EP2989192B1 - Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication - Google Patents

Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication Download PDF

Info

Publication number
EP2989192B1
EP2989192B1 EP13774145.0A EP13774145A EP2989192B1 EP 2989192 B1 EP2989192 B1 EP 2989192B1 EP 13774145 A EP13774145 A EP 13774145A EP 2989192 B1 EP2989192 B1 EP 2989192B1
Authority
EP
European Patent Office
Prior art keywords
range
acid
weight
formulation
formulation according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP13774145.0A
Other languages
German (de)
English (en)
Other versions
EP2989192A1 (fr
Inventor
Stephan Hüffer
Alejandra Garcia Marcos
Markus Hartmann
Heike Weber
Mario Emmeluth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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
Priority claimed from PCT/EP2013/058391 external-priority patent/WO2013160301A1/fr
Application filed by BASF SE filed Critical BASF SE
Priority to JP2016509313A priority Critical patent/JP6235120B2/ja
Priority to PL13774145T priority patent/PL2989192T3/pl
Publication of EP2989192A1 publication Critical patent/EP2989192A1/fr
Application granted granted Critical
Publication of EP2989192B1 publication Critical patent/EP2989192B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics

Definitions

  • the 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 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 suggests 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.
  • formulations defined above were found, also called formulations according to the invention.
  • 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 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 .
  • the heavy metals are precious metals and 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.
  • compound (A) is the free acid, particularly preferably in partially or completely neutralized form, ie as salt.
  • counterions come, for example, inorganic Cations, for example ammonium, alkali or alkaline earth metal in question, preferably Mg 2+ , Ca 2+ , Na + , K + , or organic cations, preferably ammonium substituted with one or more organic radicals, in particular triethanolammonium, N, N-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 in question, preferably Mg 2+ , Ca 2+ , Na + , K + , or organic cations, preferably ammonium substituted with one or more organic radicals
  • 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
  • MGDA methylglycine diacetate
  • IDS iminodisuccinic acid
  • GLDA glutamic acid diacetate
  • 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.
  • polyalkylenepolyamines 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 in particular polyethyleneimine has an average molecular weight (M w ) in the range of 400 to 500 g / mol, determined by light scattering.
  • Polyalkylenepolyamines can be covalently modified in partially quaternized (alkylated) form as the alkyleneimine 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, more 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 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 above-mentioned dicarboxylic acids are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
  • the aforementioned 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.
  • 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.
  • 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.
  • 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 one can use 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, with an indication in g of 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.
  • formulations according to the invention contain total in the range of 1 to 50% by weight of aminocarboxylate (A), preferably 10 to 25% by weight, in total in the range of 0.001 to 5% by weight of modified polyalkyleneimine (B), preferably 0.02 to 0.5 wt .-%, in each case based on solids content of the relevant formulation.
  • 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, wherein hydrogen phosphates are subsumed with, for example, free of trisodium phosphate, pentasodium tripolyphosphate and Hexasatriummetaphosphat.
  • free from in connection with phosphates and polyphosphates in the context of the present invention should be 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.
  • 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 monohydrate, and sodium persulfate, where the term "persulfate” respectively the salt of peracid H 2 SO 5 and the peroxodisulfate includes.
  • 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 contains zero to 50% by weight of sodium citrate (C), preferably 1 to 30% by weight, more preferably at least 5% by weight of sodium citrate (C), determined as anhydrous sodium citrate, a total of zero to 15% by weight of 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. in each case based on solids content of the relevant formulation.
  • 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 tableting aids, one or more disintegrating agents, one or more thickeners, or one or more solubilizing agents.
  • 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.
  • n and n are in the range of zero to 300, where the sum of n and m is 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.
  • 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.
  • 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, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, especially those of the formula ⁇ -Na 2 Si 2 O 5 , ⁇ -Na 2 Si 2 O 5 , and ⁇ -Na 2 Si 2 O 5 , furthermore fatty acid sulfonates , ⁇ -hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example, polycarboxylates and polyaspartic acid.
  • builders of polycarboxylates are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.
  • 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 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 one hydrophilic or hydrophobically modified monomers are used as listed 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, C 22 - ⁇ -olefin, a mixture of C 20 -C 24 - ⁇ -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 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
  • 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.
  • co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
  • 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-dioxo-hexahydroxy 1,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).
  • MMA salts N-methylmorpholinium acetonitrile salts
  • DADHT 1,5-diacetyl-2,2-dioxo-hexahydroxy 1,3,5-triazine
  • nitrile quats trimethylammonium acetonitrile salts
  • TAED tetraacetylethylenediamine
  • TAED tetraacetylhexylenediamine
  • Formulations of the invention may contain one or more corrosion inhibitors.
  • corrosion inhibitors 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 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.
  • 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 which are essentially glassware 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 glasses.
  • Machine cleaning is preferably dishwashing with a dishwasher (English: “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 of the present invention to clean glass together with metal objects, such as 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.
  • 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 a plurality of 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 Buffer or dye.
  • one or more surfactants for
  • 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 of 60 to 220 ° C.
  • 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 can be tested as follows.
  • Basic mixtures can be prepared from the starting materials according to Table 1. The starting materials are mixed dry.
  • Table 1 Basic mixtures for experiments with formulations according to the invention and comparative formulations Base 1
  • Base 2 Base 3 protease 2.5 2.5 2.5 amylase 1 1 1 nC 18 H 37 (OCH 2 CH 2 ) 9 OH 5 5
  • 10 10
  • Sodium percarbonate (D.1) 10.5 10.5 10.5 TAED 4 4 4 Na 2 Si 2 O 5 2 2 2 Na 2 CO 3 19.5 19.5 19.5 Sodium citrate dihydrate 5 22.5 30 All information in g.
  • the glasses are arranged in the upper dish rack of the dishwasher.
  • the dishwashing agent used is in each case 25 g of formulation according to the invention or 25 g of comparative formulation. Rinse at a rinse temperature of 55 ° C. The water hardness is in each case in the range of zero to 2 ° dH.
  • the weight of the glasses is 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 are rinsed in a domestic dishwasher (Bosch SGS5602) with 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid to remove any impurities.
  • the test pieces are dried, their weight determined and fixed on the grid floor insert.
  • the dry test specimens are weighed. This is followed by the visual assessment of the test specimens. Here, the surface of the test specimens is evaluated for line corrosion (scorching) and haze corrosion (areal haze).
  • 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 inventive formulation 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 (nC 18 F 37 (OCH 2 CH 2 ) 10 OH) 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.
  • 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 in terms of the inhibition of glass corrosion.
  • Table 3 Results of tests with dishwasher (endurance runner) Example no.
  • Base mixture [g] (A.1) [g] (B) [mg] Weight loss champagne glass [mg] Weight loss shot glass [mg] Visual rating champagne glass Visual rating shot glass V-1
  • Base 2:17 3 60 (B.1.1.1) 17 9 L4, T4-5 L4, T5 2
  • Base 2:17 3 30 (B.1.1.1) 19 11 L3-4, T4-5 L4, T5 V-3
  • Base 2:17 3 30 (B.1.1.3) 67 36 L2, T2 L1-2, T2-3 V-4

Landscapes

  • 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)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (15)

  1. Formulation, qui est exempte de métaux lourds, contenant :
    (A) au moins un aminocarboxylate, choisi parmi le diacétate de méthylglycine (MGDA), l'acide iminodisuccinique (IDS) et le diacétate de l'acide glutamique (GLDA), ainsi que leurs sels,
    (B) au moins un polymère d'alkylène-imine alcoxylé ayant un poids moléculaire moyen Mw dans la plage allant de 500 à moins de 800 g/mole, qui présente une densité de charge positive d'au moins 5 meq/g et qui comprend dans la plage allant de 2 à au plus 80 % en poids de chaînes latérales oxyde d'alkylène, par rapport à l'ensemble du polymère d'alkylène-imine alcoxylé, le polymère d'alkylène-imine alcoxylé (B) étant à base de polyéthylène-imine présentant un poids moléculaire moyen Mw dans la plage de 400 à 500 g/mole, déterminé par diffusion de la lumière.
  2. Formulation selon la revendication 1, caractérisée en ce qu'elle est exempte de phosphates et de polyphosphates.
  3. Formulation selon la revendication 1 ou 2, caractérisée en ce que (B) est choisi parmi les polyéthylène-imines qui ont réagi avec de l'oxyde d'éthylène ou de l'oxyde de propylène.
  4. Formulation selon l'une quelconque des revendications 1 à 3, caractérisée en ce qu'elle présente une teneur en métaux lourds de moins de 0,05 ppm, par rapport à la teneur en solides de la formulation en question.
  5. Formulation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que le polymère d'alkylène-imine (B) est choisi parmi ceux dans lesquels au plus 30 % en moles des atomes d'azote du polymère d'alkylène-imine ont réagi avec de l'oxyde de propylène.
  6. Formulation selon l'une quelconque des revendications 1 à 5, caractérisée en ce qu'elle est solide à température ambiante.
  7. Formulation selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'elle contient dans la plage allant de 0,1 à 10 % en poids d'eau.
  8. Formulation selon l'une quelconque des revendications 1 à 7, caractérisée en ce que le rapport molaire entre les atomes d'azote et les groupes oxyde d'alkylène dans le polymère d'alkylène-imine alcoxylé (B) est d'au plus 5.
  9. Formulation selon l'une quelconque des revendications 1 à 8, caractérisée en ce qu'elle contient :
    au total dans la plage allant de 1 à 50 % en poids d'aminocarboxylate (A),
    au total dans la plage allant de 0,001 à 2 % en poids de polymère d'alkylène-imine alcoxylé (B),
    à chaque fois par rapport à la teneur en solides de la formulation en question.
  10. Utilisation de formulations selon l'une quelconque des revendications 1 à 9 pour le rinçage de vaisselle et d'ustensiles de cuisine, le rinçage étant effectué avec une eau d'une dureté de 2 à 25 °dH.
  11. Utilisation de formulations selon l'une quelconque des revendications 1 à 9 pour le rinçage d'articles qui comprennent au moins une surface en verre, qui peut être décorée ou non décorée.
  12. Utilisation selon la revendication 10 ou 11, caractérisée en ce que le rinçage est un rinçage avec un lave-vaisselle.
  13. Utilisation selon l'une quelconque des revendications 10 à 12, caractérisée en ce qu'au moins une formulation selon l'une quelconque des revendications 1 à 8 est utilisée pour le rinçage de verres, de vases en verre et de récipients en verre pour la cuisine.
  14. Procédé de fabrication de formulations selon l'une quelconque des revendications 1 à 9, caractérisé en ce que
    (A) un aminocarboxylate, choisi parmi le diacétate de méthylglycine (MGDA), l'acide iminodisuccinique (IDS) et le diacétate de l'acide glutamique (GLDA), ainsi que leurs sels, et
    (B) au moins un polymère d'alkylène-imine alcoxylé ayant un poids moléculaire moyen Mw dans la plage allant de 500 à moins de 800 g/mole, qui présente une densité de charge positive d'au moins 5 meq/g et qui comprend dans la plage allant de 2 à au plus 80 % en poids de chaînes latérales oxyde d'alkylène, par rapport à l'ensemble du polymère d'alkylène-imine alcoxylé,
    et éventuellement d'autres composants sont mélangés les uns avec les autres en une ou plusieurs étapes en présence d'eau, puis l'eau est éliminée en totalité ou en partie.
  15. Procédé selon la revendication 14, caractérisé en ce que l'eau est éliminée par séchage par pulvérisation ou par granulation par pulvérisation.
EP13774145.0A 2013-04-23 2013-10-07 Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication Not-in-force EP2989192B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/EP2013/058391 WO2013160301A1 (fr) 2012-04-25 2013-04-23 Formulations, leur utilisation comme détergents pour vaisselle ou pour la production de détergents pour vaisselle, et leur préparation
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

Publications (2)

Publication Number Publication Date
EP2989192A1 EP2989192A1 (fr) 2016-03-02
EP2989192B1 true EP2989192B1 (fr) 2018-08-08

Family

ID=49322363

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13774145.0A Not-in-force 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

Country Status (8)

Country Link
US (1) US20160075972A1 (fr)
EP (1) EP2989192B1 (fr)
JP (1) JP6235120B2 (fr)
KR (1) KR20160003006A (fr)
CN (1) CN105143424B9 (fr)
PL (1) PL2989192T3 (fr)
RU (1) RU2015149916A (fr)
WO (1) WO2014173473A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2966844A1 (fr) * 2014-11-26 2016-06-02 Basf Se Solution aqueuse contenant une combinaison d'agents complexants
PL3034588T3 (pl) 2014-12-17 2019-09-30 The Procter And Gamble Company Kompozycja detergentu
EP3034596B2 (fr) 2014-12-17 2021-11-10 The Procter & Gamble Company Composition de détergent
CN107523429A (zh) * 2017-07-28 2017-12-29 广州立白企业集团有限公司 液体洗涤剂组合物及其制备方法和应用
GB202117816D0 (en) 2021-12-09 2022-01-26 Reckitt Benckiser Finish Bv Granular additive

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB30255A (fr) * 1968-06-25
US5837663A (en) 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
WO1999005248A1 (fr) * 1997-07-23 1999-02-04 Unilever Plc Compositions pour lave-vaisselle renfermant des polymeres cationiques ou amphoteres solubles dans l'eau
US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
US6376445B1 (en) * 1997-08-14 2002-04-23 Procter & Gamble Company Detergent compositions comprising a mannanase and a protease
EP0896998A1 (fr) * 1997-08-14 1999-02-17 The Procter & Gamble Company Compositions détergentes pour le linge contenant une enzyme dégradant la gomme de polysaccharide
JPH11148093A (ja) * 1997-11-18 1999-06-02 Kao Corp 洗剤組成物
EP1045892A1 (fr) * 1997-12-22 2000-10-25 The Procter & Gamble Company Compositions de nettoyage contenant une neopullulanase
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
JP2004503370A (ja) 2000-06-14 2004-02-05 ザ、プロクター、エンド、ギャンブル、カンパニー 表面の洗浄方法
US20050176599A1 (en) * 2000-11-09 2005-08-11 Bergquist Catharine J. Controlled delivery system for household products
EP1856183B1 (fr) * 2005-02-08 2014-06-25 Basf Se Méthode de fabrication d'un produit en polyéthylèneimine alcoxylée
ES2354269T3 (es) * 2005-04-15 2011-03-11 Basf Se Polialquileminas anfifílicas alcoxiladas solubles en agua con un bloque interno de óxido de polietileno y un bloque externo de óxido de polipropileno.
TR201807737T4 (tr) * 2006-05-22 2018-06-21 Procter & Gamble İyileştirilmiş yağ temizleme için sıvı deterjan bileşimi.
EP2245129B1 (fr) * 2008-01-24 2012-05-09 Unilever N.V. Compositions de détergent pour machine à laver la vaisselle
GB0815022D0 (en) * 2008-08-16 2008-09-24 Reckitt Benckiser Nv Composition
ES2412684T3 (es) * 2009-06-19 2013-07-12 The Procter & Gamble Company Composición detergente de lavado de vajillas a mano líquida
HUE031936T2 (en) * 2009-09-14 2017-10-30 Procter & Gamble Liquid detergent composition
WO2011094374A1 (fr) * 2010-01-29 2011-08-04 The Procter & Gamble Company Nouveaux copolymères de polydiméthylsiloxane linéaire-polyéther avec des groupes amino et/ou ammonium quaternaire et utilisation de ceux-ci
EP3892709A3 (fr) * 2010-02-10 2022-01-19 Novozymes A/S Variantes et compositions comprenant des variantes avec une grande stabilité en présence d'un agent chélateur
US8168579B2 (en) * 2010-03-12 2012-05-01 The Procter And Gamble Company Fluid detergent compositions comprising a di-amido gellant, and processes for making
US8697834B2 (en) * 2010-05-31 2014-04-15 Basf Se Polyalkylenepolyamines by homogeneously catalyzed alcohol amination
CA2803625C (fr) * 2010-07-02 2016-04-05 The Procter & Gamble Company Filaments comprenant des voiles non tissees a agent actif, et procedes de fabrication de ces filaments
ES2659552T3 (es) * 2011-10-19 2018-03-16 Basf Se Formulaciones, su uso como o para la fabricación de detergentes para vajillas y su preparación
US8709990B2 (en) * 2011-10-19 2014-04-29 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
CN103874756B (zh) * 2011-10-19 2017-04-05 巴斯夫欧洲公司 配制剂、其作为或用于制备洗碟机用洗涤剂的用途及其制备
JP6133971B2 (ja) * 2012-04-25 2017-05-24 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 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
US9732309B2 (en) * 2012-04-25 2017-08-15 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
BR112014026564A2 (pt) * 2012-04-25 2017-06-27 Basf Se formulação, uso de uma formulação, e, processo para a preparação de uma formulação
US20130284210A1 (en) * 2012-04-25 2013-10-31 Basf Se Solid formulations, their preparation and use
EP2662436B1 (fr) * 2012-05-11 2017-08-23 The Procter & Gamble Company Composition de détergent
US8759271B2 (en) * 2012-05-11 2014-06-24 The Procter & Gamble Company Liquid detergent composition for improved shine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
JP2016526056A (ja) 2016-09-01
CN105143424B9 (zh) 2019-01-29
CN105143424B (zh) 2018-10-23
CN105143424A (zh) 2015-12-09
JP6235120B2 (ja) 2017-11-22
KR20160003006A (ko) 2016-01-08
EP2989192A1 (fr) 2016-03-02
US20160075972A1 (en) 2016-03-17
RU2015149916A (ru) 2017-05-26
PL2989192T3 (pl) 2019-01-31
WO2014173473A1 (fr) 2014-10-30

Similar Documents

Publication Publication Date Title
EP2768937B1 (fr) Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication
EP2841549B1 (fr) Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
EP2768935B1 (fr) Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation
EP2841548B1 (fr) Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
EP2768936B1 (fr) Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication
EP2981600B1 (fr) Formules, leur utilisation comme détergent pour lave-vaisselle et leur fabrication
EP3157969B1 (fr) Formulations, leur utilisation comme détergents pour vaisselle ou pour produire des détergents pour vaisselle, et leur préparation
US9732309B2 (en) Formulations, their use as or for producing dishwashing detergents and their production
EP3448975B1 (fr) Formules, leur fabrication et utilisation, ainsi que composants adaptes
US8846593B2 (en) Dishwashing composition comprising a covalently modified alkyleneimine polymer
EP2989192B1 (fr) Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
EP2961822B1 (fr) Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
WO2013160132A1 (fr) Formulations solides et production et utilisation desdites formulations
WO2014037255A1 (fr) Particules, procédé de fabrication et utilisation

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20151123

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20170629

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20180315

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 1027011

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180815

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013010813

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180808

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2693772

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20181213

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181108

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181109

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181208

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20181031

Year of fee payment: 6

Ref country code: TR

Payment date: 20181024

Year of fee payment: 6

Ref country code: ES

Payment date: 20181127

Year of fee payment: 6

Ref country code: IT

Payment date: 20181031

Year of fee payment: 6

Ref country code: FR

Payment date: 20181025

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20180918

Year of fee payment: 6

Ref country code: DE

Payment date: 20181228

Year of fee payment: 6

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013010813

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181007

26N No opposition filed

Effective date: 20190509

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181007

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1027011

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181007

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502013010813

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180808

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180808

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20131007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20191007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191007

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191031

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191007

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20210301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191008

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191007