EP3080242A1 - Lessive liquide pour lave-vaisselle, exempte de phosphates - Google Patents

Lessive liquide pour lave-vaisselle, exempte de phosphates

Info

Publication number
EP3080242A1
EP3080242A1 EP14814812.5A EP14814812A EP3080242A1 EP 3080242 A1 EP3080242 A1 EP 3080242A1 EP 14814812 A EP14814812 A EP 14814812A EP 3080242 A1 EP3080242 A1 EP 3080242A1
Authority
EP
European Patent Office
Prior art keywords
acid
dishwashing detergent
dishwashing
composition
enzyme
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.)
Granted
Application number
EP14814812.5A
Other languages
German (de)
English (en)
Other versions
EP3080242B1 (fr
Inventor
Nina Mussmann
Thomas Eiting
Noelle Wrubbel
Thorsten Bastigkeit
Hans Hartmut Janke
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 EP3080242A1 publication Critical patent/EP3080242A1/fr
Application granted granted Critical
Publication of EP3080242B1 publication Critical patent/EP3080242B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043—Liquid or thixotropic (gel) 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to a phosphate-free, liquid dishwashing detergent which exhibits improved stability and cleaning performance, in particular of enzyme-sensitive soiling, the use of this dishwashing detergent and a method for machining
  • Dishwashing detergents with increased cleaning performance In addition, a general trend for reasons of environmental protection in machine dishwashing to dispense with phosphates is observed. Thus, there is the problem of providing phosphate-free automatic dishwashing detergents without compromising cleaning performance or stability.
  • a dishwashing detergent requires alkalinity.
  • Many other dried-on food residues require enzymes, such as amylases and proteases.
  • alkalinity and enzymes together can not be stably formulated.
  • Liquid dishwashing detergents also require special stabilizers to stabilize the enzymes. These include, inter alia, calcium salts and especially for proteases additionally polyols and / or boric acid.
  • GLDA Glutamic diacetic acid
  • complexing agents in particular phosphonates, such as 1-hydroxyethane (1, 1-diphosphonic acid) (HEDP), are suitable.
  • the object of the present invention was therefore to provide a phosphate-free, liquid dishwashing detergent which overcomes the stated stability problems and has a good cleaning performance.
  • the phosphonate used as a complexing agent must be formulated spatially separated from enzymes and enzyme stabilizers, especially calcium salts.
  • a first subject of the present invention is therefore a phosphate-free, liquid
  • Dishwashing detergent in particular a machine dishwashing detergent, comprising two spatially separate liquid compositions A and B, wherein
  • composition A is phosphonate-free and comprises at least one enzyme, preferably a protease and / or amylase, and at least one calcium salt suitable for stabilizing the at least one enzyme and having a pH of less than 9, preferably of 8.5,
  • Composition B is enzyme- and calcium-free and comprises at least one phosphonate, in particular 1-hydroxyethane- (1, 1-diphosphonic acid) (HEDP), and has a pH greater than 9, preferably greater than 10.
  • HEDP 1-hydroxyethane- (1, 1-diphosphonic acid
  • At least one includes, but is not limited to 1, 2, 3, 4, 5, 6 and more.
  • a dishwashing agent according to the invention in a machine dishwashing process, in particular the use for improving the cleaning performance of enzyme-sensitive soiling on dishes during its cleaning in an automatic dishwashing machine.
  • the present invention is also directed to a machine dishwashing process in which a dishwashing composition according to the invention, in particular for the purpose, the
  • Composition is substantially free of phosphates or phosphonates, i.
  • composition A in particular phosphates or phosphonates in amounts less than 0.1 wt .-%, preferably less than 0.01 wt .-%, based on the composition A contains.
  • Substantially free of calcium salts i. in particular calcium salts in amounts less than 0.1 wt .-%, preferably less than 0.07 wt .-%, more preferably less than 0.05 wt .-%, preferably less than 0.03 wt .-%, particularly preferably less than 0.01 wt .-%, based on the composition B contains.
  • Enzyme-free as used herein means that the subject composition is in the
  • composition B Essentially free of enzymes, i. in particular enzymes or enzyme preparations or preparations in amounts of less than 0.1% by weight, preferably less than 0.05% by weight, preferably less than 0.01% by weight, in particular less than 0.001% by weight based on the composition B contains.
  • Liquid as used herein includes liquids and gels.
  • the term "spatially separated" with respect to the compositions as used herein means that the compositions can not come into contact with each other prior to use.
  • the dishwashing detergent is provided in a multi-compartment package such as a bottle or pouch for this purpose. in particular a two-chamber bottle or a Zweichammerpouch, wherein the respective composition is separate from the other composition (s) in a separate chamber.
  • composition A contains at least one further enzyme.
  • Suitable enzymes include, but are not limited to, proteases, lipases, hemicellulases, particularly pectinases and / or mannanases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.
  • These enzymes and the amylases used are in principle of natural origin; Based on the natural molecules, improved variants are available for use in dishwashing detergents, which are preferably used accordingly.
  • Dishwashing agents according to the invention contain enzymes, including amylase, preferably in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • proteases are among the most technically important enzymes of all. For detergents and dishwashing detergents, they are the longest established enzymes and contained in virtually all modern, powerful detergents and dishwashing detergents. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range.
  • Subtilases Subtilisin-like Proteases
  • R. Siezen pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996.
  • Subtilases are naturally occurring formed by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
  • subtilisin-type proteases preferably used in washing and dishwashing detergents are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483,
  • Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, correspondingly optimized variants are known for most proteases known from the prior art.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in dishwashing detergents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention.
  • lipases or cutinases in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, those originally from Humicola lanuginosa
  • Thermomyces lanuginosus available, or further developed lipases, in particular those with one or more of the following amino acid substitutions starting from said lipase in positions D96L, T213R and / or N233R., Particularly preferably T213R and N233R.
  • enzymes can be used which are termed hemicellulases
  • 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.
  • peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or in the case of strong
  • 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.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • the dishwashing agents may contain, in addition to the calcium salts, further stabilizers, in particular polyols, in particular glycerol, propylene glycol and / or boron-containing compounds, such as boric acid and salts thereof.
  • Preferred boron-containing compounds are phenylboronic acid derivatives, in particular the phenylboronic acid derivative 4-formyl-phenylboronic acid (4-FPBA).
  • phenylboronic acid derivatives may also have further chemical modifications on the phenyl ring, in particular they may contain one or more methyl, amino, nitro, chloro, fluoro, bromo, hydroxyl, formyl, ethyl, acetyl, t-butyl, anisyl, benzyl, trifluoroacetyl, N-hydroxysuccinimide, t-butyloxycarbonyl, benzoyl, 4-methylbenzyl, thioanizyl, thiocresyl, benzyloxymethyl, 4-nitrophenyl, Benzyloxycarbonyl, 2-nitrobenzoyl, 2-nitrophenylsulphenyl, 4-toluenesulphonyl, pentafluorophenyl, diphenylmethyl, 2-chlorobenzyloxycarbonyl, 2,4,5-trichlorophenyl, 2-bromobenzyloxycarbonyl, 9-fluorenyl,
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and
  • Water-soluble calcium salts useful as enzyme stabilizers include, but are not limited to, calcium chloride (CaCk), calcium lactate or calcium acetate. Also suitable are other salts of calcium with alpha-hydroxycarboxylic acids or alpha-amino acids.
  • the at least one calcium salt suitable for the stabilization of enzymes is contained in various embodiments in an amount of 0.05 to 2% by weight, in particular 0, 1 to 0.6% by weight, based on composition A.
  • Phosphonates can be used.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • hydroxyalkane phosphonates the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance.
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are present in the compositions preferably in amounts of from 0.5 to 5% by weight, in particular in amounts of from 1 to 3% by weight, in each case based on the total weight of the composition B.
  • dishwashing agents described herein are of a liquid nature and may, in particular, be present as homogeneous solutions or suspensions. In a further preferred
  • the dishwashing detergent is in a pre-portioned form.
  • the automatic dishwashing detergent has several spatially separate compositions, making it possible, on the one hand, to separate incompatible ingredients from one another, and, on the other hand, to offer compositions in combination which are used at different times in the dishwasher.
  • the dishwashing agents preferably also contain builders and surfactants. Unless otherwise specified, the data in% by weight refers to the respective
  • usable builders include in particular carbonates, citrates, MGDA
  • GLDA glutamic acid-N, N-diacetic acid
  • EDDS ethylenediamine-N, N'-disuccinic acid
  • organic cobuilders and silicates Particularly preferred are GLDA (glutamic acid-N, N-diacetic acid) or salts thereof.
  • Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals and dextrins.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid,
  • NTA nitrilotriacetic acid
  • the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of dishwashing detergents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • dishwashing detergent compositions contain as builders citrate, for example sodium or potassium citrate.
  • Compositions containing from 1 to 15% by weight, preferably from 2 to 12% by weight of citrate are preferred according to the invention.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • the dishwashing agents as a builder also crystalline layered silicates of general formula NaMSix02x + i ⁇ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and secondary wash properties.
  • the content of silicates based on the total weight of the dishwashing detergent, to amounts below 10 wt .-%, preferably below 5 wt .-% and especially limited below 2 wt .-%.
  • Particularly preferred dishwashing detergents are silicate-free.
  • the dishwashing compositions of the invention may further comprise a sulfopolymer.
  • Weight fraction of the sulfopolymer in the total weight of the dishwashing agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1, 0 to 15 wt .-%, in particular from 4 to 14 Wt .-%, especially from 6 to 12 wt .-%.
  • the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymers.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)
  • Monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid,
  • R 5 (R 6 ) C C (R 7 ) -X-S0 3 H in which R 5 to R 7 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2, -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • 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 monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably in each case from 5 to 95% by weight, particularly preferably Proportion of sulfonic acid group-containing monomer 50 to 90 wt .-% and the proportion of
  • 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 dishwashing detergents are characterized in that the copolymers have molecular weights from 2000 to 200,000 gmol ⁇ preferably from 4000 to 25,000 gmol "and in particular from 5000 to 15,000 gmol -1.
  • the copolymers include besides
  • Carboxyl-containing monomer and sulfonic acid-containing monomer further at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • nonionic monomers are preferably monomers of the general formula
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • Acrylic acid hexyl ester methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, Octyl methacrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (lauryl) acrylamide, stearyl acrylate, methacrylic acid stearyl ester, N- (stearyl) acrylamide, behenyl acrylate, behenyl methacrylate and N- (behenyl) acrylamide or mixtures thereof.
  • the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
  • the dishwashing detergents may contain alkali metal hydroxides. These alkali carriers are preferred in dishwashing detergents only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight. and in particular between 0.5 and 5 wt .-%, each based on the total weight of
  • Dishwashing composition used used.
  • the alkali metal hydroxides are used in amounts such that the pH values according to the invention are achieved.
  • the dishwashing compositions according to the invention preferably further comprise at least one nonionic surfactant.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants which have a melting point above
  • Nonionic (s) surfactants having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • particularly preferred nonionic surfactants have been low-foaming nonionic surfactants which contain alternating ethylene oxide and ethylene oxide
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24-alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • nonionic surfactants having a C9-alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units, followed by 1 to 4
  • Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH 2 O- (AO) w- (AO) x- (A "O) y - (A"'O) z R 2 , in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical
  • R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms
  • A, ⁇ ', A "and A'" independently of one another are radicals from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 - CH (CH 3 ) -CH 2 -, - CH 2 -CH (CH 2 -CH 3 ),
  • w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • Preparations are significantly improved both in comparison to surfactant-free system as well as compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • Preference is given in particular to those end-capped, poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 0 [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R, which is linear or branched, saturated or unsaturated, aliphatic or aromatic
  • Hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22
  • Carbon atoms further having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, wherein x for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60 stands.
  • surfactants of the formula R 0 [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] yCH 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 one 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 C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] jOR 2 where R and R 2 are 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.
  • 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 1 R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 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 for a straight-chain or branched, saturated or on or
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26
  • A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3 ),
  • w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40
  • nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • dishwashing detergents are characterized in that the dishwashing detergent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant on the
  • Total weight of the dishwashing agent is preferably 0, 1 to 10 wt .-%, preferably 0.5 to 8.0 wt .-% and in particular 1, 0 to 4.0 wt .-%.
  • the pH of the dishwashing detergent can be adjusted by means of customary pH regulators.
  • the pH of Composition A is in the range of 5.5 to 8.5, preferably 6.5 to 8.0, more preferably 6.8 to 7.5
  • the pH of Composition B is in a range of 9.0 to 12, preferably 10.0 to 1 1, 5, preferably greater than 10, in particular 10.5 to 1 1, 5.
  • the pH adjusting agents are acids and / or alkalis, preferably alkalis. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular the alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred.
  • volatile alkali for example in the form of ammonia and / or alkanolamines, which may contain up to 9 carbon atoms in the molecule.
  • the alkanolamine here is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the alkanolamine is preferably contained in agents according to the invention in an amount of from 0.5 to 10% by weight, in particular in an amount of from 1 to 6% by weight.
  • the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which at the same time complexing agents or even
  • Chelating agents are.
  • Particularly preferred buffer substances are citric acid or citrates, in particular the sodium and potassium lead,
  • trisodium citrate 2H20 and tripotassium citrate ⁇ 2 ⁇ for example, trisodium citrate 2H20 and tripotassium citrate ⁇ 2 ⁇ .
  • the agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, in particular anionic surfactants, bleaching agents, bleach activators,
  • Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • fatty acid cyanamides sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-Cs-Os-alkyl esters, sulfosuccinamates,
  • Fatty acid sarcosinates Fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii ) (R iv ) (R v ) N + CH 2 COO " , in which R i is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv as well R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • Suitable cationic surfactants are the quaternary
  • surface-active compounds in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • the content of zinc salt in dishwashing agents is preferably between 0.1 to 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt.
  • the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 to 1% by weight, preferably between 0.02 to 0.5% by weight and in particular between 0.04 to 0.2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • dishwashing agents described herein can take place in different ways.
  • Solvents may be thickened, in the form of gels.
  • the detergent immediately after production has a viscosity above 2000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 2000 and 10,000 mPas.
  • the viscosity may be higher, for example greater than 10,000 mPas, for example in the range 10000-50000 mPas,
  • the dishwashing agents described herein are preferably prefabricated into dosage units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.
  • the dishwashing agents in particular the prefabricated metering units, with particular preference have a water-soluble coating.
  • the water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different.
  • Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
  • the water-soluble coating be polyvinyl alcohol or a
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose
  • Molecular weight in the range of 10,000 to 1,000,000 gmol "1 , preferably from 20,000 to 500,000 gmol 1 , more preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol.
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath is selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath
  • (Meth) acrylic acid-containing (co) polymers polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Particularly preferably contain such Polyvinyl alcohol copolymers in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
  • the film material contains further additives.
  • the film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,
  • Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.
  • water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the corresponding use of the automatic dishwasher detergents according to the invention is likewise an object of the invention.
  • the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used.
  • the subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the
  • Dishwasher is metered.
  • the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.
  • the dishwashing compositions according to the invention comprise an enzyme phase which corresponds to Formulation A and an alkali phase which corresponds to Formulation B.
  • Formulation 1 corresponds to the formulation according to the invention
  • Formulation 2 is a comparison formulation containing precipitations of
  • Table 1 Composition of the automatic dishwashing agent (% by weight)
  • Residues (perfume, dyes, preservatives, ad 100 ad 100 ad 100 ad 100 water, etc.) (wt .-%)

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne une lessive liquide, exempte de phosphates, pour lave-vaisselle, qui présente une stabilité et un pouvoir nettoyant améliorés, en particulier vis-à-vis des salissures sensibles aux enzymes, l'utilisation de cette lessive pour lave-vaisselle et un procédé de lavage de vaisselle à la machine en utilisant ladite lessive pour lave-vaisselle.
EP14814812.5A 2013-12-13 2014-12-11 Lessive liquide pour lave-vaisselle, exempte de phosphates Active EP3080242B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013225920.4A DE102013225920A1 (de) 2013-12-13 2013-12-13 Phosphatfreies flüssiges Geschirrspülmittel
PCT/EP2014/077414 WO2015086761A1 (fr) 2013-12-13 2014-12-11 Lessive liquide pour lave-vaisselle, exempte de phosphates

Publications (2)

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EP3080242A1 true EP3080242A1 (fr) 2016-10-19
EP3080242B1 EP3080242B1 (fr) 2018-08-22

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DE (1) DE102013225920A1 (fr)
ES (1) ES2691557T3 (fr)
WO (1) WO2015086761A1 (fr)

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Publication number Priority date Publication date Assignee Title
ES2884253T3 (es) 2014-03-24 2021-12-10 Chemische Fabrik Dr Weigert Gmbh & Co Kg Agente de limpieza y procedimiento para el lavado de la vajilla
EP4332208A3 (fr) 2016-09-07 2024-05-08 Ecolab USA Inc. Compositions détergentes contenant une enzyme stabilisée par des phosphonates
DE102017212561A1 (de) * 2017-07-21 2019-01-24 Henkel Ag & Co. Kgaa Geschirrspülmittel enthaltend Citratdihydrat und -anhydrat
DE102018220189A1 (de) * 2018-11-23 2020-05-28 Henkel Ag & Co. Kgaa Reinigungsmittel zur automatischen Dosierung
EP4194535A1 (fr) 2021-12-09 2023-06-14 Henkel AG & Co. KGaA Composition de nettoyage à deux phases avec des particules de détergent visiblement distinctes
EP4379028A1 (fr) * 2022-11-30 2024-06-05 Henkel AG & Co. KGaA Systeme de builder pour l'élimination des taches de protéines

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GB2355269A (en) * 2000-08-08 2001-04-18 Procter & Gamble Liquid cleaning composition
GB2373254A (en) * 2001-03-16 2002-09-18 Procter & Gamble Detergent product
US20090165821A1 (en) * 2005-09-02 2009-07-02 Henkel Kgaa Detergents
GB0611206D0 (en) * 2006-06-07 2006-07-19 Reckitt Benckiser Nv Detergent composition

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WO2015086761A1 (fr) 2015-06-18
ES2691557T3 (es) 2018-11-27
EP3080242B1 (fr) 2018-08-22

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