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WO2024126473A1 - Détergent liquide pour laver la vaisselle - Google Patents

Détergent liquide pour laver la vaisselle Download PDF

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Publication number
WO2024126473A1
WO2024126473A1 PCT/EP2023/085326 EP2023085326W WO2024126473A1 WO 2024126473 A1 WO2024126473 A1 WO 2024126473A1 EP 2023085326 W EP2023085326 W EP 2023085326W WO 2024126473 A1 WO2024126473 A1 WO 2024126473A1
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WO
WIPO (PCT)
Prior art keywords
acid
weight
total composition
composition
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.)
Ceased
Application number
PCT/EP2023/085326
Other languages
English (en)
Inventor
Marwa Amraoui-Feiler
Clemens Riecke
Sven Mueller
Roland Ettl
Heike Weber
Nilgun Esin Aksoy Abaci
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
BASF SE
Original Assignee
Henkel AG and Co KGaA
BASF SE
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA, BASF SE filed Critical Henkel AG and Co KGaA
Priority to EP23817789.3A priority Critical patent/EP4634347A1/fr
Publication of WO2024126473A1 publication Critical patent/WO2024126473A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/3788—Graft 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
    • 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
    • C11D2111/18—Glass; Plastics

Definitions

  • the invention concerns liquid, phosphate free dishwashing detergents that are essentially free of bleach and comprise a polymer combination of polyaspartic acid or modified polyaspartic acid and graft polymers based on oligo- and polysaccharides that improves shine on glass.
  • WO 2019/211231 A1 describes compositions containing a polymer mix of polyaspartic acid or modified polyaspartic acid and graft polymers based on oligo- and polysaccharides to improve shine on glass ware during automatic dishwashing.
  • A1 formulations that contain a complexing agent selected from GLDA and MGDA and a graft copolymer based on oligo- and polysaccharides.
  • the invention relates to a phosphate free dishwashing detergent formulation, liquid at 20 °C, that is essentially free of bleach, comprising
  • polyaspartic acid or modified polyaspartic acid or salts thereof wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% of aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base,
  • (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of
  • (b3) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is from 18:1 to 5:1 ; (ii) from 3 to 25% by weight of the total composition of complexing agent selected from the group of citric acid, methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) or salts thereof as complexing agent;
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetic acid
  • compositions according to the invention provide a comparable or even better cleaning performance than other liquid dishwashing compositions with the polymer mixture.
  • the shine of glassware washed in an automatic dishwasher with these compositions is improved and also glass corrosion is reduced.
  • the compositions are beneficial because the biodegradability is enhanced.
  • the active ingredients of the compositions are biodegradable which leads to a high percentage of biodegradability, preferably above 85 % by weight of the composition. This means that 85 % by weight of the components in the composition are biodegradable. More preferably more than 90 wt% of the composition is biodegradable, most preferred more than 98 % of the composition is biodegradable. Biodegradability of the components is defined according to OECD 301.
  • the dishwashing detergent formulations according to the invention are suitable in particular as dishwashing detergent composition for machine dishwashing.
  • the dishwashing detergent composition according to the invention is therefore a machine dishwashing detergent composition.
  • the dishwashing detergent formulations according to the invention can be provided in liquid or gel-like form, as one or more phases.
  • “One or more”, as used herein, relates to at least one and comprises 1 , 2, 3, 4, 5, 6, 7, 8, 9 or more of the referenced species.
  • “at least one,” as used herein, includes but is not limited to 1 , 2, 3, 4, 5, 6, and more.
  • an ingredient it refers to the type of ingredient and not to the absolute number of molecules.
  • “At least one surfactant” thus means, for example, at least one type of surfactant, meaning that one type of surfactant or a mixture of several different surfactants may be meant. Together with weight indications, the indication refers to all compounds of the indicated type contained in the composition/mixture, i.e., that the composition does not contain any further compounds of this type beyond the indicated amount of the corresponding compounds.
  • M n the numberaverage molar mass
  • M n the numberaverage molar mass
  • the number average molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1 :2007- 08 with THF as eluent.
  • the weight average molecular weight M w can also be determined by GPC as described for M n .
  • alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is naturally present only in half the amount of substance - sufficient for charge balance - as the anion.
  • fatty acids or fatty alcohols or derivatives thereof - unless otherwise indicated - are representative of branched or unbranched carboxylic acids or alcohols or derivatives thereof preferably having 6 to 22 carbon atoms.
  • the former are preferred for ecological reasons, in particular because of their vegetable basis as being based on renewable raw materials, without, however, limiting the teaching according to the invention to them.
  • the oxoalcohols obtainable, for example, according to the ROELEN oxo-synthesis or their derivatives can also be used accordingly.
  • the cleaning composition according to the invention is provided in form of a liquid.
  • liquid as used herein includes liquids and gels.
  • liquid refers to compounds or mixtures of compounds that are flowable and pourable at 20° C, 1 bar.
  • the cleaning composition according to the invention is phosphate-free.
  • Phosphate-free as used herein is to be understood as the cleaning composition being substantially free of phosphate (including orthophosphate, polyphosphate and/or pyrophosphate), in particular as comprising phosphates in an amount of less than 0.1 wt.%, preferably less than 0.01 wt.%, based on the total weight of the composition.
  • the expression “essentially free of’ means that the respective compound may in principle be contained, but is then present in an amount that does not impair a function of the other components.
  • the property “essentially free of’ a particular compound is preferably taken to mean a total weight of less than 0.1 % by weight, more preferably less than 0.001 % by weight, in particular free of it, based on the total weight of the composition.
  • the cleaning composition according to the invention is essentially free of bleach.
  • the compositions comprise less than 0.1 % by weight of percarbonate salts, alkali metal hypochlorite, H2O2 and its precursors, based on the total weight of the composition.
  • the compositions comprise less than 0.01 wt% by weight, more preferred less than 0.001 % by weight of these components based on the total weight of the composition.
  • “Bleach-free” as used herein is to be understood as the cleaning composition being substantially free of active ingredients, that are capable to release bleach, especially peroxy-containing compounds, hypohalogenic compounds or H2O2 to the wash liquor in an automatic dishwashing.
  • bleach-free means that the composition comprises bleach compounds (compounds that release bleach) in an amount of less than 0.1 wt.%, preferably less than 0.01 wt.%, based on the total weight of the composition.
  • liquid compositions that contain a polymer mix according to i) containing biodegradable polyaspartic acid or modified polyaspartic acid or salts thereof (a) and biodegradable graft polymer (b) prepared by grafting of at least one ethylenic unsaturated mono- or dicarboxylic acid and at least one N-containing cationic monomer onto oligo- and polysaccharides leads to dramatically improved cleaning re-suit.
  • the combination is especially effective in preventing film formation (scaling) on glass.
  • the weight ratio of aspartic or modified aspartic acid (a) to graft polymer (b) is preferably from 18:1 to 5:1 , more preferably from 11 : 1 to 8 : 1 particularly preferably from 11 : 1 to 9 : 1 .
  • components (a) and (b) accounts for 1 to 4% by weight of the total composition.
  • components (a) and (b) can be added separately, or can be added as a pre- compounded film inhibiting composition.
  • the amount of the component according to (i) is from 1 .2 % to 4.5%, preferably from 1 .5 % to 4.0 % by weight of the total composition.
  • Polyaspartic acid is well known as biodegradable dispersing and scale inhibiting polymer.
  • Modified polyaspartic acid which can be used according to the present invention is preparable by polycondensation of (a1) 50 to 99 mol%, preferably 60 to 95 mol%, particularly preferably 80 to 95 mol%, of aspartic acid; and (a2) 1 to 50 mol%, preferably 5 to 40 mol%, particularly preferably 5 to 20 mol%, of at least one carboxyl-containing compound, and subsequent hydrolysis of the cocondensates with the addition of a base, for example sodium hydroxide solution, wherein (a2) is not an aspartic acid.
  • a base for example sodium hydroxide solution
  • the carboxyl-containing compound (a2) used in connection with the preparation of the polyaspartic acid to be used according to the invention can be, inter alia, a carboxylic acid (monocarboxylic acid or polycarboxylic acid), a hydroxycarboxylic acid and/or an amino acid (apart from aspartic acid).
  • carboxylic acids or hydroxycarboxylic acids are preferably polybasic.
  • polybasic carboxylic acids can thus be used in the preparation of the polyaspartic acid to be used according to the invention, e.g.
  • oxalic acid adipic acid, fumaric acid, maleicacid, itaconic acid, aconitic acid, succinic acid, malonic acid, suberic acid, azelaic acid, diglycolic acid, glutaric acid, C1-C26 alkylsuccinic acids (e.g. octylsuccinic acid), C2-C26 alkenylsuccinic acids (e.g.
  • octenylsuccinic acid 1 ,2,3-propanetricarboxylic acid, 1 ,1 ,3,3-propanetetracarboxylic acid, 1 ,1 ,2,2-ethanetetracarboxylic acid, 1 ,2,3,4-butanetetracarboxylic acid, 1 ,2,2,3-propane- tetracarboxylic acid, or 1 ,3,3,5-pentanetetracarboxylic acid.
  • polybasic hydroxycarboxylic acids e. g. citric acid, isocitric acid, mucic acid, tartaric acid, tartronic acid, or malic acid.
  • Amino acids that can be used in this connection are, inter alia, aminocarboxylic acids (e.g. glutamic acid, cysteine), basic diaminocarboxylic acids (e.g. lysine, arginine, histidine, aminocaprolactam), neutral amino acids (e.g. glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactam, asparagine, iso- asparagine, glutamine, isoglutamine), aminosulfonic acids (e.g. taurine), hydroxylamino acids (e.g.
  • aminocarboxylic acids e.g. glutamic acid, cysteine
  • basic diaminocarboxylic acids e.g. lysine, arginine, histidine, aminocaprolactam
  • neutral amino acids e.g. glycine, alanine, valine, leucine, is
  • hydroxyproline, serine, threonine iminocarboxylic acids (e.g. proline, iminodiacetic acid), or aromatic and heterocyclic amino acids (e.g. anthranilic acid, tryptophan, tyrosine, histidine), but not aspartic acid.
  • iminocarboxylic acids e.g. proline, iminodiacetic acid
  • aromatic and heterocyclic amino acids e.g. anthranilic acid, tryptophan, tyrosine, histidine
  • Preferred carboxyl-containing compounds (a2) in connection with the preparation of the modified polyaspartic acids to be used according to the invention are 1 , 2,3,4- butanetetracarboxylic acid, citric acid, glycine, glutamic acid, itaconic acid, succinic acid, taurine, maleic acid and glutaric acid, particularly preferably 1 ,2,3,4-butanetetracarboxylic acid, citric acid, glycine and glutamic acid.
  • the molecular weight (Mw) of the (modified) polyaspartic acid can easily be tuned by varying the reaction conditions. Molecular weights between 1000 g/mol and 100 000 g/mol can be achieved by simple adjustion of the process parameters (temperature, catalyst, reaction time).
  • the preferred molecular weight of the (modified) polyaspartic acid used according to the present invention lies in the range between 1000 g/mol and 20 000 g/mol, preferably between 1500 and 15 000 g/mol and particularly preferably between 2000 and 10 000 g/mol.
  • the aspartic acid used in connection with the preparation of the (modified) polyaspartic acid to be used according to the invention can either be L- or D- and DL-aspartic acid. Preference is given to using L-aspartic acid.
  • the dishwashing detergent formulation contains polyaspartic acid as homopolymer in amounts and molecular weight as preferred above.
  • the preparation of the (modified) polyaspartic acids to be used according to the invention takes place generally via a poly(co)condensation of aspartic acid, optionally with at least one carboxyl- containing compound (not aspartic acid) and subsequent hydrolysis of the obtained (co)condensates with the addition of a base as illustrated and described above and below.
  • the preparation of such (modified) polyaspartic acids is also described, by way of example in DE 4221875.6 or WO 2019/211231 A1 , the disclosure of these is hereby referred to in its entirety.
  • neutralized (modified) polyaspartic acid are obtained in the form of the salts corresponding to the bases.
  • the (modified) polyaspartic acids to be used according to the invention and/or their salts can be used as aqueous solution or in solid form, e.g. in powder or granule form.
  • the powder or granule form can be obtained for example by spray drying, spray granulation, fluidized-bed spray granulation, roller drying or freeze drying of the aqueous solution of the polyaspartic acids or their salts.
  • composition according to the invention contains (b) at least one graft copolymer composed of (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of
  • oligosaccharides that may be mentioned are carbohydrates with three to ten monosaccharide units per molecule, for example glycans.
  • polysaccharides is the term used to refer to carbohydrates with more than ten monosaccharide units per molecule.
  • Oligo- and polysaccharides may be for example linear, cyclic or branched.
  • Polysaccharides to be mentioned by way of example are biopolymers such as starch and gly cogen, and cellulose, dextran and tunicin.
  • inulin as polycondensate of D-fructose (fructans), chitin and alginic acid.
  • starch degradation products for example products which can be obtained by enzymetic or so-called chemical degradation of starch. Examples of the so-called chemical degradation of starch are oxidative degradation and acid-catalyzed hydrolysis.
  • maltodextrins are maltodextrins and glucose syrup.
  • maltodextrin is the term used to refer to mixtures of monomers, dimers, oligomers and polymers of glucose.
  • the percentage composition differs depending on the degree of hydrolysis. This is described by the dextrose equivalent, which in the case of maltodextrin is between 3 and 40.
  • the graft base (b1) is selected from polysaccharides, in particular from starch, which is preferably not chemically modified.
  • starch is selected from those polysaccharides which have in the range from 20 to 30% by weight amylose and in the range from 70 to 80% amylopectin. Examples are corn starch, rice starch, potato starch and wheat starch.
  • Side chains are grafted on to the graft base (b1). Per molecule of graft copolymer (b), preferably on average one to ten side chains can be grafted on.
  • a side chain is linked with the anomeric carbon atom of a monosaccharide or with an anomeric carbon atom of the chain end of an oligo- or polysaccharide.
  • the number of side chains is limited upwards by the number of carbon atoms with hydroxyl groups of the graft base (b1) in question.
  • Examples of monocarboxylic acids (b2) are ethylenically unsaturated Cs-Cio-monocarboxylic acids and the alkali metal or ammonium salts thereof, in particular the potassium and the sodium salts.
  • Preferred monocarboxylic acids (b2) are acrylic acid and methacrylic acid, and also sodium (meth)acrylate.
  • Mixtures of ethylenically unsaturated C3-C10 monocarboxylic acids and in particular mixtures of acrylic acid and methacrylic acid are also preferred components (b2).
  • dicarboxylic acids (b2) are ethylenically unsaturated C4-Cio-dicarboxylic acids and their mono- and in particular dialkali metal or ammonium salts, in particular the dipotassium and the disodium salts, and also anhydrides of ethylenically unsaturated C4-Cio-dicarboxylic acids.
  • Preferred dicarboxylic acids (b2) are maleic acid, fumaric acid, itaconic acid, and also maleic anhydride and itaconic anhydride.
  • graft copolymer (b) comprises in at least one side chain, besides monomer (b3) at least one monocarboxylic acid (b2) and at least one dicarboxylic acid (b2).
  • graft copolymer (b) comprises in polymerized- in form in the side chains, besides monomer (b3), exclusively monocarboxylic acid (b2), but no dicarboxylic acid (b2).
  • Examples of monomers (b3) are ethylenically unsaturated N-containing compounds with a permanent cationic charge, i.e. those ethylenically unsaturated N-containing compounds which form ammonium salts with anions such as sulfate, Ci-C4-alkyl sulfates and halides, in particular with chloride, and independently of the pH. Any desired mixtures of two or more monomers (b3) are also suitable.
  • Suitable monomers (b3) are the correspondingly quaternized derivatives of vinyl- and allyl-substituted nitrogen heterocycles such as 2-vinylpyridine and 4-vinylpyrid ine, 2-allyl- pyridine and 4-allylpyridine, and also N-vinylimidazole, e.g. 1-vinyl-3-methylimidazolium chloride. Also of suitability are the correspondingly quaternized derivatives of N,N-diallylamines and N , N-diallyl-N- alkylamines, such as e.g. N,N-diallyl-N,N-dimethylammonium chloride (DADMAC).
  • DADMAC N,N-diallyl-N,N-dimethylammonium chloride
  • monomer (b3) is selected from correspondingly quaternized, ethylenically unsaturated amides of mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group. Preference is given here to those diamines which have one tertiary and one primary or secondary amino group.
  • monomer (b3) is selected from correspondingly quaternized, ethylenically unsaturated esters of mono- and dicarboxylic acids with C2-C12- amino alcohols which are mono- or dialkylated on the amine nitrogen.
  • acid component of the aforementioned esters and amides are e.g. acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof.
  • acid component preference is given to using acrylic acid, methacrylic acid and mixtures thereof.
  • Preferred monomers (b3) have the general formula (I), wherein the variables are defined as follows: Z is O or NR1 ,
  • R1 is selected from methyl and hydrogen
  • A1 is selected from C2-C4-alkylene
  • R2 are identical or different and selected from Ci-C4-alkyl
  • X is selected from halide, mono-Ci-C4-alkyl sulfate and sulfate.
  • Particular preferred monomers (b3) are trialkylaminoethyl (meth)acrylatochloride or alkyl sulfate and trialkylaminopropyl (meth)acrylatochloride or alkyl sulfate, and also (meth)acryl- amidoethyltrialkylammonium chloride or alkyl sulfate and (meth)acrylamidopropyltrialkyl- ammonium chloride or alkyl sulfate, where the respective alkyl radical is preferably methyl or ethyl or mixtures thereof.
  • (meth)acrylamidopropyltrimethylammonium halide in particular acrylamidopropyltrimethylammonium chloride (“APT AC”) or methacrylamidopropyl- trimethylammonium chloride (“MAPTAC”).
  • monomer (b3) is selected from trimethylammonium C2-C3-alkyl(meth)acrylatohalide, in particular 2-(trimethylamino)ethyl(meth)- acrylatochloride and 3-(trimethylamino)propyl(meth)acrylatochloride.
  • monomer (b3) is trimethylaminoethyl (meth)acrylatochloride or methacrylamidopropyl trimethyl ammonium Chloride, preferably co- trimethylaminoethyl (meth)acrylatochloride.
  • Graft copolymer (b) can comprise, in polymerized-in form, in one or more side chains at least one further comonomer (b4), for example hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate, or esters of alkoxylated fatty alcohols, or comonomers containing sulfonic acid groups, for example 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its alkali metal salts.
  • graft copolymer (b) comprises no further comonomers (b4) in one or more side chains apart from monomer (b3) and monocarboxylic acid (b2) or dicarboxylic acid (b2).
  • the fraction of graft base (b1) in graft copolymer (b) is in the range from 40 to 95% by weight, preferably from 50 to 90% by weight, in each case based on total graft copolymer (b).ln one embodiment of the present invention, the fraction of monocarboxylic acid (b2) or dicarboxylic acid (b2) is in the range from 2 to 40% by weight, preferably from 5 to 30% by weight and in particular from 5 to 25% by weight, in each case based on total graft copolymer (b).
  • the monomers of type (b3) are polymerized in amounts of from 5 to 50% by weight, preferably from 5 to 40% by weight and particularly preferably from 5 to 30% by weight, in each case based on total graft copolymer (b).
  • graft copolymer (b) comprises, in polymerized-in form, more monocarboxylic acid (b2) than compound (b3), and specifically based on the molar fractions, for example in the range from 1 .1 :1 to 5:1 , preferably 2:1 to 4:1 .
  • the average molecular weight (Mw) of graft copolymer (b) is in the range from 2000 to 200 000 g/mol, preferably from 5000 to 150 000 and in particular in the range from 8000 to 100 000 g/mol.
  • the average molecular weight Mw is measured preferably by gel permeation chromatography in aqueous KCI/formic acid solution.
  • Graft copolymer (b) can preferably be obtained as aqueous solution from which it can be isolated, e.g. by spray drying, spray granulation or freeze drying.
  • solution of graft copolymer (b) or dried graft copolymer (b) can be used for producing the formulations according to the invention.
  • Monomer (b3) per se can be polymerized in graft copolymer (b) or a non quaternized equivalent, in the case of APT AC for example and in the case of MAPTAC with and the copolymerization can be followed by alkylation, for example with Ci-Cs-alkyl halide or di- Ci-C4-alkyl sulfate, for example with ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate or diethyl sulfate.
  • a preferred embodiment of the dishwashing detergent formulation according to the invention is, wherein the monomer (b3) is at least one compound of the general formula (I), wherein the variables are defined as follows:
  • Z is O or NR1 .preferably Z is O,
  • R1 is selected from methyl and hydrogen
  • a 1 is selected from C2-C4-alkylene
  • R2 are identical or different and selected from C1-C4-alkyl
  • X- is selected from halide, mono-C1-C4-alkyl sulfate and sulfate.
  • monomers (b3) according to the forestanding formula (I) wherein R 2 are identical and methyl, A1 is CH2CH2, and X- is chloride.
  • composition according to the invention comprising polyaspartic acid or modified polyaspartic acid (a) and graft copolymer (b) as described herein and to be used according to the invention can be used particularly advantageously in machine dishwashing detergents. They are characterized here in particular by their film-inhibiting effect both towards inorganic and organic films. In particular, they inhibit films made of calcium and magnesium carbonate and calcium and magnesium phosphates and phosphonates. Additionally, they prevent deposits which originate from the soil constituents of the wash liquor, such as grease, protein and starch films.
  • the dishwashing detergent formulation according to the invention comprises from 3 to 25% by weight of the total composition of complexing agent selected from the group of citric acid or salts thereof, methylglycinediacetic acid (MGDA) or salts thereof and glutamic acid diacetic acid (GLDA) or salts thereof.
  • complexing agent selected from the group of citric acid or salts thereof, methylglycinediacetic acid (MGDA) or salts thereof and glutamic acid diacetic acid (GLDA) or salts thereof.
  • Particularly preferred representatives of this class are the alkali metal salts thereof, especiall the trisodium salt of methylglycinediacetic acid (MGDA) or the tetrasodium salt of glutamic diacetic acid (GLDA) and/or trisodium citrate, in particular anhydrous trisodium citrate or trisodium citrate dihydrate.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic diacetic acid
  • trisodium citrate in particular anhydrous trisodium citrate or trisodium citrate dihydrate.
  • Preferred are also combinations of citric acid or salts thereof with methylglycinediacetic acid (MGDA) or salts thereof.
  • MGDA methylglycinediacetic acid
  • MGDA trisodium citrate
  • the dishwashing detergent formulation is characterized in that the amount of methylglycinediacetic acid (MGDA) and its salts, is from 4.5 to 20 % by weight of the total composition.
  • MGDA methylglycinediacetic acid
  • the dishwashing detergent formulation is characterized in that the amount of citric acid and its salts, is from 0.5 to 15 % by weight of the total composition.
  • the dishwashing detergent formulation is characterized in that the amount of methylglycinediacetic acid (MGDA) and its salts, is from 4.5 to 20 % by weight of the total composition and the amount of citric acid and its salts, is from 0.5 to 15 % by weight of the total composition.
  • MGDA methylglycinediacetic acid
  • compositions according to the invention comprise from 0.2 to 6 % by weight of the total composition of thickener.
  • the thickener is selected from the group consisting of polysaccharide gums such as xanthan gum, guar, carageenan, pectin, alginate, and succinoglycan gum; synthetic rheology modifiers based on acrylates (such as Carbopol® Aqua 30, Acusol® 810, Acusol® 830, Acusol® 835 or Acusol® 842) or urethanes (such as Acusol® 880 and Acusol® 882); "low-molecular-weight gelators” "LMWG", such as dibenzylidene sorbitol (DBS), hydrogenated castor oil (HCO), urea derivatives (such as Rheobyk ®7420) or cyclic dipeptides.
  • polysaccharide gums such as xanthan gum, guar, carageenan, pectin, al
  • cleaning compositions that contain from 0.2 to 5.0 wt.%, preferably from 0.20 to 2.5 wt.%, more preferably to 0.25 to 1 .5 wt.% of thickeners, most preferred from 0.3 to 1 .0 wt.%, based on the weight of the liquid phase.
  • Preferred thickeners are selected from the group of xanthan gum, crosslinked polyacrylate and urea derivatives.
  • Xanthan gum, urea derivatives, such as Rheobyk® 7420, and/or crosslinked polyacrylate, such as Acusol® 810 are able to stabilize the liquid phase and minimize disintegration of this mixture. Especially, they reduce sedimentation of the detergent ingredients.
  • the dishwashing detergent formulation according to the inventions comprises xanthan gum as a thickener, preferably in an amount from 0.25 to 0.8 % by weight of the total composition.
  • the dishwashing detergent formulation according to the inventions comprises a thickener selected from crosslinked polyacrylic acids, preferably in an amount from 0.5 to 1 .0 % by weight of the total composition.
  • the cleaning composition according to the present invention comprises a significant amount of water.
  • the amount of water is at least 30 % by weight of the total composition, preferably from 40 to 70 % by weight of the total composition, most preferred from 40 to 60 % by weight of the total composition.
  • the cleaning composition contains 45 to 75 wt.% water and 0.2 to 2.5 wt.% of thickeners, each based on the weight of the composition. More preferably it contains 50 to 70 wt.% water and 0.25 to 1.5 wt.% of thickener, selected from xanthan gum or crosslinked polyacrylates or urea derivates, each based on the weight of the composition.
  • Builders and/or cobuilders according to the invention are, in particular, water-soluble or water- insoluble substances, the main task of which consists in the binding of calcium and magnesium ions.
  • These expressions “builders” and “cobuilders” according to the invention do not include citric acid, methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA) and/or salts thereof.
  • Builders and/or cobuilders may be low molecular weight carboxylic acids, and salts thereof such as alkali metal malonates, fatty acid sulfonates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, tartrate monoacetate, tartrate diacetate and a-hydroxypropionoic acid.
  • builders which can be used in connection with the dishwashing detergent formulations according to the invention are carbonates and hydrocarbonates, among which the alkali metal salts, in particular sodium salts, are preferred.
  • the dishwashing detergent formulation is characterized in that the composition comprises as builder (a component according to (v) of the main claim) from 5 to 12% by weight, preferably 7 to 10 % by weight of the total composition an alkali metal carbonate.
  • phosphonates which can be present in some embodiments of the cleaning composition to the invention are phosphonates. These are in particular hydroxylalkane- and amino- alkanephosphonates. Among the hydroxyalkanephosphonates, 1 -hydroxyethane-1 ,1 -di- phosphonate (HEDP) is of particular importance as cobuilder. It is preferably used as sodium salt, with the disodium salt giving a neutral reaction and the tetrasodium salt an alkaline reaction (pH 9). Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylene- phosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and higher homologs thereof.
  • ETMP ethylenediaminetetramethylene- phosphonate
  • DTPMP diethylenetriaminepentamethylenephosphonate
  • the builder used here from the class of phosphonates is preferably HEDP.
  • the aminoalkane- phosphonates have a marked heavy metal binding capacity.
  • the composition comprises less than 0.1 %, preferably less than 0.01 % by weight of phosphonates. Preferably the composition comprises less than 0.01 % by weight of phosphorous containing compounds. Phosphonate free compositions show better biodegradability and/or are improved from an ecological point of view. Therefore, these embodiments are most preferred.
  • the formulations are essentially free of silicate.
  • the total weight of silicates is less than 0.1 % by weight, more preferably less than 0.001 % by weight, in particular free of it, based on the total weight of the composition.
  • Copolymers of acrylic acid or of methacrylic acid might be used.
  • Suitable comonomers are, in particular, monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and anhydrides thereof such as maleic anhydride.
  • Comonomers containing sulfonic acid groups such as 2-acrylamido-2-methylpropanesulfonic acid, allylsulfonic acid and vinylsulfonic acid, are also suitable.
  • Hydrophobic comonomers are also suitable, such as, for example, isobutene, diisobutene, styrene, alpha-olefins with 10 or more carbon atoms.
  • Hydrophilic monomers with hydroxy function or alkylene oxide groups can likewise be used as comonomers.
  • graft polymers based on degraded starch and the aforementioned monomers such as (meth)acrylic acid, maleic acid, fumaric acid and 2- acrylamido-2-methylpropanesulfonic acid can be used as cobuilder.
  • these homopolymers and copolymers of acrylic acid or of methacrylic acid which preferably have a weight-average molar mass of 2000 to 50 000 g/mol are not comprised in the formulations according to the invention.
  • Cleaning compositions formulations may contain one or more surfactants selected from the group consisting of anionic surfactants, nonionic surfactants cationic, zwitterionic, and amphoteric surfactants. Combinations of the aforementioned types of surfactants are also anticipated.
  • the dishwashing detergent formulation according to any one of points 1 to 20, characterized in that the composition comprises from 0.5 to 6% by weight, preferably 1 to 4 % by weight of the total composition of nonionic surfactants.
  • All non-ionic surfactants that are known to a person skilled in the art can be used as non-ionic surfactants.
  • Low foaming non-ionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming non-ionic surfactants such as alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, or amine oxides.
  • Particularly preferred non-ionic surfactants are specified in greater detail below.
  • Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols having more than 12 EO can also be used. Examples of these are tallow fatty alcohols having 14 EO, 25 EO, 30 EO, or 40 EO.
  • Ethoxylated non-ionic surfactants are particularly preferably used which were obtained from C 6-2 o monohydroxy alkanols or C 6 ⁇ alkyl phenols or Ci 6-2 o fatty alcohols and more than 12 mol, preferably more than 15 mol, and in particular more than 20 mol, ethylene oxide per mol of alcohol.
  • a particularly preferred non-ionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (Ci6- 20 alcohol), preferably from a Cis alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide. Of these, what are referred to as “narrow range ethoxylates” are particularly preferred.
  • Surfactants that are preferably used come from the group of the alkoxylated non-ionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants).
  • structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants).
  • Such (PO/EO/PO) non-ionic surfactants are also characterized by good foam control.
  • low-foaming non-ionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred.
  • surfactants having EO-AO-EO-AO blocks are preferred, with one to ten EO groups or AO groups being bonded to one another before a block of the other group follows.
  • non-ionic surfactants of the general formula are preferred, in which R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24-alkyl or alkenyl functional group; each R2 and R3 group is selected, independently of one another, from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2; and the indices w, x, y and z represent, independently of one another, integers from 1 to 6.
  • Preferred non-ionic surfactants of the above formula can be prepared using known methods, from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the R 1 functional group in the above formula can vary depending on the origin of the alcohol. If native sources are used, the R 1 functional group has an even number of carbon atoms and is generally unbranched, with the linear functional groups of alcohols of native origin having 12 to 18 C atoms, such as coconut, palm, tallow fatty or oleyl alcohol, for example, being preferred.
  • Some examples of alcohols that are available from synthetic sources are the Guerbet alcohols or functional groups that are methyl-branched or linear and methyl-branched in the 2 position in admixture, such as those usually present in oxo alcohol functional groups.
  • non-ionic surfactants are preferred in which R 1 represents an alkyl functional group having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15, and in particular 9 to 11 , carbon atoms in the above formula.
  • butylene oxide in particular is worthy of consideration as an alkylene oxide unit that is contained alternately with the ethylene oxide unit in the preferred non-ionic surfactants.
  • R 2 and R 3 are selected, independently of one another, from -CH2CH2-CH3 and -CH(CH 3 ) 2 are also suitable.
  • non-ionic surfactants of the above formula are used in which R 2 and R 3 represent a -CH3 functional group; w and x represent, independently of one another, values of 3 or 4; and y and z represent, independently of one another, values of 1 or 2.
  • non-ionic surfactants of the solid phase are non-ionic surfactants of general formula
  • R 1 O(AlkO)xM(OAIk) y OR 2 in which R 1 and R 2 represent, independently of one another, a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl functional group having 4 to 22 carbon atoms;
  • Aik represents a branched or unbranched alkyl functional group having 2 to 4 carbon atoms;
  • x and y represent, independently of one another, values of between 1 and 70;
  • M represents an alkyl functional group from the group CH2, CHR 3 , CR 3 R 4 , CH2CHR 3 and CHR 3 CHR 4 , R 3 and R 4 representing, independently of one another, a branched or unbranched, saturated or unsaturated alkyl functional group having 1 to 18 carbon atoms.
  • R 1 -CH(OH)CH2-O(CH2CH2O)xCH2CHR(OCH2CH2)y-CH 2 CH(OH)-R 2 in which R, R 1 and R 2 represent, independently of one another, an alkyl functional group or alkenyl functional group having 6 to 22 carbon atoms; x and y represent, independently of one another, values between 1 and 40.
  • R 1 -CH(OH)CH 2 -O(CH 2 CH 2 O) x CH 2 CHR(OCH 2 CH 2 ) y O-CH 2 CH(OH)-R 2 in which R represents a linear, saturated alkyl functional group having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m represent, independently of one another, values of from 20 to 30.
  • Such compounds can be obtained, for example, by reacting alkyl diols HO-CHR-CH2- OH with ethylene oxide, a reaction with an alkyl epoxide being performed subsequently in order to close the free OH functions during formation of a dihydroxy ether.
  • preferred non-ionic surfactants are those of general formula R 1 -CH(OH)CH2O-(AO) W - (AO)x-(A"O) y -(A'"O)z-R 2 , in which
  • R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl functional group
  • R 2 represents hydrogen or a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms
  • A, A', A" and A'" represent, independently of one another, a functional group from the group -CH2CH2, -CH 2 CH2-CH2, -CH2-CH(CH 3 ), -CH2-CH2-CH2-CH2, -CH 2 -CH(CH 3 )-CH 2 -, -CH 2 - CH(CH 2 -CH 3 ); w, x, y and z represent values of between 0.5 and 120, where x, y and/or z can also be 0.
  • non-ionic surfactants of general formula R 1 -CH(OH)CH2O-(AO) W - (A'O)x-(A"O) y -(A'"O)z-R 2 , subsequently also referred to as “hydroxy mixed ethers,” surprisingly, the cleaning performance of preparations according to the invention can be significantly improved, both in comparison with surfactant-free systems and in comparison with systems containing alternative non-ionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • non-ionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl functional groups, the stability of the enzymes contained in the cleaning agent preparations according to the invention can be improved substantially.
  • those end-capped poly(oxyalkylated) non-ionic surfactants are preferred which, according to the following formula, besides a functional group R 1 , which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, also have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional group R 2 having 1 to 30 carbon atoms, where n represents values of between 1 and 90, preferably values of between 10 and 80, and in particular values of between 20 and 60.
  • Surfactants of the above formula are in particular preferred in which R 1 represents C7 to C13, n represents a whole natural number from 16 to 28 and R 2 represents Ca to C12.
  • R 1 O[CH2CH(CH3)O]x[CH2CH2O] y CH2CH(OH)R 2 are particularly preferred, in which R 1 represents a linear or branched aliphatic hydrocarbon functional group having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms or mixtures thereof, x represents values between 0.5 and 1 .5, and y represents a value of at least 15.
  • the group of these non-ionic surfactants includes for example the C2-26 fatty alcohol (PO)i-(EO)i5-4o-2-hydroxyalkyl ethers, in particular including the Cs-io fatty alcohol (PO)i-(EO)22-2-hydroxydecyl ethers.
  • non-ionic surfactants that can preferably be used are the end-capped poly(oxyalkylated) non- ionic surfactants of the formula R 1 O[CH 2 CH(R 3 )O]x[CH2]kCH(OH)[CH 2 ]jOR 2 , in which R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl functional group, x represents values between 1 and 30, and k and j represent 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[CH2]kCH(OH)[CH 2 ]jOR 2 can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon functional groups having 6 to 22 carbon atoms, with functional groups having 8 to 18 C atoms being particularly preferred.
  • R 3 H, -CH3 or -CH2CH3 are particularly preferred.
  • Particularly preferred values for x are in the range of from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula can be different if x > 2.
  • the alkylene oxide unit in square brackets can be varied.
  • the value 3 for x has been selected here by way of example and can by all means be greater, in which case the range of variation increases as the values for x increase and includes a large number of (EO) groups combined with a small number of (PO) groups, for example, or vice versa.
  • R 1 O[CH 2 CH(R 3 )O]xCH 2 CH(OH)CH 2 OR 2 .
  • R 1 , R 2 and R 3 are as defined above and x represents numbers from 1 to 30, preferably from 1 to 20, and in particular from 6 to 18.
  • Surfactants in which the functional groups R 1 and R 2 have 9 to 14 C atoms, R 3 represents H, and x assumes values from 6 to 15 are particularly preferred.
  • the non-ionic surfactants of general formula R 1 -CH(OH)CH 2 O-(AO) W -R 2 have been found to be particularly effective, in which
  • R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C6-24 alkyl or alkenyl functional group
  • R 2 represents a linear or branched hydrocarbon functional group having 2 to 26 carbon atoms
  • A represents a functional group from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH(CH3), preferably represents CH 2 CH 2 , and w represents values of between 1 and 120, preferably 10 to 80, in particular 20 to 40.
  • the group of these non-ionic surfactants includes, for example, the C4- 22 fatty alcohol-(EO)io-8o-2- hydroxyalkyl ethers, in particular including the Cs-12 fatty alcohol-(EO) 22 -2-hydroxydecyl ethers and the C4- 22 fatty alcohol-(EO)40-80-2-hydroxyalkyl ethers.
  • the non-ionic surfactant of is selected from non-ionic surfactants of general formula R 1 -O(CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y O-R 2 , in which R 1 und R 2 , independently of one another, represent an alkyl functional group or alkenyl functional group having 4 to 22 carbon atoms; R 3 und R 4 represent, independently of one another, H or an alkyl functional group of alkenyl functional group having 1 to 18 carbon atoms, and x and y represent, independently of one another, values between 1 and 40.
  • R 1 und R 2 independently of one another, represent an alkyl functional group or alkenyl functional group having 4 to 22 carbon atoms
  • R 3 und R 4 represent, independently of one another, H or an alkyl functional group of alkenyl functional group having 1 to 18 carbon atoms
  • x and y represent, independently of one another, values between 1 and 40.
  • R 1 -O(CH 2 CH 2 O)xCR 3 R 4 (OCH 2 CH 2 ) y O-R 2 are preferred, in which R 3 and R 4 represent H and the indices x and y, independently of one another, assume values from 1 to 40, preferably from 1 to 15.
  • compounds of general formula R 1 -O(CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y O-R 2 are particularly preferred, in which the functional groups R 1 and R 2 , independently of one another, represent saturated alkyl functional groups having 4 to 14 carbon atoms and the indices x and y, independently of one another, assume values from 1 to 15 and in particular from 1 to 12.
  • Such compounds of general formula R 1 -O(CH 2 CH 2 O) x CR 3 R 4 (OCH 2 CH 2 ) y O-R 2 are preferred in which one of the functional groups R 1 and R 2 is branched.
  • Most particularly preferred are compounds of general formula R 1 -O(CH2CH2O)xCR 3 R 4 (OCH2CH2) y O-R 2 , in which the indices x and y, independently of one another, assume values from 8 to 12.
  • the indicated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the non-ionic surfactants represent statistical averages that can be an integer or a fraction for a given product. Owing to the manufacturing methods, commercial products of the above-mentioned formulas generally do not consist of an individual representative, but of mixtures, for which reason average values and, resulting from those, fractional numbers can arise both for the C chain lengths and for the degrees of ethoxylation and degrees of alkoxylation.
  • non-ionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four, or more surfactants.
  • Non-ionic surfactants having a melting point above room temperature are particularly preferred.
  • the non-ionic surfactant that is solid at room temperature preferably has propylene oxide (PO) units in the molecule.
  • PO propylene oxide
  • Such PO units constitute up to 25 wt.%, particularly preferably up to 20 wt.%, and in particular up to 15 wt.% of the total molar mass of the non-ionic surfactant.
  • Particularly preferred non-ionic surfactants are ethoxylated monohydroxy alkanols or alkyl phenols that additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkyl phenol fraction of such non-ionic surfactant molecules preferably constitutes greater than 30 wt.%, particularly preferably greater than 50 wt.%, and in particular greater than 70 wt.% of the total molar mass of such non-ionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated non-ionic surfactants in which the propylene oxide units in the molecule constitute up to 25 wt.%, preferably up to 20 wt.%, and particularly up to 15 wt.% of the total molar mass of the non-ionic surfactant.
  • dishwashing detergent formulations for example anionic or zwitterionic surfactants, alkali carriers, polymeric dispersants, corrosion inhibitors, antifoams, dyes, fragrances, fillers, solubility promoters, or water can be used.
  • Alkali carriers that can be used are, for example, besides the ammonium or alkali metal carbonates, ammonium or alkali metal hydrogencarbonates and ammonium or alkali metal sesqui- carbonates already specified for the builder substances, also ammonium or alkali metal hydroxides, and mixtures of the aforementioned substances.
  • glass corrosion inhibitors are for example, magnesium, zinc and bismuth salts and complexes and polyethyleneimine.
  • silver protectors from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes, if ecologically compliant.
  • the dishwashing detergent formulations according to the invention can comprise 0 to 5 % by weight of enzymes.
  • Enzymes can be added to the dishwashing detergent in order to increase the cleaning performance or, under more mild conditions (e.g. at lower temperatures), to ensure the cleaning performance in identical quality.
  • the enzymes can be used in free form or chemically or physically immobilized form on a support, or in encapsulated form.
  • Cleaning agents according to the invention preferably contain enzymes in total quantities of from 1 x 10 -6 wt.% to 5 wt.% based on active protein.
  • the protein concentration can be determined with the aid of known methods, for example the BCA method or the Biuret method.
  • subtilisin-type proteases are preferred. Examples of these are the subtilisins BPN’ and Carlsberg, as well as the further-developed forms thereof, protease PB92, subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K and proteases TW3 and TW7, which belong to the subtilases but no longer to the subtilisins in the narrower sense.
  • amylases examples include a-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger, and A. oryzae, as well as the further developments of the above-mentioned amylases that have been improved for use in cleaning agents.
  • Others that are particularly noteworthy for this purpose are the a-amylases from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Cleaning-active proteases and amylases are generally not made available in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • These readymade preparations include, for example, the solid preparations obtained through granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel agents, solutions ofthe enzymes, advantageously maximally concentrated, low-water, and/or supplemented with stabilizers or other auxiliaries.
  • the enzymes can also be encapsulated, for example by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed in a set 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.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are enclosed in a set 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.
  • other active substances such as stabilizers, emulsifiers, pigments, or dyes, can be additionally applied.
  • Such capsules are applied using inherently known methods, for example by shaking or roll granulation or in fluidized bed processes. Such granular materials are advantageously low in dust, for example due to the application of polymeric film-formers,
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations used according to the invention contain between 1 and 40 wt.%, preferably between 2 and 30 wt.%, particularly preferably between 3 and 25 wt.% of the enzyme protein.
  • those cleaning agents are preferred which contain, based on their total weight, 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and in particular 0.5 to 8 wt.% of the respective enzyme preparations.
  • dishwashing detergent formulations comprise enzymes, they preferably comprise these in amounts of from 0.001 to 3.0 % of active enzyme protein by weight of the total composition.
  • the wt % of enzymes are calculated by mass of the active enzyme protein per weight of the total composition.
  • the dishwashing detergent formulation is characterized in that the composition comprises amylases in an amount of 0.05 to 20 mg active enzyme protein per gram of the total composition, preferably 0.10 to 10 mg active enzyme protein per gram of the total composition, most preferred 0.15 to 2 mg active enzyme protein per gram of the total composition.
  • the dishwashing detergent formulation is characterized in that the composition comprises proteases in an amount of 0.1 to 50 mg active enzyme protein per gram of the total composition, preferably 0.2 to 25 mg active enzyme protein per gram of the total composition, 0.5 to 10 mg active enzyme protein per gram of the total composition.
  • amylases and proteases preference is given to using amylases and proteases.
  • Formulations according to the invention can comprise one or more enzyme stabilizers.
  • Enzyme stabilizers serve to protect enzyme - particularly during storage - against damage such as, for example, inactivation, denaturation or decomposition for example as a result of physical influences, oxidation or proteolytic cleavage.
  • enzyme stabilizers are reversible protease inhibitors, for example benzamidine hydrochloride, borax, boric acid, boronic acids or salts or esters thereof, including in particular derivatives with aromatic groups, for example ortho-, meta- or para-substituted phenyl boronic acids, in particular 4-formylphenyl boronic acid, or the salts or esters of the aforementioned compounds.
  • Peptide aldehydes i.e. oligopeptides with a reduced carbon terminus, in particular those made of 2 to 50 monomers, are also used for this purpose.
  • Peptidic reversible protease inhibitors include inter alia ovomucoid and leupeptin.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and - propanolamine and mixtures thereof, aliphatic mono- and dicarboxylic acids up to C12-carboxylic acids, such as for example succinic acid. Terminally capped fatty acid amide alkoxylates are also suitable enzyme stabilizers.
  • enzyme stabilizers are sodium sulfite, reducing sugars and potassium sulfate.
  • a further example of a suitable enzyme stabilizer is sorbitol.
  • Organic solvents might be present as well but are preferably limited to an amount of up to 30 wt.%, based on the weight of the composition.
  • Especially preferred organic solvents are propane diol, glycerol and/or sorbitol. These amounts of organic solvents add to the pourability as well as to the stabilization of active ingredients.
  • the dishwashing detergent composition comprises one or more organic solvent selected from the group of sorbitol, glycerol and/or propane diol. More preferably, the composition comprises from 1 to 25% by weight, preferably 2 to 12 % by weight of the total composition from the group of sorbitol, glycerol and/or propane diol.
  • the dishwashing detergent formulation according to the invention is preferably characterized in that the composition has a pH of 7.0 to 11 .5 at 20 °C.
  • the pH is measured in the product itself.
  • a suitable instrument is e. g. a conventional pH-electrode.
  • the composition comprises (i) 1 - 4 % by weight of the total composition of
  • polyaspartic acid or modified polyaspartic acid or salts thereof wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% of aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base, (b) at least one graft copolymer composed of
  • (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of
  • (b3) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is from 18: 1 to 5:1 ;
  • the composition has a pH of 7.0 to 8.5, preferably 7.5 to 8.0 at 20 °C.
  • the enzyme stability is enhanced due to the pH. These compositions are surprisingly good to clean delicate dishware, without damages to glass or decors on glass or porcelain.
  • polyaspartic acid or modified polyaspartic acid or salts thereof wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% of aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base,
  • (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of
  • (b3) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is from 18: 1 to 5:1 ;
  • compositions might also be used alone or as enzyme containing component (A) of a multicomponent system.
  • the composition has a pH of 7.0 to 8.5, preferably 7.5 to 8.0 at 20 °C.
  • the enzyme stability is enhanced due to the pH.
  • polyaspartic acid or modified polyaspartic acid or salts thereof wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% of aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base,
  • (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of
  • (b3) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is from 18: 1 to 5:1 ;
  • the dishwashing detergent formulation is preferably characterized in that the composition has a pH of 9 to 11.5 at 20 °C.
  • These compositions may be used alone or as alkaline compositions (B) of a multicomponent system.
  • the composition comprises from 1 to 7% by weight, preferably 2 to 5 % by weight of the total composition as builder (component according to (v) of claim 1) a phosphonate or its salts, preferably HEDP or its salts.
  • composition A comprises at least one enzyme and composition B is preferably free from enzymes.
  • composition A and composition B are distinct from one another. In the context of the present invention, this means that composition A and B differ in terms of formulation and are further spatially separated from one another.
  • composition A comprises at least one enzyme and composition B is free from enzymes.
  • compositions A and B of the cleaning composition ofthe present invention means that the individual components of compositions A cannot come into contact with the components of composition B.
  • the cleaning composition of the present invention may be provided in the form of a multi-chambered package, such as a bottle, tube or pouch, in particular a dual-chambered bottle or pouch, wherein compositions A and B are located separately from one another in separate, distinct chambers.
  • the present invention relates to the use of a cleaning composition, as herein described above, for the cleaning of dishes, preferably dishware.
  • the compositions are preferably used in automatic dishwashing and/or automatic dishwashing machines.
  • “Dishware”, in the context of the present invention includes dishes, cups, cutlery, glassware, food storage containers, cooking utensils (cookware) and the like.
  • the present invention relates to a method of cleaning dishes, preferably in an automatic dishwashing machine, characterized in that in at least one method step at least one cleaning composition according to the invention, as herein disclosed, is used.
  • the present invention relates to a method for cleaning dishes in an automatic dishwasher, in which the agent is dispensed into the interior of an automatic dishwasher while a dishwashing program is being executed, before the main washing cycle begins, or in the course of the main washing cycle.
  • Dispensing or introduction of the agent into the interior of the automatic dishwasher can take place manually, but preferably the agent is dispensed into the interior of the automatic dishwasher by means of the dosing chamber.
  • the (washing) temperature in such dishwashing methods is preferably 50°C or lower, particularly preferably 45°C or lower, still more preferably 40°C or lower.
  • polyaspartic acid or modified polyaspartic acid or salts thereof wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% of aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base,
  • (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of
  • (b3) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is from 18: 1 to 5:1 ;
  • the dishwashing detergent formulation according to point 1 characterized in that the weight ratio of (a): (b) is from 1 1 : 1 to 8 : 1 .
  • the dishwashing detergent formulation according to any one of points 1 or 2 characterized in that the weight ratio of (a): (b) is from 11 : 1 to 9 : 1 .
  • the dishwashing detergent formulation according to any one of points 1 to 4, characterized in that the composition comprises methylglycinediacetic acid (MGDA) or salts thereof as complexing agent.
  • MGDA methylglycinediacetic acid
  • MGDA methylglycinediacetic acid
  • the dishwashing detergent formulation according to any one of points 1 to 11 , containing a modified polyaspartic acid or salt thereof obtainable by polycondensation of (a1) is 80 to
  • Z is O or NR1 ,
  • R1 is selected from methyl and hydrogen
  • a 1 is selected from C2-C4-alkylene
  • R2 are identical or different and selected from C1-C4-alkyl
  • X- is selected from halide, mono-C1-C4-alkyl sulfate and sulfate.
  • the dishwashing detergent formulation according to any one of points 1 to 18, characterized in that the composition comprises less than 0.1 %, preferably less than 0.01 % by weight of phosphonates, preferably the composition comprises less than 0.01 % by weight of phosphorous containing compounds.
  • the dishwashing detergent formulation according to any one of points 1 to 21 , characterized in that the composition comprises amylases in an amount from 0.05 to 20 mg active enzyme protein per gram of the total composition, preferably from 0.10 to 10 mg active enzyme protein per gram of the total composition, most preferred from 0.15 to 2 mg active enzyme protein per gram of the total composition.
  • the dishwashing detergent formulation according to any one of points 1 to 22, characterized in that the composition comprises proteases in an amount of 0.1 to 50 mg active enzyme protein per gram of the total composition, preferably 0.2 to 25 mg active enzyme protein per gram of the total composition, 0.5 to 10 mg active enzyme protein per gram of the total composition.
  • the dishwashing detergent formulation according to any one of points 1 to 23, characterized in that the composition comprises one or more organic solvent selected from the group of sorbitol, glycerol and/or propane diol.
  • polyaspartic acid or modified polyaspartic acid or salts thereof wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% of aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base,
  • (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of
  • (b3) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is from 18: 1 to 5:1 ;
  • polyaspartic acid or modified polyaspartic acid or salts thereof wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% of aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base,
  • (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of
  • (b3) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is from 18: 1 to 5:1 ;
  • polyaspartic acid or modified polyaspartic acid or salts thereof wherein the modified polyaspartic acid is obtainable by polycondensation of (a1) 50 to 99 mol% of aspartic acid and (a2) 1 to 50 mol% of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the cocondensates with the addition of a base,
  • (b1) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of
  • (b3) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a) : (b) is from 18: 1 to 5:1 ;
  • the dishwashing detergent formulation according to point 30 characterized in that the composition has a pH of 9 to 11 .5 at 20 °C.
  • compositions I to IV were prepared using the components summarized in Table 1 with the amounts of active ingredients given in wt.% referring to the total weight of the composition unless otherwise specified.
  • the pH of the undiluted liquid phase was adjusted to 7.8 at 20 °C.
  • the compositions were tested for filming and spotting.
  • the compositions I to IV according to the invention delivered significantly reduced spotting and filming results compared to the comparison example that showed heavy spotting and filming.
  • the results forthe formulations tested are listed in Table 3 as arithmetic mean values. Higher values mean lower drop formation/filming, i.e. better rinse performance.
  • Results of the comparative rinse experiments demonstrate that the spotting results of formula VI (according to table 2) is much better with the polymers according to a) and b); ratio a:b 10:1 and in an amount of 2.2 wt% compared to the formulas C1 (amount of polymers 5.5 wt%) and C2 (amount of polymers 12 wt%). Also, the filming results of formula VI are reduced compared to C1 and C2.
  • the amount of polymers a) and b) is important to achieve a high rinsing performance.

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Abstract

L'invention concerne des détergents liquides sans phosphates, pour laver la vaisselle, qui sont essentiellement sans javel et qui contiennent une combinaison polymère d'acide polyaspartique ou d'acide polyaspartique modifié et des polymères greffés basés sur des oligosaccharides et des polysaccharides, qui améliore la brillance sur le verre.
PCT/EP2023/085326 2022-12-15 2023-12-12 Détergent liquide pour laver la vaisselle Ceased WO2024126473A1 (fr)

Priority Applications (1)

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EP23817789.3A EP4634347A1 (fr) 2022-12-15 2023-12-12 Détergent liquide pour laver la vaisselle

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EP22213740.8A EP4386071A1 (fr) 2022-12-15 2022-12-15 Détergent liquide pour lave-vaisselle
EP22213740.8 2022-12-15

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WO2024126473A1 true WO2024126473A1 (fr) 2024-06-20

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DE102023212958A1 (de) * 2023-12-19 2025-06-26 Henkel Ag & Co. Kgaa Reinigungsmittelkonzentrat
DE102023212964A1 (de) 2023-12-19 2025-06-26 Henkel Ag & Co. Kgaa Flüssiges Reinigungsmittel

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4221875A1 (de) 1992-07-03 1994-01-05 Basf Ag Modifizierte Polyasparaginsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2015197379A1 (fr) 2014-06-23 2015-12-30 Basf Se Formulations, leur production et leur utilisation et composants appropriés
US20170145352A1 (en) * 2014-06-23 2017-05-25 Basf Se Formulations, use thereof as or for the production of dishwashing detergents, and production thereof
WO2019211231A1 (fr) 2018-05-02 2019-11-07 Basf Se Formulations détergentes pour lave-vaisselle comprenant du poly(acide aspartique) et des polymères greffés à base d'oligo et polysaccharides comme additifs inhibant la formation de film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4221875A1 (de) 1992-07-03 1994-01-05 Basf Ag Modifizierte Polyasparaginsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
WO2015197379A1 (fr) 2014-06-23 2015-12-30 Basf Se Formulations, leur production et leur utilisation et composants appropriés
US20170130168A1 (en) * 2014-06-23 2017-05-11 Basf Se Formulations, the production and use thereof, and suitable components
US20170145352A1 (en) * 2014-06-23 2017-05-25 Basf Se Formulations, use thereof as or for the production of dishwashing detergents, and production thereof
WO2019211231A1 (fr) 2018-05-02 2019-11-07 Basf Se Formulations détergentes pour lave-vaisselle comprenant du poly(acide aspartique) et des polymères greffés à base d'oligo et polysaccharides comme additifs inhibant la formation de film

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