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WO2013160259A1 - 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
WO2013160259A1
WO2013160259A1 PCT/EP2013/058311 EP2013058311W WO2013160259A1 WO 2013160259 A1 WO2013160259 A1 WO 2013160259A1 EP 2013058311 W EP2013058311 W EP 2013058311W WO 2013160259 A1 WO2013160259 A1 WO 2013160259A1
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WO
WIPO (PCT)
Prior art keywords
acid
carboxylic acid
derivative
reacted
formulation according
Prior art date
Application number
PCT/EP2013/058311
Other languages
German (de)
English (en)
Inventor
Stephan Hüffer
Alejandra Garcia Marcos
Markus Hartmann
Heike Weber
Mario Emmeluth
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 RU2014147080A priority Critical patent/RU2629112C2/ru
Priority to CN201380022145.5A priority patent/CN104284971B/zh
Priority to JP2015507490A priority patent/JP6162791B2/ja
Priority to KR1020147032912A priority patent/KR20150013590A/ko
Priority to BR112014026564A priority patent/BR112014026564A2/pt
Priority to EP13717782.0A priority patent/EP2841548B1/fr
Priority to ES13717782.0T priority patent/ES2612352T3/es
Priority to CA2870785A priority patent/CA2870785A1/fr
Priority to MX2014013010A priority patent/MX2014013010A/es
Publication of WO2013160259A1 publication Critical patent/WO2013160259A1/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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 alkyleneimine polymer which is reacted with at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of carbonic acid is covalently modified, with up to a maximum of 75 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer with carboxylic acid or
  • 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 rubbing on glasses or mechanical contact of the glasses with parts of the dishwasher, but is mainly promoted by chemical influences. For example, 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 clouding.
  • WO 2002/64719 discloses that it is possible to use certain copolymers of ethylenically unsaturated carboxylic acids with, for example, esters of ethylenically unsaturated carboxylic acids in dishwashing detergents.
  • 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.
  • dishwashing agents 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. The glass corrosion, in particular the line corrosion and the turbidity, but is not sufficiently delayed or prevented in many cases. It was therefore the object to provide formulations which are suitable as or for the production of dishwashing agents and which avoid the disadvantages known from the prior art and inhibit glass corrosion or at least reduce it particularly well. A further object was to provide a process for the preparation of formulations which are suitable as or for the production of dishwasher detergents and which avoid the disadvantages known from the prior art. It was also the task to provide uses of formulations.
  • formulations defined above were found, also called formulations according to the invention.
  • 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).
  • MGDA methylglycine diacetate
  • IDS iminodisuccinic acid
  • GLDA glutamic acid diacetate
  • compound (A) is the free acid, particularly preferably in partially or completely neutralized form, ie as salt.
  • counterions for example inorganic cations, such as ammonium, alkali or alkaline earth metal are suitable, preferably Mg 2+, Ca 2+, Na +, K +, or organic cations, preferably with one or more organic radicals, substituted ammonium, more particularly 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.
  • 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 (GLDA).
  • MGDA methylglycine diacetate
  • IDS iminodisuccinic acid
  • GLDA glutamic acid diacetate
  • 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.
  • Polyalkylenepolyamine and in particular polyethyleneimine can have, for example, an average molecular weight (M w ) of at least 300 g / mol, preferably the average molecular weight of alkyleneimine polymer is in the range from 500 to 1 000 000 g / mol, particularly preferably 800 to 25 000 g / mol , determined by gel permeation chromatography (GPC).
  • 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 , If quaternized (alkylated) polyalkylenepolyamines are covalently modified as the alkyleneimine polymer, 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.
  • Polyalkylenepolyamines and in particular polyethylenimines can furthermore be covalently modified in alkoxylated form in a partially alkoxylated form with C2-C22 epoxides as the alkyleneimine polymer.
  • suitable C 2 -C 22 epoxides are ethylene oxide, propylene oxide, n-hexylene oxide, styrene oxide.
  • the degree of alkoxylation is preferably 1 to 25, particularly preferably up to 20 mol%, based on alkoxylatable N-atoms in the relevant 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, for example, 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.
  • from 0.8 to 1.4 mol of polyalkylenepolyamine are used per mole of dicarboxylic acid.
  • polyamidoamines have primary and secondary NH groups and are soluble in water.
  • Ethyleneimine-grafted polyamidoamines 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.
  • polyethyleneimine has an average molecular weight M w in the range from 500 to 1 000 000 g / mol, preferably in the range from 600 to 75 000 g / mol, more preferably in the range from 800 to 25 000 g / mol for example by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • 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 with 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 75,000 g / mol, preferably in the range from 800 to 25,000 g / mol.
  • Alkyleneimine polymer is used in the context of the present invention in covalently modified form, in such a way that a total of up to 75 mol%, preferably a total of 5 to 60 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer at least one carboxylic acid or at least one derivative of a carboxylic acid or at least one derivative of carbonic acid are reacted.
  • the reaction (modification) may be, for example, an alkylation or an amidation.
  • a modified polyalkyleneimine (B) is selected from alkyleneimine polymers and in particular polyethyleneimines,
  • ethylenically unsaturated C 3 -C 10 -carboxylic acids are unsaturated fatty acids and preferably ⁇ , ⁇ -ethylenically unsaturated C 3 -C 10 -carboxylic acids, for example (E) - or (Z) -crotonic acid, methacrylic acid and in particular acrylic acid.
  • C 3 -C 10 -carboxylic acid (s) C 3 -C 10 -carboxylic acid is / are preferably added in the sense of a Michael addition to nitrogen atoms from Nh groups or NH groups from alkyleneimine polymer.
  • Cs-C 12 -carboxylic acid which have no ethylenic double bond are valaleic acid, caproic acid, caprylic acid, n-octanoic acid, n-decanoic acid and lauric acid.
  • a reaction with Cs-Ci2-carboxylic acid (s), which have no ethylenic double bond For example, an amidation of nitrogen atoms from Nh groups or NH groups from alkyleneimine polymer is preferably carried out.
  • esters for example the C 1 -C 4 -alkyl esters, in particular the ethyl and the methyl esters.
  • carbonic acid derivatives are the di-C 1 -C 2 -alkyl esters of carbonic acid, such as dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate, and in particular cyclic carbonates, such as ethylene carbonate and propylene carbonate. Preferred is ethylene carbonate.
  • modified polyalkyleneimine (B) up to a maximum of 75 mol% of the nitrogen atoms of the primary and secondary amino groups of the alkyleneimine polymer are reacted with carboxylic acid or derivative of carboxylic acid or carbonic acid, preferably a total of 5 to 60 mol%.
  • Tertiary nitrogen atoms in polyalkyleneimine (B) are usually not reacted with carboxylic acid or derivative of carboxylic acid or carbonic acid.
  • modified polyalkyleneimine (B) which is obtainable from alkyleneimine polymers and in particular polyethyleneimines (B1) which are reacted with at least one ethylenically unsaturated C 3 -C 10 -carboxylic acid, in the formulation according to the invention, is employed as the free acid ,
  • 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 (milliequivalents / g), preferably 5 to 22 meq / g, with no mention in g of modified polyalkyleneimine (B) relates to the counterions.
  • the cationic charge density can be determined, for example, by titration, for example by titration with polyvinyl sulfate.
  • Modified polyalkyleneimines (B) may also contain one or more anionic comonomers in copolymerized form, for example (meth) acrylic acid.
  • Cationic copolymers (B) which also contain one or more anionic comonomers polymerized, have more cationic than anionic charges per molecule.
  • 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.
  • modified polyalkyleneimine (B) has a molecular weight Mw in the range of 550 to 1, 5-10 6 g / mol.
  • formulation according to the invention contains compound (A) and modified polyalkyleneimine (B) in a weight ratio of 1000: 1 to 25: 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).
  • sodium citrate includes 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.
  • bleaching agent (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.
  • the formulation according to the invention is free from those heavy metal compounds which do not function as bleach catalysts, in particular compounds of iron and bismuth.
  • “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 Solids content.
  • the formulation according to the invention 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.
  • 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)
  • C 1 -C 10 -alkyl preferably in each case identical and ethyl and particularly preferably methyl, selected from C 5 -C 22 -alkyl, for example nC & Hn, n-doF i, n- Ci2H25, nC-uF s), n-Ci6H33 or n-Ci8H37
  • R 3 is selected from C 1 -C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
  • neo-pentyl 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or iso-decyl
  • m and n are in the range of zero to 300, the sum of n and m being at least one.
  • m is in the range of 1 to 100 and n is in the range of 0 to 30.
  • 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 nC & Hn, n-doF i, n-Ci 2 H 25, nC-uF s), n-Ci6H33, n
  • a number in the range of 1 to 6 is a number in the range of 4 to 20, 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 diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders such as polycarboxylates and polyaspartic acid.
  • builders of polycarboxylates for example, alkali metal salts of (meth) acrylic acid homo- or
  • Suitable comonomers 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 from the group consisting of monoethylenically unsaturated C3-Cio-mono- or C4-Cio-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 one hydrophilic or hydrophobically modified monomers 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, such as 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- a-olefins and polyisobutene with 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 monomers containing sulfonic acid groups 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
  • Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.
  • 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. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • 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 and cobalt, iron, copper and ruthenium-amine complexes can also be used 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 N-nonanoylsuccinimide "1, 5-diacetyl-2,2-dioxohexahydro -1, 3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • MMA salts N-methylmorpholinium acetonitrile salts
  • DADHT 3,5-triazine
  • nitrile quats trimethylammonium acetonitrile salts
  • TAED tetraacetylethylenediamine
  • TAED tetraacetylhexylenediamine
  • Formulations according to the invention may contain one or more corrosion inhibitors.
  • these are understood as meaning compounds which 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 according to 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 in the range from 0.05 to 0.5% by weight defoamer.
  • Formulations according to the invention may contain phosphonic acid or one or more phosphonic acid derivatives, for example hydroxyethane-1,1-diphosphonic acid.
  • kitchen utensils include, for example, pots, pans, casseroles, and also metal objects such as, for example, skimmers, roasting knives 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 automatic dish-washing with a dishwasher.
  • 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.
  • 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.
  • formulations according to the invention have a very good bleaching action when used for rinsing dishes and kitchen utensils and glass surfaces.
  • 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
  • compositions (A), modified polyalkyleneimine (B) and bleaching agent (D) are defined above.
  • 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
  • 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.
  • modified polyethyleneimines (B) was always determined as follows (see also: Horn, Prog. Colloid & Polym., Sci. 1978, 65, 251): 1 g of the relevant (co) polymer (B) was dissolved in 100 ml of demineralized water. A pH of 4.0 was set with a buffer solution and aqueous HCl, determined to be potentiometric. Three ml of an aqueous solution of toluidine blue (50 mg / l water) was added and titrated N / 400-KPVS (potassium polyvinyl sulfate) solution (Wako) with a concentration of 0.0004 meq / ml to a color change of blue pink. The charge density was calculated as follows:
  • LA charge density of the relevant modified polyethyleneimine (B), meq / g (milliequivalent / g)
  • MGDA methylglycine diacetic acid as trisodium salt
  • TAED ⁇ , ⁇ , ⁇ ', ⁇ '-tetraacetylethylenediamine
  • HEDP disodium salt of hydroxyethane- (1, 1-diphosphonic acid
  • the molecular weight M w was determined on the underlying polyethyleneimines, ie in each case before the modification.
  • the functionalization refers to the sum of the primary and secondary N atoms in the respective polyethylenimine.
  • 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 2, where Table 2 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.
  • the specimens were rinsed in a domestic dishwasher (Bosch SGS5602) with 1 g of surfactant (n-Ci8H37 (OCH 2 CH 2 ) ioOH) and 20 g of citric acid. acid to remove any impurities.
  • the test pieces were dried, their weight determined and fixed on the grid floor insert.
  • the dry specimens were weighed. Subsequently, the visual assessment of the test specimens was carried out. The surface of the test specimens was evaluated for line corrosion (glass scoring) and haze corrosion (areal haze).

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

Abstract

L'invention concerne des formulations contenant (A) au moins un aminocarboxylate, sélectionné parmi un méthylglycindiacétate (MGDA), un acide iminodisuccinique (IDS) et un diacétate d'acide glutamique (GLDA) ainsi que leurs sels et dérivés, et (B) au moins un polymère d'alkylènimine modifié par covalence avec au moins un acide carboxylique ou au moins un dérivé d'un acide carboxylique ou au moins un dérivé de dioxyde de carbone. Jusqu'à au maximum 75 % molaire des atomes d'azote des groupes amino primaires et secondaires du polymère d'alkylènimine réagit avec l'acide carboxylique ou un dérivé d'acide carboxylique ou un dérivé de dioxyde carbone.
PCT/EP2013/058311 2012-04-25 2013-04-22 Formulations, leur utilisation comme détergents pour vaisselle ou pour la production de détergents pour vaisselle, et leur préparation WO2013160259A1 (fr)

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RU2014147080A RU2629112C2 (ru) 2012-04-25 2013-04-22 Композиции, их применение в качестве или для получения средств для мытья посуды и их получение
CN201380022145.5A CN104284971B (zh) 2012-04-25 2013-04-22 配制剂、其作为或生产器皿洗涤用洗涤剂的用途及其生产
JP2015507490A JP6162791B2 (ja) 2012-04-25 2013-04-22 配合物、食器洗い組成物としてのそれらの使用又は食器洗い組成物を製造するためのそれらの使用、及びそれらの製造
KR1020147032912A KR20150013590A (ko) 2012-04-25 2013-04-22 제형, 식기세척 세제로서 또는 이의 제조를 위한 이들의 용도 및 이들의 제조
BR112014026564A BR112014026564A2 (pt) 2012-04-25 2013-04-22 formulação, uso de uma formulação, e, processo para a preparação de uma formulação
EP13717782.0A EP2841548B1 (fr) 2012-04-25 2013-04-22 Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
ES13717782.0T ES2612352T3 (es) 2012-04-25 2013-04-22 Formulaciones, su uso como o para la preparación de detergentes lavavajillas y su preparación
CA2870785A CA2870785A1 (fr) 2012-04-25 2013-04-22 Formulations, leur utilisation comme detergents pour vaisselle ou pour la production de detergents pour vaisselle, et leur preparation
MX2014013010A MX2014013010A (es) 2012-04-25 2013-04-22 Formulaciones, su uso como o para producir composiciones lavavajillas y su preparación.

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3026103A1 (fr) * 2014-11-26 2016-06-01 The Procter and Gamble Company Poche de nettoyage
JP2016526056A (ja) * 2013-04-23 2016-09-01 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 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
WO2018011242A1 (fr) 2016-07-14 2018-01-18 Basf Se Milieu de fermentation comprenant un agent de chélation
RU2687255C2 (ru) * 2014-06-23 2019-05-08 Басф Се Композиции, их применение в качестве или для получения средств для мытья посуды и их получение
WO2023285064A1 (fr) 2021-07-14 2023-01-19 Basf Se Composition détergente liquide exempte de phosphates pour la réduction de la libération de microfibres

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201409632D0 (en) * 2014-05-30 2014-07-16 Reckitt Benckiser Brands Ltd Improved detergent composition
RU2696284C2 (ru) * 2014-11-26 2019-08-01 Басф Се Водный раствор, содержащий комбинацию комплексообразователей
RU2714202C2 (ru) * 2015-07-09 2020-02-13 Басф Се Способ очистки посуды
CN116583584A (zh) * 2020-12-07 2023-08-11 联合利华知识产权控股有限公司 洗涤剂组合物

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0851023A2 (fr) 1996-12-23 1998-07-01 Unilever N.V. Tablettes pour machine à laver la vaisselle contenant un peracide
WO1999005248A1 (fr) * 1997-07-23 1999-02-04 Unilever Plc Compositions pour lave-vaisselle renfermant des polymeres cationiques ou amphoteres solubles dans l'eau
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
WO2001096516A1 (fr) 2000-06-14 2001-12-20 The Procter & Gamble Company Procede de nettoyage d'une surface
WO2002064719A1 (fr) 2001-02-01 2002-08-22 Basf Aktiengesellschaft Copolymeres pour empecher la corrosion du verre
WO2005073357A2 (fr) * 2004-01-30 2005-08-11 Basf Aktiengesellschaft Polymere pour le traitement de surfaces
WO2006000020A1 (fr) 2004-06-29 2006-01-05 European Nickel Plc Lixiviation amelioree de metaux de base
JP2006335908A (ja) * 2005-06-02 2006-12-14 Diversey Ip Internatl Bv 自動洗浄機用液体洗浄剤組成物
WO2007054126A1 (fr) * 2005-11-09 2007-05-18 Ecolab Inc. Composition ayant des proprietes de modification de surface
WO2009092699A1 (fr) * 2008-01-24 2009-07-30 Unilever Nv Compositions de détergent pour machine à laver la vaisselle
WO2010000020A1 (fr) 2008-06-30 2010-01-07 Cathrx Ltd Cathéter
WO2010020765A1 (fr) * 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0892848B1 (fr) * 1996-04-09 2002-12-18 JohnsonDiversey, Inc. Solution servant a laver une bouteille sans provoquer d'attaque chimique
JP4015778B2 (ja) * 1999-06-17 2007-11-28 ディバーシー・アイピー・インターナショナル・ビー・ヴイ 食器洗浄機用液体洗浄剤組成物
JP4005855B2 (ja) * 2002-04-01 2007-11-14 株式会社日本触媒 洗剤組成物
US7196044B2 (en) * 2003-07-02 2007-03-27 Ecolab, Inc. Warewashing composition for use in automatic dishwashing machines, comprising a zinc ion and aluminum ion corrosion inhibitor
JP4942284B2 (ja) * 2003-09-26 2012-05-30 株式会社日本触媒 ポリアルキレンイミン誘導体およびその用途
JP5213091B2 (ja) * 2006-08-22 2013-06-19 ディバーシー株式会社 自動食器洗浄機用粒状洗浄剤組成物およびその製法、並びにその使用方法
EP2083067A1 (fr) * 2008-01-25 2009-07-29 Basf Aktiengesellschaft Utilisation de complexants organiques et/ou de liaisons contenant des groupes d'acides de carbone polymères dans une composition de produit de lavage ou de nettoyage

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0851023A2 (fr) 1996-12-23 1998-07-01 Unilever N.V. Tablettes pour machine à laver la vaisselle contenant un peracide
WO1999005248A1 (fr) * 1997-07-23 1999-02-04 Unilever Plc Compositions pour lave-vaisselle renfermant des polymeres cationiques ou amphoteres solubles dans l'eau
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
WO2001096516A1 (fr) 2000-06-14 2001-12-20 The Procter & Gamble Company Procede de nettoyage d'une surface
WO2002064719A1 (fr) 2001-02-01 2002-08-22 Basf Aktiengesellschaft Copolymeres pour empecher la corrosion du verre
WO2005073357A2 (fr) * 2004-01-30 2005-08-11 Basf Aktiengesellschaft Polymere pour le traitement de surfaces
WO2006000020A1 (fr) 2004-06-29 2006-01-05 European Nickel Plc Lixiviation amelioree de metaux de base
JP2006335908A (ja) * 2005-06-02 2006-12-14 Diversey Ip Internatl Bv 自動洗浄機用液体洗浄剤組成物
WO2007054126A1 (fr) * 2005-11-09 2007-05-18 Ecolab Inc. Composition ayant des proprietes de modification de surface
WO2009092699A1 (fr) * 2008-01-24 2009-07-30 Unilever Nv Compositions de détergent pour machine à laver la vaisselle
WO2010000020A1 (fr) 2008-06-30 2010-01-07 Cathrx Ltd Cathéter
WO2010020765A1 (fr) * 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HORN, PROG. COLLOID & POLYM. SCI., vol. 65, 1978, pages 251

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016526056A (ja) * 2013-04-23 2016-09-01 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 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
RU2687255C2 (ru) * 2014-06-23 2019-05-08 Басф Се Композиции, их применение в качестве или для получения средств для мытья посуды и их получение
EP3026103A1 (fr) * 2014-11-26 2016-06-01 The Procter and Gamble Company Poche de nettoyage
WO2016085671A1 (fr) * 2014-11-26 2016-06-02 The Procter & Gamble Company Sachet de nettoyage
JP2017534736A (ja) * 2014-11-26 2017-11-24 ザ プロクター アンド ギャンブル カンパニー 洗浄用パウチ
EP3026103B1 (fr) 2014-11-26 2018-07-25 The Procter and Gamble Company Poche de nettoyage
WO2018011242A1 (fr) 2016-07-14 2018-01-18 Basf Se Milieu de fermentation comprenant un agent de chélation
WO2023285064A1 (fr) 2021-07-14 2023-01-19 Basf Se Composition détergente liquide exempte de phosphates pour la réduction de la libération de microfibres

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PL2841548T3 (pl) 2017-04-28
EP2841548A1 (fr) 2015-03-04
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CN104284971B (zh) 2017-08-08
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RU2014147080A (ru) 2016-06-10
JP2015519428A (ja) 2015-07-09

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