R 4 is a straight or branched chain saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
  • 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, oc-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • Machine dishwashing detergent comprising at least one anionic copolymer
  • Total weight of the automatic dishwashing agent is preferably 2.0 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 2.5 to 10 wt .-%.
  • Some exemplary formulations for preferred phosphate-free automatic dishwasher detergents according to the invention can be found in Table 6 below:
  • Anionic copolymer comprising
  • Preferred automatic dishwasher detergents contain, as further constituents, surfactants,
  • nonionic and / or amphoteric surfactants preferably nonionic and / or amphoteric surfactants.
  • At least one of the surfactants used has a melting point above 25 ° C.
  • machine dishwashing detergents according to the invention in which at least one nonionic surfactant has a melting point above 28 ° C., preferably above 31 ° C.
  • Dishwashing agent is preferably from 0.1 to 15 wt .-%, preferably from 0.2 to 10 wt .-%, particularly preferably from 0.5 to 8 wt .-% and in particular from 1, 0 to 6 wt .-% ,
  • the deposit-inhibiting effect of automatic dishwasher detergents according to the invention is furthermore influenced by the structure of the nonionic surfactants used. So were particularly convincing results in terms of the
  • Another preferred ingredient of the automatic dishwashing compositions according to the invention are therefore nonionic surfactants of the general formula R -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 , in which
  • R and R 2 are a C 2 -26 alkyl
  • A, ⁇ ', A "and A'” independently represent a radical from the group
  • Machine dishwashing detergents according to the invention in which at least one of the nonionic surfactants has the abovementioned general formula, are preferred on account of their better coating appearance.
  • Hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22
  • Carbon atoms further having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, wherein x for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60 stands.
  • surfactants of the formula R 0 [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 Carbon atoms or mixtures thereof, R 2 is a linear or branched
  • Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands.
  • nonionic surfactants include, for example, the C 2 -26 fatty alcohol (PO) i (EO) i 5 . 4o-2-hydroxyalkyl ethers, in particular also the C 8 -io-fatty alcohol (PO) i (EO) 22 -2-hydroxydecyl ethers.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 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-methyl-2-butyl radical, x is Values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5.
  • k and j represent values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R 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 are 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.
  • R 0 [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R, 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 and R 2 Have 9 to 14 carbon atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactants of the general formula R -CH (OH) CH 2 O- (AO) w -R 2 have proved to be particularly effective, in which
  • R is a linear or branched, saturated or mono- or polyunsaturated C 6 - 2 4 represents alkyl or alkenyl radical;
  • R 2 is a linear or branched hydrocarbon radical having from 2 to 20 carbon atoms
  • A is a radical from the group CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), and w is from 10 to 120, preferably from 10 to 80, in particular from 20 to 40
  • the group of these nonionic surfactants includes, for example, the C 4 . 22 fatty alcohol (EO) i 0 -8o-2-hydroxyalkyl ethers, in particular also the C 8 -i 2 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4 . 22 fatty alcohol (EO) 40 -8o-2-hydroxyalkyl ethers
  • Automatic dishwashing detergents preferred according to the invention are free of anionic surfactants.
  • Nonionic surfactant of the general formula C 4 . 2 2 fatty alcohol (EO) i 0 -8o-2-hydroxyalkyl ethers
  • the automatic dishwashing compositions according to the invention preferably contain further washing and cleaning-active ingredients, in particular active ingredients from the group of enzymes
  • 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
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • Particularly preferred automatic dishwasher detergents also contain enzyme (s), preferably protease and / or amylase, in particular amylase.
  • 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 oc-amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens, from ⁇ . stearothermophilus, from Aspergillus niger and A. oryzae, as well as those improved for use in detergents and cleaners
  • lipases or cutinases are also usable according to the invention.
  • lipases or cutinases 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, those originally from Humicola lanuginosa
  • enzymes can be used which are termed hemicellulases
  • mannanases xanthan lyases
  • pectin lyases pectinases
  • pectin esterases pectate lyases
  • xyloglucanases xylanases
  • pullulanases and ⁇ -glucanases.
  • 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.
  • oxidases oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, more preferably aromatic, enzyme-interacting compounds to enhance the activity of the respective oxidoreductases (enhancers) or to react at greatly varying redox potentials between the oxidizing enzymes and the
  • a preferred machine dishwashing detergent according to the invention is characterized in that the dishwashing detergent, 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 .-%.
  • 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.
  • 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, more preferably between 0.4 and 20% by weight and
  • Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred.
  • oxygen bleaches being preferred.
  • the compounds which serve as bleaches and deliver in water H 2 O 2 the sodium percarbonate, the
  • Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate.
  • the weight fraction of the bleaching agent based on the total weight of the washing or cleaning agent, is in preferred Embodiments between 2.0 and 30 wt .-%, preferably between 4.0 and 20 wt .-% and in particular between 6.0 and 15 wt .-%.
  • dishwasher detergents according to the invention can be used as bleach activators.
  • TAED tetraacetylethylenediamine
  • Automatic dishwashing detergent characterized in that it is a bleach activator bleach activator from the group of acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention.
  • bleach activators in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 10% by weight, especially 0.5 to 8% by weight and more preferably 1, 0 to 6 Wt .-%, used.
  • Machine dishwashing detergents preferably at least one
  • Bleach catalyst These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligand (s) with the
  • ligands are used, having the nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
  • suitable bleach catalyst (s) in the compositions of the invention which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9
  • Automatic dishwashing detergent characterized in that it further comprises a
  • Bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me 3 -TACN) or 1, 2, 4,7- tetramethyl-1, 4,7-triazacyclononane (Me 4 -TACN) are preferred according to the invention, as by the aforementioned
  • Bleaching catalysts, in particular the cleaning result can be significantly improved.
  • the abovementioned bleach-enhancing transition metal complexes are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0, 01 wt .-% to 0.30 wt .-%, each based on the total weight of
  • bleach catalyst-containing agent used. In special cases, however, more can be done
  • Bleaching catalyst can be used.
  • Phosphonate 1 0 to 8.0 1, 2 to 6.0 1, 2 to 6.0 1, 5 to 4.0
  • Amphoteric polymer 0.05 to 10 0.05 to 7.0 0.05 to 5.0 0.05 to 5.0
  • Enzyme preparation 0, 1 to 12 0.2 to 10 0.2 to 10 0.5 to 8.0
  • nonionic surfactant of the general formula C 4 . 2 2 fatty alcohol (EO) i 0 -8o-2-hydroxyalkyl ethers
  • 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.
  • preferred automatic dishwasher detergents according to the invention contain, based on their total weight, a water content of preferably 20 to 70% by weight, preferably 30 and 60% by weight and in particular 35 and 55% by weight.
  • 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 multiphasic agents may be the same or different
  • 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. Especially preferred are two- or more-phase tablets, for example
  • Two-layer tablets in particular two-layer tablets with a trough and a molded body located in the trough.
  • Automatic dishwashing agents preferred according to the invention are in the form of a tablet, preferably in the form of a multilayer tablet.
  • 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 on the
  • 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.
  • Metering units are particularly preferred to have a water-soluble coating.
  • disintegration aids so-called tablet disintegrants
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • PVP polyvinylpyrrolidone
  • natural polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • 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.
  • Disintegrating agents based on cellulose are used as preferred disintegrating agents, so that preferred washing or cleaning agents comprise such a disintegrating agent
  • Cellulose base in amounts of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%.
  • the cellulose used as a disintegration aid is 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-%.
  • the particle sizes of such disintegrating agents are generally above 200 ⁇ , preferably at least 90 wt .-% between 300 and 1600 ⁇ and in particular at least 90 wt .-% between 400 and 1200 ⁇ .
  • Preferred disintegration aids preferably a disintegration aid
  • Cellulose base preferably in granular, cogranulated or compacted form, are in the disintegrating agent-containing agents in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 Wt .-% 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.
  • Acidifiers which release carbon dioxide from the alkali salts in aqueous solution are, for example, citric acid.
  • Another object of the present application is a method for cleaning dishes in a dishwasher, using a machine dishwashing agent according to the invention, wherein the automatic dishwashing detergent preferably metered during the passage of a dishwasher, before the main wash cycle or in the course of the main wash cycle in the interior of a dishwasher become.
  • the automatic dishwashing detergent preferably metered during the passage of a dishwasher, before the main wash cycle or in the course of the main wash cycle in the interior of a dishwasher become.
  • agent according to the invention in the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber of the dishwasher in the interior of the dishwasher. In the course of the cleaning process preferably no additional water softener and no additional rinse aid is dosed into the interior of the dishwasher.
  • a kit for a dishwasher comprising
  • the dishwasher detergents according to the invention exhibit their advantageous cleaning and drying properties, in particular also in low-temperature cleaning processes.
  • 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.
  • compositions according to the invention are distinguished from conventional automatic dishwashing compositions by reduced deposit formation.
  • a dishwasher detergent according to the invention for reducing the formation of deposits on glass surfaces in automatic dishwashing is a further subject matter of the present application.

Abstract

L'invention concerne des détergents pour lave-vaisselle sans phosphate, qui contiennent 0,05 à 20 % en poids d'un polymère amphotère, ainsi que 2 à 40 % en poids d'acide éthylènediamine-disuccinique. Les détergents pour lave-vaisselle selon l'invention se caractérisent par une remarquable inhibition des dépôts, ainsi que par un bon pouvoir nettoyant et une bonne performance de rinçage.
EP10749666A 2009-09-21 2010-09-08 Détergent pour lave-vaisselle Withdrawn EP2480647A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009029636A DE102009029636A1 (de) 2009-09-21 2009-09-21 Maschine Geschirrspülmittel
PCT/EP2010/063177 WO2011032870A1 (fr) 2009-09-21 2010-09-08 Détergent pour lave-vaisselle

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EP2480647A1 true EP2480647A1 (fr) 2012-08-01

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US (1) US20120178663A1 (fr)
EP (1) EP2480647A1 (fr)
KR (1) KR20120083351A (fr)
DE (1) DE102009029636A1 (fr)
WO (1) WO2011032870A1 (fr)

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JP2014521770A (ja) * 2011-07-27 2014-08-28 ザ プロクター アンド ギャンブル カンパニー 多相液体洗剤組成物
CN103849498A (zh) * 2012-11-29 2014-06-11 埃科莱布美国股份有限公司 清洗添加剂及使用该清洗添加剂的清洗方法

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE169331T1 (de) * 1992-03-10 1998-08-15 Rohm & Haas Verwendung von wasserlöslichen polymeren in reinigungsmittelzusammensetzungen und für solche anwendungen geeignete wasserlösliche polymere
DE4232170C2 (de) 1992-09-25 1999-09-16 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
DE4315048A1 (de) 1993-04-01 1994-10-06 Henkel Kgaa Verfahren zur Herstellung stabiler, bifunktioneller, phosphat-, metasilikat- und polymerfreier niederalkalischer Reinigungsmitteltabletten für das maschinelle Geschirrspülen
AU6413096A (en) * 1995-07-13 1997-02-10 Joh. A. Benckiser Gmbh Dish washer product in tablet form
ATE205250T1 (de) 1996-06-21 2001-09-15 Reckitt Benckiser Nv Mgda-haltige maschinengeschirrspülmittel niederer alkalität
EP0835925A3 (fr) * 1996-09-09 1999-01-27 Unilever N.V. Compositions pour lave-vaisselle contenant des polymères amphotères
ATE277998T1 (de) * 1997-07-23 2004-10-15 Unilever Nv Maschinengeschirrspülmittel enthaltend wasserlösliche kationische oder amphotere polymere
US6599871B2 (en) * 1997-08-02 2003-07-29 The Procter & Gamble Company Detergent tablet
DE10153554A1 (de) * 2001-07-07 2003-05-15 Henkel Kgaa Wäßrige "3in1"-Geschirrspülmittel II
US6974790B2 (en) * 2003-11-06 2005-12-13 Colgate-Palmolive Company Cleaning compositions in the form of a tablet
GB2409207B (en) * 2003-12-20 2006-08-09 Reckitt Benckiser Nv Use of metal complex compounds as oxidation catalysts
ES2293198T3 (es) * 2004-01-12 2008-03-16 THE PROCTER & GAMBLE COMPANY Pastillas con resistencia a la rotua mejorada.
DE102004005344A1 (de) * 2004-02-04 2005-09-01 Henkel Kgaa Maschinelles Geschirrspülmittel ####
DE102004044411A1 (de) 2004-09-14 2006-03-30 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophob modifizierte Polycarboxylate
DE102004045685A1 (de) * 2004-09-17 2006-04-06 Henkel Kgaa Reinigungsmittelkomponente
ATE532847T1 (de) * 2007-03-20 2011-11-15 Procter & Gamble Verfahren zum reinigen von wäsche oder harten oberflächen
DE102008063801A1 (de) * 2008-12-19 2010-06-24 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2011032870A1 *

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US20120178663A1 (en) 2012-07-12
KR20120083351A (ko) 2012-07-25
WO2011032870A1 (fr) 2011-03-24
DE102009029636A1 (de) 2011-03-24

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