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WO2013160301A1 - Formulations, leur utilisation comme détergents pour vaisselle ou pour la production de détergents pour vaisselle, et leur préparation - Google Patents

Formulations, leur utilisation comme détergents pour vaisselle ou pour la production de détergents pour vaisselle, et leur préparation Download PDF

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Publication number
WO2013160301A1
WO2013160301A1 PCT/EP2013/058391 EP2013058391W WO2013160301A1 WO 2013160301 A1 WO2013160301 A1 WO 2013160301A1 EP 2013058391 W EP2013058391 W EP 2013058391W WO 2013160301 A1 WO2013160301 A1 WO 2013160301A1
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WO
WIPO (PCT)
Prior art keywords
range
acid
formulation
formulations
formulation according
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PCT/EP2013/058391
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German (de)
English (en)
Inventor
Alejandra Garcia Marcos
Stephan Hüffer
Markus Hartmann
Heike Weber
Mario Emmeluth
Frank-Peter Lang
Ralf Bohlander
Original Assignee
Basf Se
Basf Schweiz Ag
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 Basf Se, Basf Schweiz Ag filed Critical Basf Se
Priority to BR112014026565A priority Critical patent/BR112014026565A2/pt
Priority to KR1020147032948A priority patent/KR102007148B1/ko
Priority to EP13720303.0A priority patent/EP2841549B1/fr
Priority to CN201380033256.6A priority patent/CN104379717B/zh
Priority to CA2871210A priority patent/CA2871210A1/fr
Priority to ES13720303.0T priority patent/ES2612342T3/es
Priority to JP2015507501A priority patent/JP6133971B2/ja
Priority to RU2014147082A priority patent/RU2623440C2/ru
Priority to MX2014013009A priority patent/MX2014013009A/es
Priority to JP2016509313A priority patent/JP6235120B2/ja
Priority to PL13774145T priority patent/PL2989192T3/pl
Priority to KR1020157033213A priority patent/KR20160003006A/ko
Priority to BR112015026763A priority patent/BR112015026763A2/pt
Priority to US14/786,327 priority patent/US20160075972A1/en
Priority to ES13774145.0T priority patent/ES2693772T3/es
Priority to EP13774145.0A priority patent/EP2989192B1/fr
Priority to RU2015149916A priority patent/RU2015149916A/ru
Priority to CN201380075863.9A priority patent/CN105143424B9/zh
Priority to PCT/EP2013/070857 priority patent/WO2014173473A1/fr
Publication of WO2013160301A1 publication Critical patent/WO2013160301A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/37—Polymers

Definitions

  • the present invention relates to formulations containing
  • A at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts
  • B at least one alkoxylated alkyleneimine polymer having an average molecular weight Mw in the range from 800 to 25,000 g / mol having a positive charge density of at least 5 meq / g and having in the range of 2 to at most 80 wt .-% alkylene oxide side chains, based on the total alkoxylated alkyleneimine polymer.
  • the present invention relates to a process for the preparation of formulations according to the invention and their use as or for the production of dishwashing agents, in particular dishwasher detergents for automatic dishwashing.
  • Dishwashing detergents have many requirements to fulfill. So they have to clean the dishes thoroughly, they should have no harmful or potentially harmful substances in the wastewater, they should allow the draining and drying of the water from the dishes, and they should not cause problems when operating the dishwasher. Finally, they should not lead to aesthetically undesirable consequences on the good to be cleaned. Especially in this context is the glass corrosion.
  • Glass corrosion is caused not only by mechanical effects, for example, by juxtaposition of glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences.
  • certain ions can be released from the glass by repeated mechanical cleaning, adversely altering the optical and thus the aesthetic properties.
  • Glass corrosion has several effects. On the one hand, one can observe the formation of microscopically fine cracks, which are noticeable in the form of lines. On the other hand, one can often observe a general cloudiness, for example a roughening, which makes the glass in question look unaesthetic. Overall, such effects are also subdivided into iridescent discoloration, scoring and surface and annular opacities.
  • WO 2006/108857 discloses alkoxylated polyethyleneimines as additives to detergents.
  • Detergents containing zeolites or polyaminocarboxylates such as EDTA or triethylenediamine pentaacetate as complexing agents are disclosed by way of example.
  • WO 01/96516 proposes formulations containing alkoxylated polyethylenimine for cleaning hard surfaces. For rinsing, purified water is used. From WO 2010/020765 dishwashing agents are known which contain polyethyleneimine. Such dishwashing agents may contain phosphate or be phosphate-free. It is attributed to them a good inhibition of glass corrosion. Zinc and bismuth-containing dishwashing detergents are not recommended. However, glass corrosion, in particular line corrosion and turbidity, is in many cases not sufficiently delayed or prevented.
  • Formulations of the invention are heavy metal-free. This is to be understood in the context of the present invention that formulations according to the invention are free of those heavy metal compounds which do not act as bleach catalysts, in particular of compounds of iron and bismuth. In the context of the present invention, "free from” is to be understood in connection with heavy metal compounds as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in the range from 0 to 100 ppm, determined by the Leach method and based on The formulation according to the invention preferably has a heavy metal content below 0.05 ppm, based on the solids content of the relevant formulation.
  • heavy metals are all metals having a specific density of at least 6 g / cm 3.
  • heavy metals are noble metals and also zinc, bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
  • formulation of the invention contains no measurable levels of zinc and bismuth compounds, that is, for example, less than 1 ppm. Contain formulations according to the invention
  • A at least one aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and salts thereof, in the context of the present invention also referred to as aminocarboxylate (A) or compound (A), and preferably their salts.
  • MGDA methylglycine diacetate
  • IDS iminodisuccinic acid
  • GLDA glutamic acid diacetate
  • inorganic cations for example ammonium, alkali or alkaline earth metal, preferably Mg 2+ , Ca 2+ , Na + , K + , or organic cations, preferably ammonium substituted with one or more organic radicals, in particular triethanolammonium, ⁇ , ⁇ -diethanolammonium, N-mono-C 1 -C 4 -alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N, N-di-C 1 -C 4 -alkylethanolammonium.
  • inorganic cations for example ammonium, alkali or alkaline earth metal, preferably Mg 2+ , Ca 2+ , Na + , K + , or organic cations, preferably ammonium substituted with one or more organic radicals, in particular triethanolammonium, ⁇ , ⁇ -diethanolammonium, N-mono-C 1 -C
  • Very particularly preferred compounds (A) are the alkali metal salts, in particular the sodium salts of methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GL DA).
  • MGDA methylglycine diacetate
  • IDS iminodisuccinic acid
  • GL DA glutamic acid diacetate
  • MGDA methylglycine diacetate
  • IDS iminodisuccinic acid
  • GLDA glutamic acid diacetate
  • Formulations according to the invention also contain
  • modified alkyleneimine polymers are also briefly referred to as modified polyalkyleneimine (B) in the context of the present invention.
  • alkyleneimine polymers are to be understood as meaning those polymeric materials which are obtained by homo- or copolymerization of one or more cyclic imines or by grafting a (co) polymer with at least one cyclic imine.
  • examples are polyalkylenepolyamines and polyamidoamines grafted with ethyleneimine.
  • polyalkylene polyamines are preferably understood as meaning those polymers which contain at least six nitrogen atoms and at least five C 2 -C 10 -alkylene units, preferably C 2 -C 3 -alkylene units per molecule, for example pentaethylenehexamine, and in particular polyethyleneimines.
  • Alkyleneimine polymer and especially polyethyleneimine may have, for example, an average molecular weight (M w ) of at least 300 g / mol, preferably the average molecular weight of polyethylenimine is in the range from 800 to 20,000 g / mol, determined by light scattering.
  • M w average molecular weight
  • Polyalkylenepolyamines can be covalently modified in partially quaternized (alkylated) form as Alkylenimin- polymer.
  • Suitable quaternizing agents are, for example, alkyl halides, in particular C 1 -C 10 -alkyl chloride, such as methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, n-butyl chloride, tert-butyl chloride, n-hexyl chloride, furthermore epichlorohydrin, dimethyl sulfate, diethyl sulfate and benzyl chloride.
  • the degree of quaternization (alkylation) is preferably 1 to 25, particularly preferably up to 20 mol%, based on quaternizable (alkylatable) N atoms in alkyleneimine. Polymer.
  • polyamidoamines grafted with ethyleneimine are suitable as alkyleneimine polymers.
  • Suitable polyamidoamines are obtainable, for example, by reacting C 4 -C 10 -dicarboxylic acids with polyalkylenepolyamines, which preferably contain from 3 to 10 basic nitrogen atoms in the molecule.
  • suitable dicarboxylic acids are succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid or terephthalic acid. It is also possible to use mixtures of the abovementioned dicarboxylic acids, for example mixtures of adipic acid and glutaric acid or mixtures of maleic acid and adipic acid.
  • Adipic acid is preferably used for the preparation of polyamidoamines.
  • Suitable polyalkylenepolyamines which are condensed with the abovementioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
  • the abovementioned polyalkylenepolyamines can also be used in the form of mixtures in the preparation of polyamidoamine.
  • the preparation of polyamidoamine is preferably carried out in bulk, but may also be carried out in inert solvents, if appropriate.
  • the condensation of dicarboxylic acid with polyalkylenepolyamine takes place at higher temperatures, for example in the range from 120 to 220.degree.
  • the water formed during the reaction is distilled off from the reaction mixture.
  • the condensation may optionally be carried out in the presence of lactones or lactams of carboxylic acids having 4 to 8 carbon atoms.
  • lactones or lactams of carboxylic acids having 4 to 8 carbon atoms In general, from 0.8 to 1.4 mol of a polyalkylenepolyamine are used per mole of dicarboxylic acid.
  • polyamidoamines have primary and secondary NH groups and are soluble in water.
  • Polyamidoamines grafted with ethyleneimine can be prepared by allowing ethyleneimine to act on polyamidoamine described above in the presence of Bronsted acids or Lewis acids, for example sulfuric acid, phosphoric acid or boron trifluoride etherate.
  • ethyleneimine is grafted onto the relevant polyamidoamine.
  • polyamidoamine per basic nitrogen atom in the polyamidoamine, one can graft 1 to 10 ethyleneimine units, i. H. to 100 parts by weight of polyamidoamine is used about 10 to 500 parts by weight of ethyleneimine.
  • Preferred alkyleneimine polymer is polyethyleneimine.
  • polyethyleneimines are selected from highly branched polyethyleneimines.
  • Highly branched polyethylenimines are characterized by their high degree of branching (DB).
  • highly branched polyethyleneimines are polyethylene imines having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90, more preferably in the range from 0.30 to 0.80 and very particularly preferably at least 0.5.
  • polyethylenimine is highly branched polyethyleneimines (homopolymers) having an average molecular weight M w in the range from 600 to 20,000 g / mol, preferably in the range from 800 to 15,000 g / mol.
  • Alkyleneimine polymer is used in the context of the present invention in covalently modified form, specifically in the range from 2 to 80% by weight, preferably from 5 to 60% by weight, of alkylene oxide side chains, based on the total alkoxylated alkyleneimine Polymer (B).
  • alkoxylation can be used epoxides, for example ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2,3-butylene oxide, styrene oxide or epichlorohydrin.
  • Preferred alkoxylation reagents are ethylene oxide and propylene oxide and mixtures of ethylene oxide and propylene oxide.
  • alkoxylated alkyleneimine polymer (B) alkoxylates in the range of 5 to 60 mole percent of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer.
  • modified polyalkyleneimine (B) is selected from polyethyleneimines reacted with ethylene oxide or propylene oxide.
  • Modified polyalkyleneimine (B) can have as counter ions high molecular weight or low molecular weight anions, organic or preferably inorganic.
  • High molecular weight anions in the context of the present invention have an average molecular weight of 200 g / mol or more, for example up to 2500 g / mol
  • low molecular weight anions have a molecular weight of less than 200 g / mol, for example from 17 to 150 g / mol.
  • Examples of low molecular weight organic counterions are acetate, propionate and benzoate.
  • Examples of low molecular weight inorganic counterions are sulfate, chloride, bromide, hydroxide, carbonate, methanesulfonate and bicarbonate.
  • modified polyalkyleneimine (B) has a cationic charge density of at least 5 meq / g to a maximum of 25 meq / g (milliequivalents / g), preferably to 22 meq / g, where g is modified polyalkyleneimine (B) without taking into account the counterions.
  • the cationic charge density can be determined, for example, by titration, for example with polyvinyl sulfate solution.
  • modified polyalkyleneimine (B) has a molecular weight distribution M w / M n in the range of 1.1 to 10, preferably 1.5 to 5.
  • formulation according to the invention contains compound (A) and modified polyalkyleneimine (B) in a weight ratio in the range from 1000 to 1 to 25 to 1.
  • formulation according to the invention is free of phosphates and polyphosphates, with hydrogen phosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexanatrium ummetaphosphate.
  • hydrogen phosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexanatrium ummetaphosphate.
  • the term "free from”, in the context of phosphates and polyphosphates is understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 0.2% by weight, determined by gravimetry.
  • Formulations of the invention may contain other components which are advantageous, for example, for use in washing dishes and / or kitchen utensils.
  • formulations according to the invention contain no further components, which are advantageous, for example, for use in dishwashing and / or kitchen utensils, but can easily be formulated with further components and are therefore suitable as starting material.
  • formulations according to the invention contain sodium citrate (C).
  • the term sodium citrate comprises the mono- and preferably the disodium salt with.
  • Sodium citrate can be used as anhydrous salt or as a hydrate, for example as a dihydrate.
  • formulations according to the invention contain (D) at least one compound chosen from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, in the context of the present invention also referred to as "bleaching agent (D).”
  • Preferred bleaching agents (D) are selected from sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called Dihydrate, sodium percarbonate, anhydrous or, for example, as a monohydrate, and sodium persulfate, wherein the term “persulfate” in each case comprises the salt of the peracid H2SO5 and the peroxodisulfate with.
  • the alkali metal salts may each also be alkali metal hydrogencarbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulphate. However, preference is given in each case to the dialkali metal salts.
  • formulation according to the invention comprises zero to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, particularly preferably at least 5% by weight of sodium citrate (C), determined as anhydrous sodium citrate,
  • bleaching agent (D) preferably at least 0.5% by weight of bleaching agent (D), selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.
  • formulation according to the invention is solid at room temperature, for example a powder or a tablet.
  • formulation of the invention is liquid at room temperature.
  • the formulation according to the invention is a granulate, a liquid preparation or a gel.
  • the formulation according to the invention contains from 0.1 to 10% by weight of water, based on the sum of all solids of the relevant formulation.
  • formulation according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more several tabletting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizers.
  • surfactants for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more a plurality of bleaching agents, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers
  • surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants.
  • Preferred nonionic Surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)
  • R 1 is identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case the same and ethyl and particularly preferably methyl
  • R 2 is selected from C 1 -C 22 -alkyl, for example nC & Hn, n-doF i, n-C 12H 25, nC-uF s), n-Ci6H33 selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl,
  • Compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.
  • alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II) where the variables are defined as follows:
  • R 1 is identical or different and selected from linear C 1 -C 10 -alkyl, preferably in each case identical and ethyl and particularly preferably methyl
  • R 4 is selected from C 6 -C 20 -alkyl, in particular n-CsH-i, n-doH-i, n-C 12 H 25, n-Ci4H29, n-C 16 H 33, n-
  • a is a number in the range of 1 to 6,
  • b is a number in the range of 4 to 20
  • d is a number in the range of 4 to 25.
  • these may be block copolymers or random copolymers, preference being given to block copolymers.
  • suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide.
  • suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters.
  • amine oxides or alkyl glycosides are also suitable. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187.
  • anionic surfactants are C 8 -C 20 -alkyl sulfates, C 8 -C 20 -alkyl sulfonates and C 8 -C 20 -alkyl ether sulfates having one to six ethylene oxide units per molecule.
  • formulation of the invention may contain in the range of from 3 to 20% by weight of surfactant.
  • Formulations of the invention may contain one or more enzymes.
  • enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.
  • Formulations according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, in each case based on the total solids content of the formulation according to the invention.
  • Formulations according to the invention may comprise, in addition to sodium citrate (C), one or more builders, in particular phosphate-free builders.
  • suitable builders are silicates, especially sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula a-Na 2 Si 2 O, ⁇ -Na 2 Si 2 O, and 5-Na 2 Si 2 O, furthermore fatty acid sulfonates, ⁇ -hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl- and alkenyl disuccina tartaric acid, tartaric acid acetate, oxidized starch, and polymeric builders, for example, polycarboxylates and polyaspartic acid.
  • builders of polycarboxylates for example, alkali metal salts of (meth) acrylic acid homo- or
  • (Meth) acrylic acid copolymers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid.
  • a suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight M w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.
  • copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C 3 -C 10 -mono- or C 4 -C 10 -dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid with at least a hydrophilic or hydrophobically modified monomers are used as enumerated below.
  • Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 - Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C22- ⁇ -olefin, a mixture of C2o-C24- ⁇ -olefins and polyisobutene having an average of 12 to 100 carbon atoms per molecule.
  • Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples which may be mentioned are: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate.
  • Polyalkylene glycols may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.
  • Particularly preferred sulfonic acid-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2 hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and salt
  • amphoteric polymers can also be used as builders.
  • Formulations according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.
  • formulations according to the invention may contain one or more co-builders.
  • cobuilders are phosphonates, for example hydroxyalkanephosphonates and aminoalkanephosphonates.
  • hydroxyalkane phosphonates the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • Formulations of the invention may contain one or more alkali carriers.
  • Alkaline carriers for example, provide the pH of at least 9 when an alkaline pH is desired.
  • Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates.
  • Preferred alkali metal is in each case potassium, particularly preferred is sodium.
  • Formulations according to the invention may contain, in addition to bleaching agent (D), one or more chlorine-containing bleaching agents.
  • Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.
  • formulations according to the invention may contain in the range of from 3 to 10% by weight of chlorine-containing bleach.
  • Formulations of the invention may contain one or more bleach catalysts.
  • Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or carbonyl complexes.
  • Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands can also be used.
  • cobalt, iron, copper and ruthenium amine complexes are useful as bleach catalysts.
  • Formulations according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide ,, 1, 5-diacetyl-2,2- dioxo-hexahydro-1,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.
  • Formulations of the invention may contain one or more corrosion inhibitors. This is to be understood in the present case, such compounds that inhibit the corrosion of metal.
  • suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.
  • formulations according to the invention contain a total of in the range of 0.1 to 1, 5 wt .-% corrosion inhibitor.
  • Formulations of the invention may contain one or more builders, for example, sodium sulfate.
  • Formulations of the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils.
  • formulations according to the invention contain in total from 0.05 to 0.5% by weight of defoamer.
  • Formulations according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
  • Another object of the present invention is the use of formulations according to the invention for the automatic cleaning of dishes and kitchen utensils.
  • kitchen utensils in the context of the present invention, for example, pots, pans, casseroles to call, and metal objects such as, for example, skimmers, roasters and garlic presses.
  • a surface of glass is to be understood as meaning that the object in question has at least one piece of glass which comes into contact with the ambient air and can be contaminated when the object is used.
  • the objects in question may be those that are essentially glassy, such as drinking glasses or glass bowls. But it can also be, for example, cover that have individual components of a different material, such as pot lid with edging and metal handle.
  • Glass surface may be decorated, for example colored or printed, or not decorated.
  • glass includes any glass, for example lead glass and, in particular, soda lime glass, crystal glass and borosilicate glass, preferably a dishwasher with automatic dishwashing.
  • At least one formulation according to the invention for automated cleaning of drinking glasses, glass vases and glass jars is used for cooking.
  • water having a hardness in the range from 1 to 30 ° dH, preferably from 2 to 25 ° dH, is used for cleaning, German hardness being taken to mean in particular the calcium hardness.
  • rinsing water with a hardness in the range of 1 to 30 ° dH preferably 2 to 25 ° dH can be used.
  • machine-cleaning formulations according to the invention are used, even with repeated mechanical cleaning of objects which have at least one surface made of glass, there is very little tendency for glass corrosion, even if objects comprising at least one surface made of glass are used have, along with heavily soiled cutlery or dishes cleans. In addition, it is much less harmful to use the formulation according to the invention to clean glass together with metal objects, for example together with pots, pans or garlic presses.
  • a further subject of the present invention is a process for the preparation of formulations according to the invention, in short also called production process according to the invention.
  • preparation process according to the invention it is possible, for example, to proceed in such a way that
  • a aminocarboxylate selected from methylglycine diacetate (MGDA), iminodisuccinic acid (IDS) and glutamic acid diacetate (GLDA) and their salts, and
  • Compound (A), modified polyalkyleneimine (B) and bleaching agent (D) are defined above.
  • one or more surfactants for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, one or more builders several co-builders, in particular phosphorus-free builders, one or more alkali carriers, one or more bleaches, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders , with buffer or dye.
  • the water is completely or partially removed, for example, to a residual moisture in the range from 0.1 to 10% by weight of the formulation according to the invention by evaporation, in particular by spray drying, spray granulation or compaction.
  • the water is removed, in whole or in part, at a pressure in the range of 0.3 to 2 bar.
  • the water is removed, in whole or in part, at temperatures in the range from 60 to 220.degree.
  • the cleaning formulations according to the invention can be provided in liquid or solid form, single- or multiphase, as tablets or in the form of other dosage units, packaged or unpackaged.
  • the water content of liquid formulations can vary from 35 to 90% water.
  • the invention is illustrated by working examples.
  • LA charge density of the relevant modified polyethyleneimine (B), meq / g (milliequivalent / g)
  • MGDA methylglycine diacetic acid as trisodium salt
  • TAED ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetylethylenediamine
  • M w PEI refers to the molecular weight of the polyethylenimine used for the alkoxylation, ie to unmodified polyethyleneimine.
  • PEI refers to unmodified polyethyleneimine.
  • the glasses were placed in the upper dish rack of the dishwasher.
  • the dishwashing agent used was in each case 25 g of formulation according to the invention or 25 g of comparison formulation according to Table 3, where Table 3 shows the active components (A.1), base mixture, silicate (C.1 or C.2) and compound (D) or (E) and (B) of formulation according to the invention each individually specified.
  • Rinsing was carried out at a rinse temperature of 55 ° C.
  • the water hardness was in each case in the range of zero to 2 ° dH.
  • the evaluation was carried out gravimetrically and visually after 100 rinsing cycles.
  • the weight of the glasses was determined before the beginning of the first rinse cycle and after drying after the last rinse cycle.
  • the weight loss is the difference between the two values.
  • a visual assessment of the washware was made after 100 cycles in a darkened chamber under light behind a pinhole using a grading scale from 1 (very poor) to 5 (very good). In each case grades for area corrosion / turbidity or line corrosion were awarded.
  • test pieces were rinsed for the purpose of pretreatment, the test pieces in a domestic dishwashing machine (Bosch SGS5602) with 1 g of surfactant (n-Ci8H37 (OCH 2 CH 2) ioOH) and 20 g of citric acid, to remove any impurities.
  • the test pieces were dried, their weight determined and fixed on the grid floor insert.
  • To assess the gravimetric removal the dry specimens were weighed. This was followed by the visual assessment of the test specimens. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).
  • Interim scores (e.g., L3-4) were also allowed on the match.
  • formulations according to the invention were also always superior to the corresponding comparative formulations with regard to the inhibition of glass corrosion.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Washing And Drying Of Tableware (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne des formulations contenant (A) au moins un aminocarboxylate choisi parmi méthylglycine-diacétate (MGDA), acide imidosuccinique (IDS) et diacétate d'acide glutamique (GLDA) ainsi que leurs sels et dérivés, et (B) au moins un polymère alkylène-imine alkoxylé ayant un poids moléculaire moyen Mw entre 800 et 25000 g/mol, présentant une densité de charge positive d'au moins 5 meq/g et comprenant entre 2 et au plus 80 % en poids de chaînes latérales oxyde d'alkylène par rapport au polymère alkylène-imine alkoxylé total.
PCT/EP2013/058391 2012-04-25 2013-04-23 Formulations, leur utilisation comme détergents pour vaisselle ou pour la production de détergents pour vaisselle, et leur préparation WO2013160301A1 (fr)

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BR112014026565A BR112014026565A2 (pt) 2012-04-25 2013-04-23 formulação, uso de uma formulação, e, processo para produzir uma formulação
KR1020147032948A KR102007148B1 (ko) 2012-04-25 2013-04-23 제형, 식기세척 세제로서 또는 이의 제조를 위한 이들의 용도 및 이들의 제조
EP13720303.0A EP2841549B1 (fr) 2012-04-25 2013-04-23 Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
CN201380033256.6A CN104379717B (zh) 2012-04-25 2013-04-23 配制剂、其作为或用于生产器皿洗涤用洗涤剂的用途及其制备
CA2871210A CA2871210A1 (fr) 2012-04-25 2013-04-23 Formulations, leur utilisation comme detergents pour vaisselle ou pour la production de detergents pour vaisselle, et leur preparation
ES13720303.0T ES2612342T3 (es) 2012-04-25 2013-04-23 Formulaciones, su uso como o para la preparación de detergentes lavavajillas y su preparación
JP2015507501A JP6133971B2 (ja) 2012-04-25 2013-04-23 配合物、食器洗い洗剤としての又は食器洗い洗剤を製造するためのそれらの使用方法、及びそれらの製造
RU2014147082A RU2623440C2 (ru) 2012-04-25 2013-04-23 Препаративная форма, ее получение и применение в качестве или для получения посудомоечного средства
MX2014013009A MX2014013009A (es) 2012-04-25 2013-04-23 Formulaciones, su uso como o para la producir detergentes lavavajillas y su produccion.
JP2016509313A JP6235120B2 (ja) 2013-04-23 2013-10-07 処方物、食器用洗剤としてのそれらの使用方法、又は食器用洗剤の製造のためのそれらの使用方法、及びそれらの製造
PL13774145T PL2989192T3 (pl) 2013-04-23 2013-10-07 Preparaty, ich zastosowanie jako środków do zmywania naczyń lub do wytwarzania środków do zmywania naczyń i ich wytwarzanie
KR1020157033213A KR20160003006A (ko) 2013-04-23 2013-10-07 제형, 식기세척 세제로서 또는 이를 제조하기 위한 이의 용도 및 이의 제조
BR112015026763A BR112015026763A2 (pt) 2012-04-25 2013-10-07 formulação, uso de formulações, e, processo para a produção de formulações
US14/786,327 US20160075972A1 (en) 2013-04-23 2013-10-07 Formulations, their use as or for producing dishwashing detergents and their production
ES13774145.0T ES2693772T3 (es) 2012-04-25 2013-10-07 Formulaciones, su uso como o para la preparación de detergentes lavavajillas y su preparación
EP13774145.0A EP2989192B1 (fr) 2013-04-23 2013-10-07 Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
RU2015149916A RU2015149916A (ru) 2013-04-23 2013-10-07 Композиции, их применение в качестве или для получения средств для мытья посуды и их получение
CN201380075863.9A CN105143424B9 (zh) 2013-04-23 2013-10-07 配制剂、其作为或用于制备器皿洗涤清净剂的用途及其制备
PCT/EP2013/070857 WO2014173473A1 (fr) 2013-04-23 2013-10-07 Formulations, utilisation desdites formulations en tant que liquide vaisselle ou pour la production de liquide vaisselle et production desdites formulations

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US201261637901P 2012-04-25 2012-04-25
US201261637891P 2012-04-25 2012-04-25
EP12165545.0 2012-04-25
EP12165556 2012-04-25
US61/637,901 2012-04-25
US61/637,891 2012-04-25
EP12165550.0 2012-04-25
EP12165545 2012-04-25
EP12165550 2012-04-25
EP12165556.7 2012-04-25
EP12168054 2012-05-15
EP12168044 2012-05-15
EP12168038 2012-05-15
EP12168054.0 2012-05-15
EP12168038.3 2012-05-15
EP12168044.1 2012-05-15
US201261697817P 2012-09-07 2012-09-07
EP12183437 2012-09-07
US61/697,817 2012-09-07
EP12183437.8 2012-09-07

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JP2016525585A (ja) * 2013-05-27 2016-08-25 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 高濃度で錯化剤を含有する水溶液
EP2961822B1 (fr) * 2013-02-28 2017-04-12 Basf Se Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
EP3034596B1 (fr) 2014-12-17 2018-08-22 The Procter and Gamble Company Composition de détergent
EP3320068B1 (fr) 2015-07-09 2020-10-07 Basf Se Processus de lavage de vaisselle
JP2020196890A (ja) * 2014-11-26 2020-12-10 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 錯化剤の組み合わせを含有する水溶液

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EP2981600B1 (fr) * 2013-04-02 2018-03-21 Basf Se Formules, leur utilisation comme détergent pour lave-vaisselle et leur fabrication
JP2015086295A (ja) * 2013-10-30 2015-05-07 花王株式会社 食器用洗浄剤組成物
CN109415662A (zh) 2016-06-20 2019-03-01 巴斯夫欧洲公司 粉末和颗粒以及制备该粉末和颗粒的方法

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EP2961822B1 (fr) * 2013-02-28 2017-04-12 Basf Se Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
WO2014173473A1 (fr) * 2013-04-23 2014-10-30 Basf Se Formulations, utilisation desdites formulations en tant que liquide vaisselle ou pour la production de liquide vaisselle et production desdites formulations
US20160075972A1 (en) * 2013-04-23 2016-03-17 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
JP2016525585A (ja) * 2013-05-27 2016-08-25 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 高濃度で錯化剤を含有する水溶液
JP2020196890A (ja) * 2014-11-26 2020-12-10 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 錯化剤の組み合わせを含有する水溶液
JP7076506B2 (ja) 2014-11-26 2022-05-27 ビーエーエスエフ ソシエタス・ヨーロピア 錯化剤の組み合わせを含有する水溶液
EP3034596B1 (fr) 2014-12-17 2018-08-22 The Procter and Gamble Company Composition de détergent
EP3034596B2 (fr) † 2014-12-17 2021-11-10 The Procter & Gamble Company Composition de détergent
EP3320068B1 (fr) 2015-07-09 2020-10-07 Basf Se Processus de lavage de vaisselle

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PL2841549T3 (pl) 2017-04-28
KR20150013593A (ko) 2015-02-05
BR112014026565A2 (pt) 2017-06-27
EP2841549B1 (fr) 2016-10-26
CN104379717A (zh) 2015-02-25
ES2612342T3 (es) 2017-05-16
CN104379717B (zh) 2017-08-11
RU2014147082A (ru) 2016-06-10
KR102007148B1 (ko) 2019-08-05
MX2014013009A (es) 2015-08-06
ES2693772T3 (es) 2018-12-13
JP6133971B2 (ja) 2017-05-24

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