EP2480645A1 - Détergent pour lave-vaisselle - Google Patents

Détergent pour lave-vaisselle

Info

Publication number
EP2480645A1
EP2480645A1 EP10749664A EP10749664A EP2480645A1 EP 2480645 A1 EP2480645 A1 EP 2480645A1 EP 10749664 A EP10749664 A EP 10749664A EP 10749664 A EP10749664 A EP 10749664A EP 2480645 A1 EP2480645 A1 EP 2480645A1
Authority
EP
European Patent Office
Prior art keywords
weight
automatic dishwashing
acid
detergent according
dishwashing detergent
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Withdrawn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
EP10749664A
Other languages
German (de)
English (en)
Inventor
Dorota SENDOR-MÜLLER
Johannes Zipfel
Arnd Kessler
Christian Nitsch
Thorsten Bastigkeit
Thomas Eiting
Volker Blank
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 EP2480645A1 publication Critical patent/EP2480645A1/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Withdrawn legal-status Critical Current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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • This application relates to phosphate-free automatic dishwashing detergents which contain a combination of nonionic surfactants.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be completely free from food debris but also, for example, should have no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets.
  • Modern automatic dishwashing detergents fulfill these requirements by integrating cleansing, caring, water-softening and clear-rinsing active ingredients and are suitable for this purpose
  • 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 is therefore in the Literature discussed a number of substitutes, 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 therefore a builder-containing
  • Non-phosphate machine dishwashing detergent containing, in each case based on the
  • nonionic surfactant A a) 0.5 to 7.0% by weight of nonionic surfactant A b) 0.2 to 5.0 wt .-% of nonionic surfactant B having a melting point above 25 ° C, characterized in that the nonionic surfactant A has a melting point which is at least 5 ° C below the melting point of the nonionic surfactant B.
  • Melting point above 25 ° C are therefore preferably used.
  • machine dishwashing detergents according to the invention in which both nonionic surfactants A and B have a melting point above 28 ° C., preferably above 31 ° C.
  • the temperature difference between the melting points of the nonionic surfactants A and B is preferably at least 6 ° C and especially at least 8 ° C.
  • the deposit-inhibiting effect of automatic dishwashing agents according to the invention is, in addition to the melting points of the nonionic surfactants, also determined by their weight ratio.
  • the proportion by weight of the lower melting nonionic surfactant A based on the surfactant system of surfactants A and B, should be between 50 and 95% by weight.
  • dishwasher detergents according to the invention are preferred in which the weight fraction of nonionic surfactant A in the total amount of nonionic surfactants A and B is between 50 and 95% by weight, preferably between 55 and 90% by weight and in particular between 60 and 80 wt .-% is.
  • Dishwashing agent is preferably between 0.5 and 7.0 wt .-%, preferably between 1, 0 and 6.0 wt .-% and in particular between 2.0 and 5.0 wt .-%, while the nonionic surfactant B in Automatic dishwashing detergents according to the invention, based on the latter
  • Total weight preferably in amounts between 0.2 and 5.0 wt .-%, preferably between 0.5 and 4.0 wt .-%, preferably between 1, 0 and 3.0 wt .-% and in particular between 0, 5 and 2.5 wt .-% is included.
  • the deposit-inhibiting effect of automatic dishwashing detergents according to the invention is furthermore also due to the structure of the non-ionic detergents used Surfactants influenced. So were particularly convincing results in terms of the
  • a further preferred constituent of the automatic dishwashing detergents according to the invention are therefore nonionic surfactants of the general formula R -CH (OH) CH 2 O- (AO) w - (AO) x - (A'O) y - (A '"O) z - R 2 , in the
  • R and R 2 are a C 2 -26 alkyl
  • A, ⁇ ', A "and A'” independently represent a radical from the group
  • w, x, y and z independently represent values between 0.5 and 120, where x, y and / or z can also be 0.
  • Machine dishwashing detergents according to the invention in which at least one of the nonionic surfactants A or B 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 furthermore a linear or branched, saturated or
  • x stands for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • 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.
  • R 0 [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2
  • R and R 2 are independent each other for a linear or branched, saturated or single or multiple unsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 , but preferably -CH 3
  • 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 stands for a straight-chain or branched, saturated or mono- or polyunsaturated C6 -24 alkyl or alkenyl group;
  • 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 . 2 2 fatty alcohol (EO) 40 -8o-2-hydroxyalkyl ethers
  • Automatic dishwashing detergents preferred according to the invention are free of anionic surfactants.
  • the automatic dishwashing agents of the invention contain builders but no phosphate.
  • a first group of useful builders are the inorganic builders, in particular the carbonates and silicates.
  • Dishwashing detergent characterized in that the automatic dishwashing detergent contains carbonate, wherein the proportion by weight of the carbonate in the total weight of the machine
  • Dishwashing agent is preferably between 5 and 50 wt .-%, preferably between 10 and 45 wt .-% and in particular between 15 and 40 wt.%, According to the invention are preferred.
  • 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 compositions of the invention preferably contain a weight proportion of crystalline layered silicate of the formula NaMSi x 0 2x + y i ⁇ H 2 0 of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-% and in particular 0, 4 to 10 wt .-%, each based on the total weight of these agents. With regard to the formation of deposits, it has proven to be advantageous to reduce the proportion by weight of silicate on the
  • 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.
  • organic co-builders are, in particular, polycarboxylates / as the citrate, ethylenediamine-N, N'-disuccinate (EDDS) and phosphonates mentioned.
  • Automatic dishwashing agent characterized in that the automatic dishwashing agent at least one builder from the group of organic complexing agent, preferably at least an organic complexing agent from the group of citrate, ethylenediamine-N, N '- disuccinate (EDDS), and phosphonate are preferred in the invention.
  • the automatic dishwashing agent at least one builder from the group of organic complexing agent, preferably at least an organic complexing agent from the group of citrate, ethylenediamine-N, N '- disuccinate (EDDS), and phosphonate are preferred in the invention.
  • 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.
  • Nonionic surfactant of the general formula C 4 . 2 2 fatty alcohol (EO) 40 -8o-2-hydroxyalkyl ethers
  • polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts
  • polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof.
  • NTA nitrilotriacetic acid
  • the free acids 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.
  • 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 agents 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.
  • Preferred 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 dishwasher detergents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol 1 , preferably from 4000 to 25,000 gmol 1 and in particular from 5000 to 15,000 gmol -1 .
  • the polymeric sulfonates in addition to carboxyl-containing monomer and sulfonic acid-containing monomer further comprise at least one nonionic, preferably hydrophobic monomer.
  • 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
  • Methacrylic acid stearyl ester A / (stearyl) acrylamide, behenyl acrylate,
  • 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 .-%.
  • Nonionic surfactant of the general formula C 4 . 2 2 fatty alcohol (EO) i 0 -3o-2-hydroxyalkyl ethers
  • nonionic surfactant of the general formula C 4 .
  • EO fatty alcohol
  • co-builders are the homopolymers or copolymers of acrylic acid or methacrylic acid.
  • examples of such polymers are the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.
  • Suitable anionic 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 preferred automatic dishwashing agents on (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight, in each case based on the total weight of the automatic dishwashing detergent.
  • Nonionic surfactant of the general formula C 4 . 2 2 fatty alcohol (EO) 40 -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
  • Bleaching agents bleach activators and bleach catalysts, glass corrosion inhibitors, corrosion inhibitors, fragrances or dyes.
  • 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 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
  • 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.
  • 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.
  • 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.
  • nonionic surfactant of the general formula C 4 . 2 2 fatty alcohol (EO) i 0 -3o-2-hydroxyalkyl ethers
  • nonionic surfactant of the general formula C 4 . 2 2 fatty alcohol (EO) 40 -8o-2-hydroxyalkyl ether
  • 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.
  • solid offer forms are particularly suitable powders, granules, extrudates or
  • 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 those for a cleaning cycle necessary amount of washing or cleaning 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.
  • the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • disintegration aids so-called tablet disintegrants
  • 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 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 preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • 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 based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • preferred effervescent systems consist of at least two components which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • 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 during 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 during 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 metered 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.
  • the use of a A machine dishwashing agent 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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des détergents pour lave-vaisselle adjuvantés sans phosphate, qui contiennent, respectivement par rapport au poids total du détergent pour lave-vaisselle, a) 0,5 à 7,0 % en poids d'un agent tensio-actif A non ionique et b) 0,2 à 5,0 % en poids d'un agent tensio-actif B non ionique ayant un point de fusion supérieur à 25°C, l'agent tensio-actif A non ionique présentant un point de fusion inférieur d'au moins 5°C au point de fusion de l'agent tensio-actif B non ionique. 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.
EP10749664A 2009-09-21 2010-09-08 Détergent pour lave-vaisselle Withdrawn EP2480645A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009029637A DE102009029637A1 (de) 2009-09-21 2009-09-21 Maschinelles Geschirrspülmittel
PCT/EP2010/063175 WO2011032868A1 (fr) 2009-09-21 2010-09-08 Détergent pour lave-vaisselle

Publications (1)

Publication Number Publication Date
EP2480645A1 true EP2480645A1 (fr) 2012-08-01

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EP10749664A Withdrawn EP2480645A1 (fr) 2009-09-21 2010-09-08 Détergent pour lave-vaisselle

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US (1) US20120167922A1 (fr)
EP (1) EP2480645A1 (fr)
KR (1) KR20120083347A (fr)
DE (1) DE102009029637A1 (fr)
WO (1) WO2011032868A1 (fr)

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US9796947B2 (en) 2014-03-07 2017-10-24 Ecolab Usa Inc. Detergent composition comprising a polymer that performs both a cleaning and rinsing function
WO2015134404A1 (fr) * 2014-03-07 2015-09-11 Ecolab Usa Inc. Composition détergente remplissant à la fois la fonction de nettoyage et de rinçage
DE102015213942A1 (de) 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel enthaltend Bleichmittel und Polymere
US10889783B2 (en) 2017-11-14 2021-01-12 Ecolab Usa Inc. Solid controlled release caustic detergent compositions
CN114222808A (zh) 2019-09-27 2022-03-22 埃科莱布美国股份有限公司 浓缩二合一洗碗机洗涤剂和漂洗助剂
DE102019219861A1 (de) * 2019-12-17 2021-06-17 Henkel Ag & Co. Kgaa Nichtionisches Tensid zur Verbesserung der Klarspülleistung beim automatischen Geschirrspülen
KR102295499B1 (ko) 2021-04-05 2021-08-31 주식회사 자우버 식기세척 세제

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DE19603760A1 (de) * 1996-02-02 1997-08-07 Henkel Kgaa Feste Reinigungsmittelzubereitungen
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DE102005034752A1 (de) * 2005-07-21 2007-01-25 Henkel Kgaa Reinigungs- und Pflegemittel mit verbesserter Emulgierfähigkeit
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US20120167922A1 (en) 2012-07-05
WO2011032868A1 (fr) 2011-03-24
KR20120083347A (ko) 2012-07-25
DE102009029637A1 (de) 2011-03-24

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