EP2768937B1 - Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication - Google Patents

Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication Download PDF

Info

Publication number
EP2768937B1
EP2768937B1 EP12769436.2A EP12769436A EP2768937B1 EP 2768937 B1 EP2768937 B1 EP 2768937B1 EP 12769436 A EP12769436 A EP 12769436A EP 2768937 B1 EP2768937 B1 EP 2768937B1
Authority
EP
European Patent Office
Prior art keywords
weight
zinc
glass
ethyleneimine
formulations
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.)
Active
Application number
EP12769436.2A
Other languages
German (de)
English (en)
Other versions
EP2768937A1 (fr
Inventor
Stephan Hueffer
Alejandra Garcia Marcos
Markus Hartmann
Heike Weber
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=46982615&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2768937(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF SE filed Critical BASF SE
Priority to EP12769436.2A priority Critical patent/EP2768937B1/fr
Priority to PL12769436T priority patent/PL2768937T3/pl
Publication of EP2768937A1 publication Critical patent/EP2768937A1/fr
Application granted granted Critical
Publication of EP2768937B1 publication Critical patent/EP2768937B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/0005—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3953—Inorganic bleaching agents

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 detergents, in particular dishwashing detergents for machine 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, in many cases one can 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.
  • EP 2 118 254 It is known that one can use zinc salts in combination with certain vinyl polymers as inhibitors to prevent glass corrosion.
  • 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.
  • EP 1 721 962 A1 discloses a dishwashing detergent containing MGDA and zinc sulfate.
  • 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 according to the invention contain at least one zinc salt (B).
  • Zinc salts (B) can be selected from water-soluble and non-water-soluble zinc salts. In the context of the present invention, such Zinc salts (B) referred to as not water-soluble, which have a solubility of 0.1 g / l or less in distilled water at 25 ° C. Zinc salts (B), which have a higher water solubility, are accordingly referred to in the context of the present invention as water-soluble zinc salts.
  • zinc salt (B) is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnCl 2 , ZnSO 4 , zinc acetate, zinc citrate, Zn (NO 3 ) 2 , Zn (CH 3 SO 3 ) 2 and zinc gallate ZnCl 2 , ZnSO 4 , zinc acetate, zinc citrate, Zn (NO 3 ) 2 , Zn (CH 3 SO 3 ) 2 and zinc gallate are preferred.
  • zinc salt (B) is selected from ZnO, ZnO-aq, Zn (OH) 2 and ZnCO 3 .
  • ZnO-aq is preferred.
  • zinc salt (B) is selected from zinc oxides having an average particle diameter (weight average) in the range of 10 nm to 100 ⁇ m.
  • the cation in zinc salt (B) can be complexed, for example, complexed with ammonia ligands or water ligands, and especially present hydrated.
  • ligands are usually omitted in the context of the present invention, if they are water ligands.
  • zinc salt (B) can convert. It is thus possible, for example, to use zinc acetate or ZnCl 2 to prepare the formulation according to the invention, but this converts to ZnO, Zn (OH) 2 or ZnO-aq at a pH of 8 or 9 in an aqueous environment can not be complexed or complexed.
  • Zinc salt (B) is present in such formulations according to the invention which are solid at room temperature, preferably in the form of particles having, for example, a number average molecular weight in the range of 10 nm to 100 ⁇ m, preferably 100 nm to 5 ⁇ m, determined, for example, by X-ray scattering.
  • Zinc salt (B) is present in such inventive formulations, which are liquid at room temperature, in dissolved or solid or in colloidal form.
  • copolymers of ethyleneimine also include copolymers of ethyleneimine (aziridine) with one or more higher homologues of ethyleneimine, such as propyleneimine (2-methylaziridine), 1- or 2-butylenimine (2-ethylaziridine or dimethylaziridine) to understand, for example, with 0.01 to 75 mol% of one or more homologs of ethyleneimine, based on the proportion of ethyleneimine.
  • copolymers of ethyleneimine (C) are selected from graft copolymers of ethyleneimine (C). Such graft copolymers are also referred to in the context of the present invention as ethyleneimine graft copolymers (C). Ethyleneimine graft copolymers (C) may be crosslinked or uncrosslinked.
  • ethyleneimine graft copolymers (C) are selected from those polymers obtainable by grafting polyamidoamines with ethyleneimine.
  • ethyleneimine graft copolymers (C) are composed of 10 to 90% by weight of polyamidoamine as grafting base and 90 to 10% by weight of ethyleneimine as grafting support, each based on ethyleneimine graft copolymer (C).
  • Polyamidoamines are obtainable for example by condensation of polyalkylenepolyamines in pure form, as a mixture with one another or in a mixture with diamines.
  • polyalkylenepolyamines are understood as meaning compounds which contain at least 3 basic nitrogen atoms in the molecule, for example diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N- (2-aminoethyl) -1,3-propanediamine and N , N'-bis (3-aminopropyl) ethylenediamine.
  • diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, isophoronediamine, 4,4'-diaminodiphenylmethane, 1,4-bis ( 3-aminopropyl) piperazine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1,13-diamine and ⁇ , ⁇ -diamino compounds of polyalkylene oxides.
  • ethyleneimine graft copolymers (C) are selected from those polymers which can be prepared by grafting polyvinylamines as a grafting base with ethyleneimine or oligomers of ethyleneimine, for example dimerren or trimers of ethyleneimine.
  • ethyleneimine graft copolymers (C) are composed of 10 to 90% by weight of polyvinylamine as grafting base and 90 to 10% by weight of ethyleneimine as grafting support, in each case based on ethyleneimine graft copolymer (C).
  • polyethyleneimine (C) in the form of a homopolymer, preferably uncrosslinked, is chosen as the component of the formulation according to the invention.
  • polyethyleneimine (C) has an average molecular weight M n of from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 100,000 g / mol.
  • polyethyleneimine (C) has an average molecular weight M w in the range of 500 to 1,000,000 g / mol, preferably in the range of 600 to 75,000 g / mol, particularly preferably in the range of 800 to 25,000 g / mol, determinable for example by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • polyethyleneimines (C) are selected from highly branched polyethyleneimines.
  • Highly branched polyethylenimines (C) are characterized by their high degree of branching (DB).
  • Polyethyleneimines (C) having DB in the range from 0.1 to 0.95, preferably 0.25 to 0.90 and more preferably in the range from 0.30 to 0.80%, are considered highly branched polyethylenimines (C) within the scope of the present invention. and most preferably at least 0.5.
  • polyethylene dendrimers (C) which are dendritic polyethylenimines (C) are understood as meaning polyethylenimines (C) having a structurally and molecularly uniform structure.
  • polyethylenimine (C) 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.
  • polyethylenimine (C) is highly branched polyethyleneimines (homopolymers) having an average molecular weight M n of from 500 g / mol to 125,000 g / mol, preferably from 750 g / mol to 100,000 g / mol is selected from dendrimers.
  • formulations according to the invention contain in total in the range from 1 to 50% by weight of compound (A), preferably 10 to 25% by weight, in total in the range from 0.05 to 0.4% by weight of zinc salt (B), preferably 0, 1 to 0.2 wt .-%, and total in the range of 0.05 to 0.4 wt .-% zinc salt (B), preferably 0.1 to 0.2 wt .-%, and a total of from 0.05 to 2% by weight of homopolymer or copolymer of ethyleneimine (C), preferably from 0.1 to 0.5% by weight, optionally a total of 0.5 to 15% by weight of bleaching agent (D), in each case based on solids content of the relevant formulation.
  • the proportion of zinc salt is given as zinc or zinc ions. This allows you to calculate the proportion of the counterion.
  • 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.
  • zinc salt (B) may be present in formulations of the invention which are complexed by polyethylenimine (C).
  • formulation according to the invention is free of phosphates and polyphosphates, wherein hydrogen phosphates are subsumed, for example, free of trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate.
  • 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.
  • 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, preferably from 1 to 30 ppm, determined according to Leach method.
  • heavy metals are all metals having a specific density of at least 6 g / cm 3 , but not zinc.
  • the heavy metals are precious metals and bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.
  • formulation according to the invention contains no measurable proportions of bismuth compounds, that is to say, for example, less than 1 ppm.
  • formulation according to the invention contains one or more bleaching agents (D), for example one or more oxygen bleaching agents or one or more chlorine-containing bleaching agents.
  • D bleaching agents
  • formulations according to the invention may contain from 0.5 to 15% by weight of bleach (D).
  • oxygen bleaching agents are sodium perborate, anhydrous or, for example, monohydrate or tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy- ⁇ -naphthoic acid, 1,12-diperoxydodecanedioic acid , Perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as the free acid or as the alkali metal salt, in particular as the sodium salt, furthermore sulfonyl peroxyacids and cationic peroxyacids.
  • organic peracids such as peroxylauric acid, peroxystearic acid, peroxy- ⁇ -naphthoic acid, 1,12-diperoxydodecanedioic acid , Perbenzoic acid
  • formulations according to the invention may contain in the range of 0.5 to 15% by weight of oxygen bleach.
  • Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-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.
  • 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 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 tableting aids, or several 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 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,
  • 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.
  • 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 contain one or more builders, in particular phosphate-free builders.
  • suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, 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 citric acid and their alkali metal salts, succinic acid and its alkali metal salts, fatty acid sulfonates, ⁇ -hydroxypropionic acid, alkali metal malates, 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.
  • 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-hexadecene and 1-octadecene.
  • 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.
  • the polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.
  • 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 in the form of the neutral reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • Formulations of the invention may contain one or more alkali carriers.
  • Alkaline carriers for example, provide the pH of at least 9 when an alkaline pH is desired.
  • Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates.
  • Preferred alkali metal is in each case potassium, particularly preferred is sodium.
  • Formulations 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 manganese, iron, cobalt, ruthenium or molybdenum 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-hexahydro-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 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, phloroglucin 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 one or more acids, for example methanesulfonic acid.
  • formulations according to the invention have a pH in the range from 5 to 14, preferably 8 to 13.
  • 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 during use of the object can be contaminated.
  • 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.
  • 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.
  • Compound (A), zinc salt (B) and polyethyleneimine (C) and bleaching agent (D) are defined above.
  • ingredients (E) for formulation according to the invention before at least partially removing the water, it is possible to mix with one or more other ingredients (E) for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus free builder, one or more cobuilders, one or more alkali carriers, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, with buffer or dye.
  • surfactants for formulation according to the invention, for example with one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus free builder, one or more cobuilders, one or more alkali carriers, one or more bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, with buffer or dye.
  • the water is removed completely or partially, for example to a residual moisture in the range from zero to 5% by weight, from 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 dosing units, packaged or unpackaged.
  • the water content of liquid formulations can vary from 35 to 90% water.
  • % and ppm always denote wt .-% and wt ppm, unless expressly stated otherwise, and in the case of formulations according to the invention based on the total solids content.
  • Base mixtures were prepared containing the feedstocks according to Table 1. The starting materials were 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 5
  • Polyacrylic acid M w 4,000 g / mol as sodium salt, completely neutralized 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 0 22.5
  • HEDP 0.5 0.5 0.5
  • the glasses were placed in the upper basket of the dishwasher.
  • the dishwashing agent used was in each case 25 g of formulation according to the invention or comparison formulation according to Table 2, where Table 2 individually specifies the active components (A.1), optionally (B), optionally (C) and base mixture of formulation according to the invention.
  • 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.
  • One rinsed 100 rinsing cycles, ie, the program was run 100 times.
  • 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.
  • test specimens were each a champagne glass and a shot glass from the company Libbey (NL), a, material: soda-lime glasses.
  • the specimens were rinsed in a domestic dishwasher (Bosch SGS5602) with a 1 g surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g citric acid to remove any impurities.
  • the test pieces were dried, their weight determined and fixed on the grid floor insert.
  • the stainless steel pot was filled with 5.5 liters of water and added 25 g of formulation or comparison formulation according to the invention, wherein Table 3 shows the active components (A.1), optionally (B), optionally (C) and base mixture of formulation according to the invention or comparison formulation each individually specified.
  • the resulting cleaner liquor was stirred by means of the magnetic stirrer at 550 revolutions per minute. They installed the contact thermometer and covered the stainless steel pot with the lid, so that no water could evaporate during the experiment. It was heated to 75 ° C and put the grid bottom insert with the two specimens in the stainless steel pot, taking care that the specimens were completely immersed in the liquid.
  • test pieces were taken out and rinsed under running distilled water. Thereafter, the test pieces were rinsed in the domestic dishwasher with a formulation consisting of 1 g of surfactant (nC 18 H 37 (OCH 2 CH 2 ) 10 OH) and 20 g of citric acid again with the 55 ° C program to remove any deposits ,
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Washing And Drying Of Tableware (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (13)

  1. Formulation contenant
    (A) au total dans la plage de 1 à 50% en poids d'au moins un composé choisi parmi le méthylglycinediacétate (MGDA) et le sel trisodique du MGDA,
    (B) au total dans la plage de 0,05 à 0,4% en poids d'au moins un sel de zinc, indiqué en tant que Zn,
    (C) au total 0,05 à 2% en poids d'au moins un homopolymère ou copolymère de l'éthylèneimine et
    (D) le cas échéant 0,5 à 15% en poids d'agent de blanchiment (D),
    à chaque fois par rapport à la teneur en solides de la formulation en question.
  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 qu'on choisit (C) parmi les homopolymères de l'éthylèneimine, linéaires ou ramifiés, et les copolymères greffés de l'éthylèneimine.
  4. Formulation selon l'une quelconque des revendications 1 à 3, caractérisée en ce qu'on choisit de sel de zinc parmi le ZnCl2, le ZnSO4, l'acétate de zinc, le citrate de zinc, le Zn(NO3)2, le Zn(CH3SO3)2 et le gallate de zinc.
  5. Formulation selon l'une quelconque des revendications 1 à 4, caractérisée en ce qu'elle est solide à température ambiante.
  6. Formulation selon l'une quelconque des revendications 1 à 5, caractérisée en ce qu'elle contient de l'eau dans la plage de 0,1 à 10% en poids.
  7. Formulation selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'elle contient (D) au moins un agent de blanchiment choisi parmi les agents de blanchiment oxygénés et les agents de blanchiment contenant du chlore.
  8. Utilisation de formulations selon l'une quelconque des revendications 1 à 7 pour le nettoyage en machine de vaisselle et d'ustensiles de cuisine.
  9. Utilisation de formulations selon l'une quelconque des revendications 1 à 7 pour le nettoyage en machine d'objets qui présentent au moins une surface en verre, qui peut être décorée ou non décorée.
  10. Utilisation selon la revendication 8 ou 9, caractérisée en ce qu'il s'agit, pour le nettoyage en machine, d'un rinçage ou d'un nettoyage à l'aide d'un lave-vaisselle.
  11. Utilisation selon l'une quelconque des revendications 8 à 10, caractérisée en ce qu'on utilise au moins une formulation selon l'une quelconque des revendications 1 à 7 pour le nettoyage en machine de verres à boisson, de vases en verre et de récipients en verre pour cuisiner.
  12. Procédé pour la préparation de formulations selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'on mélange
    (A) au moins un composé, choisi parmi le méthylglycinediacétate (MGDA) et le sel trisodique du MGDA,
    (B) au moins un sel de zinc,
    (C) au moins un homopolymère ou copolymère de l'éthylèneimine
    (D) et le cas échéant au moins un agent de blanchiment choisi parmi les agents de blanchiment oxygénés et les agents de blanchiment contenant du chlore,
    et le cas échéant d'autres constituants, en une ou plusieurs étapes, les uns avec les autres en présence d'eau et on élimine ensuite l'eau.
  13. Procédé selon la revendication 12, caractérisé en ce qu'on élimine l'eau par séchage par pulvérisation, granulation par pulvérisation ou compactage.
EP12769436.2A 2011-10-19 2012-10-08 Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication Active EP2768937B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP12769436.2A EP2768937B1 (fr) 2011-10-19 2012-10-08 Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication
PL12769436T PL2768937T3 (pl) 2011-10-19 2012-10-08 Preparaty, ich zastosowanie jako środków do mycia naczyń lub do wytwarzania środków do mycia naczyń i ich wytwarzanie

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11185824 2011-10-19
EP12769436.2A EP2768937B1 (fr) 2011-10-19 2012-10-08 Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication
PCT/EP2012/069816 WO2013056996A1 (fr) 2011-10-19 2012-10-08 Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation

Publications (2)

Publication Number Publication Date
EP2768937A1 EP2768937A1 (fr) 2014-08-27
EP2768937B1 true EP2768937B1 (fr) 2016-01-13

Family

ID=46982615

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12769436.2A Active EP2768937B1 (fr) 2011-10-19 2012-10-08 Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication

Country Status (13)

Country Link
US (1) US8574374B2 (fr)
EP (1) EP2768937B1 (fr)
JP (1) JP5941153B2 (fr)
KR (1) KR101884618B1 (fr)
CN (1) CN103874756B (fr)
BR (1) BR112014006030A2 (fr)
CA (1) CA2844293A1 (fr)
ES (1) ES2564231T3 (fr)
IN (1) IN2014CN03506A (fr)
MX (1) MX2014002014A (fr)
PL (1) PL2768937T3 (fr)
RU (1) RU2607085C2 (fr)
WO (1) WO2013056996A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023117494A1 (fr) 2021-12-20 2023-06-29 Basf Se Polymères de polypropylène imine (ppi), leur préparation, leurs utilisations et compositions comprenant de tels ppi

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2491619B (en) 2011-06-09 2014-10-01 Pq Silicas Bv Builder granules and process for their preparation
US8846593B2 (en) 2012-04-25 2014-09-30 Basf Se Dishwashing composition comprising a covalently modified alkyleneimine polymer
US9732309B2 (en) * 2012-04-25 2017-08-15 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
US10301576B2 (en) 2013-02-28 2019-05-28 Basf Se Formulations, their use as or for producing dishwashing detergents and their production
EP2981600B1 (fr) * 2013-04-02 2018-03-21 Basf Se Formules, leur utilisation comme détergent pour lave-vaisselle et leur fabrication
PL2989192T3 (pl) * 2013-04-23 2019-01-31 Basf Se Preparaty, ich zastosowanie jako środków do zmywania naczyń lub do wytwarzania środków do zmywania naczyń i ich wytwarzanie
KR20160012209A (ko) * 2013-05-27 2016-02-02 바스프 에스이 고농도의 착물화제를 함유하는 수용액
EP3004311B1 (fr) 2013-05-27 2017-04-05 Basf Se Solutions aqueuses contenant un agent complexant en concentration élevée
EP2821471A1 (fr) * 2013-07-02 2015-01-07 Basf Se Solutions aqueuses contenant un agent complexant en concentration élevée
JP2015086295A (ja) * 2013-10-30 2015-05-07 花王株式会社 食器用洗浄剤組成物
EA030203B1 (ru) 2014-01-29 2018-07-31 Юнилевер Н.В. Очищающие композиции, содержащие стабильное серебро
MX2016009880A (es) 2014-01-29 2016-10-28 Unilever Nv Composicion de limpieza que contiene metal oligodinamico y agente potenciador de eficacia.
WO2015113924A1 (fr) 2014-01-29 2015-08-06 Unilever N.V. Composition aqueuse contenant un métal oligodynamique
WO2015197379A1 (fr) * 2014-06-23 2015-12-30 Basf Se Formulations, leur production et leur utilisation et composants appropriés
ES2670687T3 (es) * 2014-06-23 2018-05-31 Basf Se Formulaciones, su uso como o para la preparación de agentes lavavajillas y su preparación
DE102014212728A1 (de) * 2014-07-01 2016-01-07 Henkel Ag & Co. Kgaa Geschirrspülmittel
WO2016076033A1 (fr) * 2014-11-13 2016-05-19 三菱瓦斯化学株式会社 Liquide de nettoyage pour élément semi-conducteur inhibant les dommages sur du cobalt, et procédé de nettoyage d'élément semi-conducteur mettant en œuvre celui-ci
EP3026103B1 (fr) 2014-11-26 2018-07-25 The Procter and Gamble Company Poche de nettoyage
EP3050952A1 (fr) * 2015-02-02 2016-08-03 The Procter and Gamble Company Procédé de lavage de vaisselle
EP3050951A1 (fr) * 2015-02-02 2016-08-03 The Procter and Gamble Company Procédé de lavage de vaisselle
CA3081788C (fr) 2017-11-14 2022-08-09 Ecolab Usa Inc. Compositions detergentes caustiques a liberation controlee de matieres solides
CN111788291B (zh) 2018-02-23 2021-08-24 联合利华知识产权控股有限公司 包含氨基多羧酸盐和无机酸的洗涤剂固体组合物
DE102018205971A1 (de) * 2018-04-19 2019-10-24 Henkel Ag & Co. Kgaa Korrosionsschutz für Glaswaren in einer Geschirrspülmaschine
CN112074593B (zh) * 2018-05-04 2022-08-30 巴斯夫欧洲公司 颗粒或粉末及其制备方法
BR112021009135A2 (pt) * 2018-12-13 2021-08-10 Dow Global Technologies Llc formulação de detergente líquido para roupas
CN110408476A (zh) * 2019-07-19 2019-11-05 武汉东湖星科技有限公司 一种高效低泡洗瓶剂及其制备方法
CN114222808A (zh) 2019-09-27 2022-03-22 埃科莱布美国股份有限公司 浓缩二合一洗碗机洗涤剂和漂洗助剂

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1721962A1 (fr) 2005-05-11 2006-11-15 Unilever N.V. Compositions detergentes pour lave vaisselle et procédé pour nettoyer la vaiselle
WO2010020765A1 (fr) 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3841982A (en) * 1972-04-17 1974-10-15 Oxy Metal Finishing Corp Method to improve the brightness of zinc from an alkaline zincate electrodeposition bath
US4917812A (en) 1989-02-13 1990-04-17 The Procter & Gamble Company Granular automatic dishwasher detergent composition providing glassware protection containing insoluble zinc compound
EP0561452A1 (fr) * 1992-03-20 1993-09-22 Unilever N.V. Composition détergente pour le lavage en machine de la vaisselle contenant des acides aminés polymères en tant qu'adjuvants
US5714447A (en) * 1996-01-24 1998-02-03 Church & Dwight Co., Inc. Deodorant soap or detergent composition containing a zinc compound and a polyamine
US5837663A (en) 1996-12-23 1998-11-17 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing tablets containing a peracid
CA2296719A1 (fr) 1997-07-23 1999-02-04 Joseph Oreste Carnali Compositions pour lave-vaisselle renfermant des polymeres cationiques ou amphoteres solubles dans l'eau
US5981456A (en) * 1997-07-23 1999-11-09 Lever Brothers Company Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
JPH11148093A (ja) * 1997-11-18 1999-06-02 Kao Corp 洗剤組成物
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
DE10010209A1 (de) * 2000-03-02 2001-09-13 Reckitt Benckiser Nv Keramisches Material als Korrosionsschutz in einer Geschirrspülmaschine
DE10104469A1 (de) 2001-02-01 2002-08-08 Basf Ag Copolymere zur Verhinderung von Glaskorrosion
DE10225116A1 (de) 2002-06-06 2003-12-24 Henkel Kgaa Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz II
US20040176264A1 (en) * 2002-12-30 2004-09-09 The Procter & Gamble Company Rinse aid composition containing water-soluble metal salt for use in automatic dishwashing for glassware corrosion protection
WO2006051932A1 (fr) * 2004-11-11 2006-05-18 Kao Corporation Adoucissant en crème
JP5025097B2 (ja) * 2005-06-02 2012-09-12 ディバーシー・アイピー・インターナショナル・ビー・ヴイ 自動洗浄機用液体洗浄剤組成物
DE102007006627A1 (de) 2007-02-06 2008-08-07 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102007019458A1 (de) * 2007-04-25 2008-10-30 Basf Se Phosphatfreies Maschinengeschirrspülmittel mit ausgezeichneter Klarspülleistung
GB0716228D0 (en) 2007-08-20 2007-09-26 Reckitt Benckiser Nv Detergent composition
JP5398292B2 (ja) * 2009-02-10 2014-01-29 ライオン株式会社 液体洗浄剤組成物
GB0906281D0 (en) * 2009-04-09 2009-05-20 Reckitt Benckiser Nv Detergent compositions
US20110150817A1 (en) * 2009-12-17 2011-06-23 Ricky Ah-Man Woo Freshening compositions comprising malodor binding polymers and malodor control components

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1721962A1 (fr) 2005-05-11 2006-11-15 Unilever N.V. Compositions detergentes pour lave vaisselle et procédé pour nettoyer la vaiselle
WO2010020765A1 (fr) 2008-08-16 2010-02-25 Reckitt Benckiser N.V. Composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023117494A1 (fr) 2021-12-20 2023-06-29 Basf Se Polymères de polypropylène imine (ppi), leur préparation, leurs utilisations et compositions comprenant de tels ppi

Also Published As

Publication number Publication date
WO2013056996A1 (fr) 2013-04-25
CA2844293A1 (fr) 2013-04-25
KR101884618B1 (ko) 2018-08-02
JP2014530930A (ja) 2014-11-20
RU2607085C2 (ru) 2017-01-10
RU2014119760A (ru) 2015-11-27
JP5941153B2 (ja) 2016-06-29
PL2768937T3 (pl) 2016-07-29
US20130102515A1 (en) 2013-04-25
MX2014002014A (es) 2014-03-27
IN2014CN03506A (fr) 2015-10-09
BR112014006030A2 (pt) 2017-04-04
EP2768937A1 (fr) 2014-08-27
ES2564231T3 (es) 2016-03-21
CN103874756B (zh) 2017-04-05
US8574374B2 (en) 2013-11-05
KR20140088566A (ko) 2014-07-10
CN103874756A (zh) 2014-06-18

Similar Documents

Publication Publication Date Title
EP2768937B1 (fr) Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication
EP2768936B1 (fr) Formules, leur utilisation comme ou pour fabriquer des produits lave-vaisselle ainsi que leur fabrication
EP2768935B1 (fr) Formulations, leur utilisation comme détergents pour vaisselle ou pour la fabrication de détergents pour vaisselle, et leur préparation
EP2981600B1 (fr) Formules, leur utilisation comme détergent pour lave-vaisselle et leur fabrication
EP2841549B1 (fr) Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
EP2841548B1 (fr) Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
EP3157969B1 (fr) Formulations, leur utilisation comme détergents pour vaisselle ou pour produire des détergents pour vaisselle, et leur préparation
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
EP3448975B1 (fr) Formules, leur fabrication et utilisation, ainsi que composants adaptes
EP2989192B1 (fr) Formules, leur utilisation comme détergent pour lave-vaisselle ou destinées à sa fabrication, ainsi que leur fabrication
EP2788466B1 (fr) Utilisation de préparations pour lavage en lave-vaisselle
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: 20140519

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

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150722

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

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: AT

Ref legal event code: REF

Ref document number: 770527

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502012005728

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2564231

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20160321

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160113

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

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: 20160113

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: 20160113

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: 20160414

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: 20160113

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: 20160413

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

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: 20160113

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: 20160513

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: 20160513

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: 20160113

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: 20160113

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: 20160113

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502012005728

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

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: 20160113

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: 20160113

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20161013

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

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: 20160113

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: 20160113

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: 20160113

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: 20160113

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: 20161031

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: 20160413

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: 20160113

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: CH

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

Effective date: 20161031

Ref country code: LI

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

Effective date: 20161031

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

Ref country code: LU

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

Effective date: 20161008

RDAE Information deleted related to despatch of communication that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSDREV1

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 502012005728

Country of ref document: DE

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: 20161008

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20161031

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

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

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20171113

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

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: 20121008

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160113

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: 20160113

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: 20160113

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: 20160113

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

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

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: 20160113

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 770527

Country of ref document: AT

Kind code of ref document: T

Effective date: 20171008

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

Ref country code: AT

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

Effective date: 20171008

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

RDAE Information deleted related to despatch of communication that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSDREV1

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

Ref country code: TR

Payment date: 20230919

Year of fee payment: 12

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

Ref country code: PL

Payment date: 20230915

Year of fee payment: 12

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

Ref country code: GB

Payment date: 20231024

Year of fee payment: 12

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

Ref country code: ES

Payment date: 20231110

Year of fee payment: 12

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

Ref country code: IT

Payment date: 20231024

Year of fee payment: 12

Ref country code: FR

Payment date: 20231026

Year of fee payment: 12

Ref country code: DE

Payment date: 20231027

Year of fee payment: 12