[go: up one dir, main page]

EP1507844B1 - Use of an amphoteric copolymer in a dish washing composition - Google Patents

Use of an amphoteric copolymer in a dish washing composition Download PDF

Info

Publication number
EP1507844B1
EP1507844B1 EP03755203A EP03755203A EP1507844B1 EP 1507844 B1 EP1507844 B1 EP 1507844B1 EP 03755203 A EP03755203 A EP 03755203A EP 03755203 A EP03755203 A EP 03755203A EP 1507844 B1 EP1507844 B1 EP 1507844B1
Authority
EP
European Patent Office
Prior art keywords
water
soluble
use according
washing
amphoteric copolymer
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.)
Expired - Lifetime
Application number
EP03755203A
Other languages
German (de)
French (fr)
Other versions
EP1507844A1 (en
Inventor
Eric Aubay
Garry Embleton
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.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
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=29415106&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1507844(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1507844A1 publication Critical patent/EP1507844A1/en
Application granted granted Critical
Publication of EP1507844B1 publication Critical patent/EP1507844B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/08—Silicates
    • 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
    • C11D3/3796—Amphoteric polymers or zwitterionic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds

Definitions

  • the subject of the present invention is the use, in a "two-in-one" or “three-in-one” washing and rinsing composition of machine crockery, of an amphoteric water-soluble or water-dispersible copolymer as an anti-redeposition agent for soiling (" repellent agent "). It also relates, as a new industrial product, a solid preformulation, especially in the form of granules, comprising said amphoteric copolymer adsorbed and / or absorbed on a water-soluble solid inorganic support, and the use, in a composition "two in one "or” three in one "washing and rinsing machine dishware, said preformulation as a soil repellent agent agent (" soil repellent agent ").
  • compositions for the treatment of hard surfaces water-soluble or water-dispersible amphoteric copolymers derived from at least one cationic monomer of the family of diallyldimethylammonium chloride (DADMAC for diallyldimethylammonium chloride), at least one anionic monomer (acrylic acid in particular) and optionally at least one nonionic monomer, to give the treated surface hydrophilization properties.
  • DMDMAC diallyldimethylammonium chloride
  • anionic monomer acrylic acid in particular
  • nonionic monomer optionally at least one nonionic monomer
  • compositions confer, in particular, on the treated surfaces anti-flow, anti-fogging, anti-stain or anti-stick remanent properties; anti-stick or anti-stain properties means that the treated surface retains these properties over time, including after subsequent contact with water, whether it is rainwater, distribution system water or rinse water with or without rinse aid. This is to avoid essentially stains or traces of water and limestone.
  • the ion X - is advantageously chosen from halide ions (chloride, ...) sulfate, hydrosulphate, phosphate, citrate, formate and acetate.
  • the copolymer according to the invention advantageously has a molecular weight of at least 1,000, advantageously at least 10,000; it can go preferentially from 50,000 to 500,000.
  • GPC gel permeation chromatography
  • the copolymer is preferably random.
  • the monomer (a) has the following structure:
  • a particularly preferred monomer is that of the above formula wherein X - represents CI - , referred to as DADMAC.
  • the monomers (b) are advantageously water-soluble monoethylenic unsaturated C 3 -C 8 carboxylic, sulphonic, sulfuric, phosphonic or phosphoric acids, their anhydrides and their water-soluble salts.
  • carboxylic acids such as acrylic acid, methacrylic acid, ⁇ -ethacrylic acid, ⁇ , ⁇ -dimethylacrylic acid, methylenemalonic acid and vinylacetic acid. allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacrylate alanine, N-acryloyl-hydroxy-glycine. and the alkali metal and ammonium salts thereof.
  • carboxylic acids such as acrylic acid, methacrylic acid, ⁇ -ethacrylic acid, ⁇ , ⁇ -dimethylacrylic acid, methylenemalonic acid and vinylacetic acid. allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-
  • acrylamide vinyl alcohol
  • C 1 -C 4 alkyl esters of acrylic acid and methacrylic acid C 1 -C 4 hydroxyalkyl esters of acrylic acid and methacrylic acid, especially acrylate and methacrylate of ethylene glycol and propylene glycol
  • polyalkoxylated esters of acrylic acid and of methacrylic acid especially the polyethylene glycol and polypropylene glycol esters.
  • the level of monomers (c) is advantageously between 0 and 50%, preferably 0 to 30 mol%.
  • the most preferred copolymers are DADMAC / acrylic acid copolymers whose molar ratio is between 15/85 and less than 50/50, preferably between 25/75 and 45/55.
  • the "two-in-one" or “three-in-one” washing and rinsing composition according to the invention comprises at least one copolymer as described above at a content of between 0.01% and 10%, preferably between 0.02% and % and 0.5% by weight relative to the total weight of the composition.
  • composition according to the invention generally comprises at least one surfactant.
  • This is advantageously nonionic and / or anionic and / or amphoteric; preferably it is a nonionic surfactant.
  • alkylene oxide condensates especially of ethylene oxide and optionally of propylene with alcohols, polyols, alkylphenols, fatty acid esters, amides of fatty acids and fatty amines; amine oxides, sugar derivatives such as alkylpolyglycosides or esters of fatty acids and sugars, especially sucrose monopalmitate; long-chain tertiary phosphine oxides; dialkyl sulfoxides; block copolymers of polyoxyethylene and polyoxypropylene; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly (ethylene oxide) and amides of fatty acids modified so as to confer a hydrophobic character (for example, mono- and diethanolamides of fatty acids containing from 10 to 18 carbon atoms ).
  • alkylene oxide condensates especially of ethylene oxide and optionally of propylene with alcohols, polyols, alkylphenols, fatty acid esters, amide
  • amphoteric surfactants mention may be made of sodium alkyl iminopropionates or iminodipropionates, such as Mirataine H2C HA and Mirataine JC HA from Rhodia.
  • the surfactants may be present in an amount of 0.1 to 20%, preferably 0.2 to 10% by weight.
  • the copolymer weight ratio of general formula (I) / surfactant is between 1/2 and 1/100, advantageously 1/5 and 1/50.
  • a washing and rinsing composition "3 in 1" differs from a washing and rinsing "2 in 1" in particular by a higher concentration of organic builders and sodium tripolyphosphate.
  • the "two-in-one" or “three-in-one” washing and rinsing composition may be in the form of a liquid, a gel, a compacted powder or no ; in a preferential manner, it is in the form of a monolayer or multilayer tablet.
  • a particularly advantageous embodiment consists in the use, according to the invention, of said amphoteric water-soluble or water-dispersible copolymers in the form of a solid preformulation, in particular in the form of granules, comprising said amphoteric copolymer adsorbed and / or absorbed on an inorganic support water-soluble solid.
  • a second subject of the invention consists, as a new industrial product, in a dry solid preformulation intended for a "two-in-one" or "three-in-one” washing and rinsing composition for an automatic dishwashing machine, said preformulation consisting essentially of a solution or dispersion of said amphoteric copolymer adsorbed and / or absorbed on a particulate solid support into at least one water-soluble inorganic material.
  • water-soluble inorganic carriers there may be mentioned sulphates, tripolyphosphates, carbonates, bicarbonates, sesquicarbonates of alkali metals, preferably sodium.
  • said support is sodium tripolyphosphate, preferably in anhydride form obtained by atomization.
  • the weight ratio, expressed as dry, amphoteric copolymer / inorganic support is from 5/95 to 50/50, preferably from 10/90 to 30/70.
  • said preformulation is in the form of cogranules having a median diameter of 250 to 1000 ⁇ m (measurement by sieve size).
  • Said preformulation may be obtained by granulation of the support material in particulate form with the aid of an aqueous solution or dispersion of amphoteric copolymer, said solution or dispersion having a solids content of 10 to 40%, preferably from 15 to 35%.
  • the support material in particulate form may have a median diameter of 150 to 700 ⁇ m.
  • the granulation operation can be carried out in a known manner using a granulation apparatus such as drum, plate, fluidized bed, etc. If necessary the cogranules obtained are dried, in fluidized bed in particular, to improve their flowability.
  • Said preformulation may further contain other components, including nonionic surfactants and organic cobuilders already mentioned above.
  • a third object of the invention consists in a method for improving the anti-redeposition properties of soils of a "two-in-one" or "three-in-one” washing and rinsing composition for machine dishwashing, by addition to said composition of an effective amount of at least one water-soluble or water-dispersible amphoteric copolymer described above or a preformulation as described above.
  • the amounts of amphoteric copolymer, as well as the nature and amounts of the other additives possibly present have already been mentioned above.
  • the sodium silicate is a cogranulate of sodium silicate hydrated SiO 2 / Na 2 O ratio ranging from 1.5 to 3.5, and sodium carbonate, the weight ratio of silicate to carbonate ranging from 5/95 to 45/55, preferably from 15/85 to 35/65, such as NABION 15 marketed by Rhodia.
  • Said “2 in 1” or “3 in 1” formulation may further comprise usual additives present in the dishwashing compositions, such as those described above and in amounts already mentioned above.
  • the washing and rinsing formulation is implemented in the dishwashing machine, by introduction into the compartment of the machine provided for this purpose. 20 g of conventional washing powder containing 0.1% or 0.2% of polymer to be tested are thus used.
  • the test is performed on 10 soda glasses regularly placed in the machine.
  • the dirt used is a mixture of salad dressing (50%), Ketchup (5%), mayonnaise (10%), milk (25%) and cream (10%).
  • Example 1 Powder or tablet formula "3 in 1"
  • the test is performed in hard water (40 ° TH), without rinsing salts or regenerating salt.
  • the tested formulation is as follows: NABION 15 (builder, co-granulated Carbonate / Sodium silicate) 25% Rhodiaphos HD7 (STPP) 52% Antarox B12 DF (non-ionic surfactant, defoamer) 0.9% Antarox B79R (nonionic surfactant) 0.9% Briquest 543-25S (phosphonates) 1.1% Perborate Monohydrate (bleaching agent) 8% TAED (bleach catalyst) 2% Rhodoline DP 226 35 (polymer builder) 2% Amylase (enzyme) 1.3% Protease (enzyme) 0.7% Polymer to test 0.2% Na 2 SO 4 5.9%
  • the formulation is in powder form or in the form of a tablet of 44 mm in diameter and 1 cm in thickness, obtained by compacting 20 g of powder under a pressure of 2 MPa.
  • a real anti-redeposition benefit of the stains and rinses brought about by the presence of 0.2% of AA / DADMAC copolymers with a molar distribution of 85/15 and 60/40, compared with the control, as well as with respect to AA / DIQUAT copolymers with a molar distribution of 60/40 and 50/50 or AA / MAPTAC with a molar distribution of 60/40.
  • Example 2 Powder or tablet "2 in 1" formula:
  • the test is performed in fresh water ( ⁇ 5 ° TH), without rinsing salt.
  • the tested formulation is as follows: NABION 15 (builder, co-granulated Carbonate / Sodium silicate) 34% Rhodiaphos HD7 (STPP) 30% Antarox B12 DF (non-ionic surfactant, defoamer) 0.8% Antarox B79R (nonionic surfactant) 0.8% Briquest 543-45AS (phosphonates) 0.8% Perborate Monohydrate (bleaching agent) 8% TAED (bleach catalyst) 2% Rhodoline DP 226 35 (polymer builder) 1.5% Amylase (enzyme) 1.3% Protease (enzyme) 0.7% Na 2 SO 4 20% Polymer to test 0.1%
  • the formulation is in powder form or in the form of a tablet of 44 mm in diameter and 1 cm in thickness, obtained by compacting 20 g of powder under a pressure of 4 MPa.
  • Example 1 The operation described in Example 1 is carried out using the formulations given in the following table: Formulation Nonionic surfactant 0.9% 0.9% Anhydrous STPP 50% 50% Sodium perborate monohydrate 8% 8% Sodium disilicate 14% * 3.48% ** Sodium carbonate 6.6% 6.6% ** Sokalan CP5 (polymer builder) 2% 2% phosphonate 1% 1% DAT 2% 2% Enzymes (protease + amylase) 2% 2% AA / DADMAC 60/40 Polymer 0.1% 0.1% Sodium sulphate qs 100 qs 100 Test result 5 9 * supplied by atomized sodium disilicate (80%) ** contributed by 12% of Nabion 15
  • Example 1 The operation described in Example 1 is carried out using the formulations given in the following table: Formulation Nonionic surfactant 1.8% 1.8% 1.8% 1.8% Anhydrous STPP 52% 52% 52% 52% Sodium perborate monohydrate 8% 8% 8% Sodium disilicate 3.48% ** 7% * 12% * 18% * Sodium carbonate 6.6% ** 6.6% 6.6% 6.6% Briquest 543-25S (phosphonates) 1.1% 1.1% 1.1% 1.1% Rhodoline DP 226 35 (polymer builder) 2% 2% 2% 2% 2% 2% 2% 2% DAT 2% 2% 2% 2% 2% 2% 2% 2% 2% 2% Enzymes (protease + amylase) 2% 2% 2% 2% 2% 2% 2% Polymer AA / DADMAC 70/30 0.1% 0.1% 0.1% 0.1% Sodium sulphate qs 100 qs 100 qs 100 qs 100 Test result 9 8 5 3 * supplied by atomized sodium disilicate (80%

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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Water-soluble or water-dispersible amphoteric copolymer (I) derived from a dialkenylammonium monomer and hydrophilic acid-functional monomer is used in a two-in-one or three-in-one washing and rinsing composition for dishwashing machines. Water-soluble or -dispersible amphoteric copolymer (I) derived from a dialkenylammonium monomer of formula (II) and hydrophilic acid-functional monomer is used in a two-in-one or three-in-one washing and rinsing composition for dishwashing machines. R1, R4 = H or 1-6C alkyl; R2, R3 = 1-6C alkyl, hydroxyalkyl or aminoalkyl; n, m = 1-3; and X = an anion. Independent claims are also included for: (1) dry solid preformulation comprising (I) adsorbed and/or absorbed on a particulate water-soluble inorganic support; and (2) two-in-one or three-in-one dishwasher detergent formulation comprising at least 20% sodium tripolyphosphate, less than 15% sodium silicate (SiO2/Na2O molar ratio = 1-4), 0.02-0.5% (I) and 0.1-20% nonionic surfactant.

Description

La présente invention a pour objet l'utilisation, dans une composition « deux en un » ou « trois en un » lavante et rinçante de la vaisselle en machine, d'un copolymère amphotère hydrosoluble ou hydrodispersable comme agent anti-redéposition des salissures (« soil repellent agent »). Elle a également pour objet, à titre de produit industriel nouveau, une préformulation solide, notamment sous forme de granulés, comprenant ledit copolymère amphotère adsorbé et/ou absorbé sur un support inorganique solide hydrosoluble, ainsi que l'utilisation, dans une composition « deux en un » ou « trois en un » lavante et rinçante de la vaisselle en machine, de ladite préformulation comme agent anti-redéposition des salissures (« soil repellent agent »).The subject of the present invention is the use, in a "two-in-one" or "three-in-one" washing and rinsing composition of machine crockery, of an amphoteric water-soluble or water-dispersible copolymer as an anti-redeposition agent for soiling (" repellent agent "). It also relates, as a new industrial product, a solid preformulation, especially in the form of granules, comprising said amphoteric copolymer adsorbed and / or absorbed on a water-soluble solid inorganic support, and the use, in a composition "two in one "or" three in one "washing and rinsing machine dishware, said preformulation as a soil repellent agent agent (" soil repellent agent ").

Il a été proposé dans la demande WO 01/5921 , déposée au nom de la Demanderesse d'utiliser, dans les compositions pour le traitement des surfaces dures, des copolymères amphotères hydrosolubles ou hydrodispersables dérivés d'au moins un monomère cationique de la famille du chlorure de diallyldiméthylammonium (DADMAC pour diallyldimethylammonium chloride), d'au moins un monomère anionique (acide acrylique notamment) et éventuellement d'au moins un monomère non-ionique, pour conférer à la surface traitée des propriétés d'hydrophilisation. Les compositions décrites sont destinées au lavage ou au rinçage de la vaisselle en machine ou à la main, au nettoyage des vitres, des céramiques (salles de bains, lavabos, cuvettes de toilettes), des parois de douches, des carrosseries automobiles. Ces compositions confèrent en particulier aux surfaces traitées des propriétés anti-écoulement, anti-buée, anti-taches ou anti-traces rémanentes ; par propriétés anti-traces ou anti-taches rémanentes, on entend que la surface traitée conserve ces propriétés au cours du temps, y compris après les contacts ultérieurs avec de l'eau, qu'il s'agisse d'eau de pluie, d'eau du réseau de distribution ou de l'eau de rinçage addtitionnée ou non de produits de rinçage. Il s'agit donc ici d'éviter essentiellement les taches ou les traces d'eau et de calcaire.It was proposed in the application WO 01/5921 , filed in the name of the Applicant to use, in the compositions for the treatment of hard surfaces, water-soluble or water-dispersible amphoteric copolymers derived from at least one cationic monomer of the family of diallyldimethylammonium chloride (DADMAC for diallyldimethylammonium chloride), at least one anionic monomer (acrylic acid in particular) and optionally at least one nonionic monomer, to give the treated surface hydrophilization properties. The compositions described are intended for washing or rinsing dishes in the machine or by hand, cleaning windows, ceramics (bathrooms, wash basins, toilet bowls), shower walls, car bodies. These compositions confer, in particular, on the treated surfaces anti-flow, anti-fogging, anti-stain or anti-stick remanent properties; anti-stick or anti-stain properties means that the treated surface retains these properties over time, including after subsequent contact with water, whether it is rainwater, distribution system water or rinse water with or without rinse aid. This is to avoid essentially stains or traces of water and limestone.

Il a été constaté que l'utilisation de ces copolymères dans des compositions lavantes et rinçantes pour le nettoyage de la vaisselle en machine, ne permettait pas toujours de résoudre les problèmes de redéposition des salissures.It has been found that the use of these copolymers in washing and rinsing compositions for machine dishwashing does not did not always solve the problems of redeposition of dirt.

La Demanderesse a maintenant trouvé qu'un choix judicieux de rapport de charges permettait la mise en oeuvre des copolymères amphotères à base de DADMAC comme agent anti-redéposition des salissures dans les compositions dites « deux en un » (lavage et rinçage) ou « trois en un » (adoucissage, lavage et rinçage) pour le lavage en machine de la vaisselle.The Applicant has now found that a judicious choice of charge ratio allows the use of amphoteric copolymers based on DADMAC as an anti-redeposition agent for soiling in so-called "two-in-one" compositions (washing and rinsing) or "three-in-one" compositions. in one "(softening, washing and rinsing) for machine washing dishes.

Un premier objet de l'invention consiste en l'utilisation, dans une composition lavante et rinçante « deux en un » (« two in one ») ou « trois en un » (« three in one ») pour le nettoyage de la vaisselle en machine, d'un copolymère amphotère hydrosoluble ou hydrodispersable comprenant, sous la forme d'unités polymérisées :

  • * (a) au moins un composé monomère de formule générale I:
    Figure imgb0001
     dans laquelle :
    • R1 et R4 représentent indépendamment l'un de l'autre un atome d'hydrogène ou un groupe alkyle en C1-C6 linéaire ou ramifié ;
    • R2 et R3 représentent indépendamment l'un de l'autre un groupe alkyle, hydroxyalkyle, ou aminoalkyle dans lesquelles le groupe alkyle est une chaîne en C1-C6, linéaire ou ramifiée, de préférence un groupe méthyle ;
    • n et m sont des nombres entiers compris entre 1 et 3 ;
    • X représente un contre-ion compatible avec le caractère hydrosoluble ou hydrodispersible du polymère;
  • * (b) au moins un monomère hydrophile portant une fonction à caractère acide copolymérisable avec (a) et susceptible de s'ioniser dans le milieu d'application,
  • * (c) éventuellement au moins un composé monomère hydrophile à insaturation éthylénique de charge neutre portant un ou plusieurs groupes hydrophiles, copolymérisable avec (a) et (b),
    dans lequel le rapport molaire a/b est compris entre 15/85 et moins de 50/50, de préférence entre 25/75 et 45/55,
    comme agent anti-redéposition des salissures (« soil repellent agent »).
A first object of the invention is the use, in a washing and rinsing composition "two in one"("two in one") or "three in one"("three in one") for cleaning the dishes in a machine, a water-soluble or water-dispersible amphoteric copolymer comprising, in the form of polymerized units:
  • (a) at least one monomeric compound of general formula I:
    Figure imgb0001
     in which :
    • R 1 and R 4 represent independently of each other a hydrogen atom or a linear or branched C 1 -C 6 alkyl group;
    • R 2 and R 3 represent, independently of one another, an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a linear or branched C 1 -C 6 chain, preferably a methyl group;
    • n and m are integers between 1 and 3;
    • X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer;
  • (b) at least one hydrophilic monomer carrying a function of acid character copolymerizable with (a) and capable of ionizing in the application medium,
  • (c) optionally at least one neutral charge ethylenically unsaturated hydrophilic monomer compound bearing one or more hydrophilic groups, copolymerizable with (a) and (b),
    wherein the molar ratio a / b is from 15/85 to less than 50/50, preferably 25/75 to 45/55,
    as an anti-soil redeposition agent ("soil repellent agent").

De manière préférée,

  • R1 représente hydrogène,
  • R2 représente méthyle,
  • R3 représente méthyle,
  • R4 représente hydrogène, et
  • m et n sont égaux à 1
Preferably,
  • R 1 represents hydrogen,
  • R 2 represents methyl,
  • R 3 represents methyl,
  • R 4 represents hydrogen, and
  • m and n are equal to 1

L'ion X- est avantageusement choisi parmi les ions halogénures (chlorure, ...) sulfate, hydrosulfate, phosphate, citrate, formiate et acétate.The ion X - is advantageously chosen from halide ions (chloride, ...) sulfate, hydrosulphate, phosphate, citrate, formate and acetate.

Le copolymère selon l'invention présente avantageusement une masse moléculaire d'au moins 1 000, avantageusement d'au moins 10 000 ; elle peut aller préférentiellement de 50 000 à 500 000.The copolymer according to the invention advantageously has a molecular weight of at least 1,000, advantageously at least 10,000; it can go preferentially from 50,000 to 500,000.

Sauf indications contraires, lorsqu'on parlera de masse moléculaire, il s'agira de la masse moléculaire en poids, exprimée en g/mol.Unless otherwise indicated, when reference is made to molecular weight, it will be the molecular weight in weight, expressed in g / mol.

Celle-ci peut être déterminée par chromatographie de perméation de gel aqueux (GPC) ou mesure de la viscosité intrinsèque dans une solution 1 N de NaNO3 à 30°C.This can be determined by aqueous gel permeation chromatography (GPC) or measurement of the intrinsic viscosity in a 1 N solution of NaNO 3 at 30 ° C.

Le copolymère est de préférence statistique.The copolymer is preferably random.

De façon préférentielle, le monomère (a) a la structure suivante :

Figure imgb0002
Preferably, the monomer (a) has the following structure:
Figure imgb0002

X- étant est tel que défini précédemment.X - being is as defined above.

Un monomère particulièrement préféré est celui de formule ci-dessus dans laquelle X- représente CI-, dénommé DADMAC.A particularly preferred monomer is that of the above formula wherein X - represents CI - , referred to as DADMAC.

Les monomères (b) sont avantageusement des acides carboxyliques, sulfoniques, sulfuriques, phosphoniques ou phosphoriques en C3-C8 à insaturation monoéthylénique hydrosolubles, leurs anhydrides et leurs sels hydrosolubles.The monomers (b) are advantageously water-soluble monoethylenic unsaturated C 3 -C 8 carboxylic, sulphonic, sulfuric, phosphonic or phosphoric acids, their anhydrides and their water-soluble salts.

Parmi les monomères (b) préférés, on peut citer les acides carboxyliques comme l'acide acrylique, l'acide méthacrylique, l'acide α-éthacrylique, l'acide β,β-diméthylacrylique, l'acide méthylènemalonique, l'acide vinylacétique, l'acide allylacétique, l'acide éthylidineacétique, l'acide propylidineacétique, l'acide crotonique, l'acide maléique, l'acide fumarique, l'acide itaconique, l'acide citraconique, l'acide mésaconique, la N-méthacroyl-alanine, la N-acryloyl-hydroxy-glycine. et les sels de métal alcalin et d'ammonium de ceux-ci.Among the preferred monomers (b), mention may be made of carboxylic acids such as acrylic acid, methacrylic acid, α-ethacrylic acid, β, β-dimethylacrylic acid, methylenemalonic acid and vinylacetic acid. allylacetic acid, ethylidineacetic acid, propylidineacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, N-methacrylate alanine, N-acryloyl-hydroxy-glycine. and the alkali metal and ammonium salts thereof.

Parmi les monomères (c), on peut citer l'acrylamide, l'alcool vinylique, les esters d'alkyle en C1-C4 de l'acide acrylique et de l'acide méthacrylique, les esters d'hydroxyalkyle en C1-C4 de l'acide acrylique et de l'acide méthacrylique, notamment l'acrylate et le méthacrylate d'éthylène glycol et de propylène glycol, les esters polyalkoxylés de l'acide acrylique et de l'acide méthacrylique, notamment les esters de polyéthylène glycol et de polypropylène glycol.Among the monomers (c), mention may be made of acrylamide, vinyl alcohol, C 1 -C 4 alkyl esters of acrylic acid and methacrylic acid, C 1 -C 4 hydroxyalkyl esters of acrylic acid and methacrylic acid, especially acrylate and methacrylate of ethylene glycol and propylene glycol, polyalkoxylated esters of acrylic acid and of methacrylic acid, especially the polyethylene glycol and polypropylene glycol esters.

Le taux de monomères (c) est avantageusement compris entre 0 et 50%, de préférence 0 à 30% molaire.The level of monomers (c) is advantageously between 0 and 50%, preferably 0 to 30 mol%.

Les copolymères suivants sont tout particulièrement préférés :

  • copolymères DADMAC/acide acrylique ;
  • copolymères DADMAC/acide maléique;
  • copolymères DADMAC/acide itaconique ;
    le rapport molaire DADMAC/monomère acide étant compris entre 15/85 et moins de 50/50, de préférence entre 25/75 et 45/55.
The following copolymers are very particularly preferred:
  • DADMAC / acrylic acid copolymers;
  • DADMAC / maleic acid copolymers;
  • DADMAC / itaconic acid copolymers;
    the molar ratio DADMAC / acidic monomer being between 15/85 and less than 50/50, preferably between 25/75 and 45/55.

Les copolymères tout préférentiels sont les copolymères DADMAC/acide acrylique dont le rapport molaire est entre 15/85 et moins de 50/50, de préférence entre 25/75 et 45/55.The most preferred copolymers are DADMAC / acrylic acid copolymers whose molar ratio is between 15/85 and less than 50/50, preferably between 25/75 and 45/55.

La composition lavante et rinçante « deux en un » ou « trois en un » selon l'invention comprend au moins un copolymère tel que décrit ci-dessus à une teneur comprise entre 0,01% et 10%, de préférence entre 0,02% et 0,5% en poids par rapport au poids total de la composition.The "two-in-one" or "three-in-one" washing and rinsing composition according to the invention comprises at least one copolymer as described above at a content of between 0.01% and 10%, preferably between 0.02% and % and 0.5% by weight relative to the total weight of the composition.

La composition selon l'invention comprend généralement au moins un agent tensioactif. Celui-ci est avantageusement non-ionique et/ou anionique et/ou amphotère ; de préférence il s'agit d'un agent tensioactif non-ionique.The composition according to the invention generally comprises at least one surfactant. This is advantageously nonionic and / or anionic and / or amphoteric; preferably it is a nonionic surfactant.

Parmi les agents tensioactifs non ioniques, on peut citer en particulier les condensats d'oxyde d'alkylène, notamment d'oxyde d'éthylène et éventuellement de propylène avec des alcools, des polyols, des alkylphénols, des esters d'acides gras, des amides d'acides gras et des amines grasses ; les amines-oxydes, les dérivés de sucre tels que les alkylpolyglycosides ou les esters d'acides gras et de sucres, notamment le monopalmitate de saccharose; les oxydes de phosphine tertiaire à longue chaîne; les dialkylsulfoxydes; les copolymères séquencés de polyoxyéthylène et de polyoxypropylène; les esters de sorbitane polyalkoxylés ; les esters gras de sorbitane, les poly(oxyde d'éthylène) et amides d'acides gras modifiés de manière à leur conférer un caractère hydrophobe (par exemple, les mono- et diéthanolamides d'acides gras contenant de 10 à 18 atomes de carbone).Among the nonionic surfactants, mention may in particular be made of alkylene oxide condensates, especially of ethylene oxide and optionally of propylene with alcohols, polyols, alkylphenols, fatty acid esters, amides of fatty acids and fatty amines; amine oxides, sugar derivatives such as alkylpolyglycosides or esters of fatty acids and sugars, especially sucrose monopalmitate; long-chain tertiary phosphine oxides; dialkyl sulfoxides; block copolymers of polyoxyethylene and polyoxypropylene; polyalkoxylated sorbitan esters; fatty esters of sorbitan, poly (ethylene oxide) and amides of fatty acids modified so as to confer a hydrophobic character (for example, mono- and diethanolamides of fatty acids containing from 10 to 18 carbon atoms ).

On peut citer tout notamment

  • les acides carboxyliques aliphatiques en C8-C18 polyoxyalkylénés contenant de 2 à 50 motifs oxyalkylènes (oxyéthylène et/ou oxypropylène), en particulier ceux en C12 (moyenne) ou en C18 (moyenne)
  • les alcools aliphatiques en C6-C24 polyoxyalkylénés contenant de 2 à 50 motifs oxyalkylènes (oxyéthylène et/ou oxypropylène), en particulier ceux en C12 (moyenne) ou en C18 (moyenne); on peut mentionner les Antarox B12DF, Antarox FM33, Antarox FM63, Antarox V74 de Rhodia, Plurafac LF 400, Plurafac LF 220 de BASF, Rhodasurf ID 060, Rhodasurf ID 070, Rhodasurf LA 42 de Rhodia, Synperonic A5, A7, A9 de ICI.
We can mention everything especially
  • polyoxyalkylenated C 8 -C 18 aliphatic carboxylic acids containing from 2 to 50 oxyalkylene units (oxyethylene and / or oxypropylene), in particular those containing C 12 (average) or C 18 (average)
  • polyoxyalkylenated C 6 -C 24 aliphatic alcohols containing from 2 to 50 oxyalkylene units (oxyethylene and / or oxypropylene), in particular those containing C 12 (average) or C 18 (average); we can mention Antarox B12DF, Antarox FM33, Antarox FM63, Rhodia Antarox V74, Plurafac LF 400, Plurafac LF 220 from BASF, Rhodasurf ID 060, Rhodasurf ID 070, Rhodasurf LA 42 from Rhodia, Synperonic A5, A7, A9 from ICI .

Parmi les agents tensioactifs amphotères, on peut mentionner les alkyl iminopropionates ou iminodipropionates de sodium, comme les Mirataine H2C HA et Mirataine JC HA de Rhodia.Among the amphoteric surfactants, mention may be made of sodium alkyl iminopropionates or iminodipropionates, such as Mirataine H2C HA and Mirataine JC HA from Rhodia.

Les agents tensioactifs peuvent être présent à raison de 0,1 à 20%, de préférence de 0,2 à 10% en poids.The surfactants may be present in an amount of 0.1 to 20%, preferably 0.2 to 10% by weight.

Avantageusement, le rapport pondéral copolymère de formule générale (I) / agent tensioactif, est compris entre 1/2 et 1 /100, avantageusement 1/5 et1/50.Advantageously, the copolymer weight ratio of general formula (I) / surfactant is between 1/2 and 1/100, advantageously 1/5 and 1/50.

Dans ce qui suit, sauf indications contraires, les proportions sont indiquées en poids.In what follows, unless otherwise indicated, the proportions are given by weight.

Parmi les additifs autres usuels entrant dans la formulation des compositions détergentes pour le lavage en machine à laver la vaisselle, on peut mentionner :

  • ◆ des "builders" ou « cobuilders » (adjuvants de détergence améliorant les propriétés de surface des tensioactifs) organiques du type :
    • phosphonates organiques et aminophosphonates hydrosolubles tels que les
      • éthane 1-hydroxy-1, 1-diphosphonates,
      • aminotri(méthylène diphosphonate)
      • vinyldiphosphonates
      • sels des oligomères ou polymères de l'acide vinylphosphonique ou vinyldiphosphonique
      • sels de co-oligomères ou copolymères statistiques de l'acide vinylphosphonique ou vinyldiphosphonique et de l'acide acrylique et/ou de l'anhydride maleïque et/ou de l'acide vinylsulfonique et/ou de l'acrylamidométhylpropane sulfonique
      • sels d'acides polycarboxyliques phosphonés
      • polyacrylates à terminaison(s) phosphonate(s)
      • sels de cotélomères de l'acide vinylphosphonique ou vinyldiphosphonique et d'acide acrylique
  • comme ceux de la gamme BRIQUEST® ou MIRAPOL A300 ou 400 de RHODIA (à raison de 0 à 2% du poids total de composition détergente exprimé en matière sèche);
    • acides polycarboxyliques ou leurs sels hydrosolubles et les sels hydrosolubles de polymères ou de copolymères carboxyliques tels que
      • éthers polycarboxylates ou hydroxypolycarboxylates
      • acides polyacétiques ou leurs sels (acide nitriloacétique, acide N,N-dicarboxyméthyl-2-aminopentane dioïque, acide éthylènediamine-tétraacétique, acide diéthylènetriamine pentaacétique, éthylènediamine-tetraacétates, nitrilotriacétates, N-(2 hydroxyéthyl)-nitrilodiacétates), (à raison de 0 à 10% du poids total de composition détergente exprimé en matière sèche) ;
      • sels d'acides alkyl C5-C20 succiniques
      • esters polyacétals carboxyliques
      • sels d'acides polyaspartiques ou polyglutamiques
      • acide citrique, acide gluconique ou acide tartrique ou leurs sels (à raison de 0 à 10% du poids total de composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
        • des copolymères d'acide acrylique et d'anhydride maléïque ou des homopolymères d'acide acrylique, tels que le Rhodoline DP 226 35 de Rhodia et le Sokalan CP5 de BASF (à raison de 0 à 10%, du poids total de ladite composition détergente exprimé en matière sèche) ;
  • ◆ des "builders" (adjuvants de détergence améliorant les propriétés de surface des tensioactifs) minéraux du type :
    • polyphosphates de métaux alcalins, d'ammonium ou d'alcanolamines tels que le RHODIAPHOS HD7 commercialisé par la société RHODIA, (à raison de 0 à 70% du poids total de composition détergente exprimé en matière sèche) ;
    • pyrophosphates de métaux alcalins
    • silicates de métaux alcalins, de rapport SiO2/M2O pouvant aller de 1 à 4, de préférence de 1,5 à 3,5, tout particulièrement de 1,7 à 2,8 ; il peut s'agir de silicates amorphes ou de silicates lamellaires comme les phases α-, β-, γ- et δ- de Na2Si2O5, commercialisées sous les références NaSKS-5, NaSKS-7, NaSKS-11 et NaSKS-6 par CLARIAN ;
    • borates, carbonates, bicarbonates, sesquicarbonates alcalins ou alcalino-terreux (en quantité pouvant aller jusqu'à 50% environ du poids total de ladite composition détergente exprimé en matière sèche);
    • cogranulés de silicates hydratés de métaux alcalins de rapport SiO2M2O pouvant aller de 1,5 à 3,5, et de carbonates de métaux alcalins (sodium ou de potassium) ; on peut citer en particulier les cogranulés dans lesquels la teneur pondérale en eau associée au silicate par rapport au silicate sec est d'au moins 33/100, le rapport pondéral du silicate au carbonate pouvant aller de 5/95 à 45/55, de préférence de 15/85 à 35/65, tels que décrits dans EP-A-488 868 et EP-A-561 656 , comme le NABION 15 commercialisé par la société RHODIA ; (la quantité totale de "builders", organiques et/ou minéraux, pouvant représenter jusqu'à 90% du poids total de ladite composition détergente exprimé en matière sèche) ;
  • ◆ des agents de blanchiment du type perborates, percarbonates associés ou non à des activateurs de blanchiment acétylés comme la N, N, N', N'-tétraacétyl-éthylènediamine (TAED) ou des produits chlorés du type chloroisocyanurates, ou des produits chlorés du type hypochlorites de métaux alcalins, (à raison de 0 à 30% du poids total de ladite composition détergente exprimé en matière sèche dans le cas d'une composition pour lave-vaisselle) ;
  • ◆ des charges du type sulfate de sodium, chlorure de sodium à raison de 0 à 50% du poids total de ladite composition exprimé en matière sèche;
  • ◆ des catalyseurs de blanchiment contenant un métal de transition, les complexes de fer, manganèse et cobalt notamment, comme ceux du type [MnIV2(µ-O)3(Me3TACN)2](PF6)2, [FeII(MeN4py)(MeCN)](CIO4)2, [(CoIII)(NH3)5(OAc)](OAc)2, décrits dans US-A-4,728,455 , 5,114,606 , 5,280,117 , EP-A-909 809 , US-A-5,559,261 , WO 96/23859 , 96/23860 et 96/23861 ;
  • ◆ d'autres additifs divers comme des agents influant sur le pH de la composition détergente, notamment des additifs alcalinisants solubles dans le milieu lessiviel ou des enzymes ou des parfums, colorants, agents inhibiteurs de corrosion des métaux ;
Among the other usual additives used in the formulation of detergent compositions for washing in a dishwashing machine, mention may be made of:
  • ◆ "builders" or "cobuilders" (detergency builders improving the surface properties of surfactants) organic type:
    • organic phosphonates and water-soluble aminophosphonates such as
      • ethane 1-hydroxy-1,1-diphosphonates,
      • aminotri (methylene diphosphonate)
      • vinyldiphosphonates
      • salts of oligomers or polymers of vinylphosphonic acid or vinyldiphosphonic acid
      • random co-oligomer or copolymer salts of vinylphosphonic acid or vinyldiphosphonic acid and acrylic acid and / or maleic anhydride and / or vinylsulfonic acid and / or acrylamidomethylpropane sulfonic acid
      • salts of phosphonated polycarboxylic acids
      • Phosphonate-terminated polyacrylates
      • salts of cotellomers of vinylphosphonic acid or vinyldiphosphonic acid and acrylic acid
  • as those of the range BRIQUEST ® or MIRAPOL A300 or 400 of RHODIA (at a rate of 0 to 2% of the total weight of detergent composition expressed as dry matter);
    • polycarboxylic acids or their water-soluble salts and the water-soluble salts of carboxylic polymers or copolymers such as
      • polycarboxylate ethers or hydroxypolycarboxylates
      • polyacetic acids or their salts (nitriloacetic acid, N, N-dicarboxymethyl-2-aminopentane dioic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, ethylenediamine tetraacetates, nitrilotriacetates, N- (2 hydroxyethyl) -nitrilodiacetates), (at 0 to 10% of the total weight of detergent composition expressed as dry matter);
      • C 5 -C 20 alkyl succinic acid salts
      • polyacetal carboxylic esters
      • salts of polyaspartic or polyglutamic acids
      • citric acid, gluconic acid or tartaric acid or their salts (in a proportion of 0 to 10% of the total weight of detergent composition expressed as dry matter in the case of a dishwashing composition);
        • copolymers of acrylic acid and maleic anhydride or homopolymers of acrylic acid, such as Rhodoline DP 226 from Rhodia and Sokalan CP5 from BASF (from 0 to 10%), of the total weight of said detergent composition expressed in dry matter);
  • ◆ "builders" (detergency adjuvants improving the surface properties of surfactants), of the type:
    • polyphosphates of alkali metals, of ammonium or of alkanolamines such as RHODIAPHOS HD7 marketed by RHODIA, (at a rate of 0 to 70% of the total weight of detergent composition expressed as dry matter);
    • pyrophosphates of alkali metals
    • alkali metal silicates with an SiO 2 / M 2 O ratio of from 1 to 4, preferably from 1.5 to 3.5, most preferably from 1.7 to 2.8; they may be amorphous silicates or lamellar silicates, such as the α-, β-, γ- and δ- phases of Na 2 Si 2 O 5 , sold under the references NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6 by CLARIAN;
    • alkali or alkaline earth borates, carbonates, bicarbonates, sesquicarbonates (in an amount of up to about 50% of the total weight of said detergent composition expressed as dry matter);
    • cogranulates of alkali metal hydrated silicates of SiO 2 M 2 O ratio ranging from 1.5 to 3.5, and of alkali metal carbonates (sodium or potassium); mention may in particular be made of cogranules in which the weight content of water associated with silicate with respect to dry silicate is at least 33/100, the weight ratio of silicate to carbonate may range from 5/95 to 45/55, preferably from 15/85 to 35/65, as described in US Pat. EP-A-488,868 and EP-A-561 656 like the NABION 15 marketed by RHODIA; (the total amount of "builders", organic and / or inorganic, may represent up to 90% of the total weight of said detergent composition expressed in dry matter);
  • Perborate bleaching agents, percarbonates associated or not acetylated bleaching activators such as N, N, N ', N'-tetraacetyl-ethylenediamine (TAED) or chloroisocyanurate-type chlorinated products, or chlorinated products of the type hypochlorites of alkali metals, (in a proportion of 0 to 30% of the total weight of said detergent composition expressed as dry matter in the case of a dishwashing composition);
  • ◆ fillers of sodium sulfate type, sodium chloride in a proportion of 0 to 50% of the total weight of said composition expressed as dry matter;
  • Transition metal-containing bleach catalysts, especially iron, manganese and cobalt complexes, such as those of the type [Mn IV 2 (μ-O) 3 (Me 3 TACN) 2 ] (PF 6 ) 2 , [Fe II (MeN 4 py) (MeCN)] (CIO 4 ) 2 , [(Co III ) (NH 3 ) 5 (OAc)] (OAc) 2 , described in US Patent 4,728,455 , 5114606 , 5280117 , EP-A-909 809 , US Patent 5,559,261 , WO 96/23859 , 96/23860 and 96/23861 ;
  • Other miscellaneous additives such as agents affecting the pH of the detergent composition, especially alkalizing additives soluble in the washing medium or enzymes or perfumes, dyes, metal corrosion inhibitors;

Une composition lavante et rinçante « 3 en 1 » se différencie d'une composition lavante et rinçante « 2 en 1 » notamment par une concentration plus élevée en builders organiques et en tripolyphosphate de sodium.A washing and rinsing composition "3 in 1" differs from a washing and rinsing "2 in 1" in particular by a higher concentration of organic builders and sodium tripolyphosphate.

De manière préférentielle, une composition lavante et rinçante « 3 en 1 » comprend

  • plus de 40% de tripolyphosphate de sodium
  • plus de 1% d'au moins un phosphonate organique ou aminophosphonate hydrosoluble
  • au moins 2% de builders organiques polymères ou copolymères acryliques.
Preferably, a "3 in 1" washing and rinsing composition comprises
  • more than 40% sodium tripolyphosphate
  • more than 1% of at least one organic phosphonate or water-soluble aminophosphonate
  • at least 2% of organic polymer builders or acrylic copolymers.

La composition lavante et rinçante « deux-en-un » ou « trois-en-un », peut se présenter sous forme de liquide, de gel, de poudre compactée ou non ; d'une manière préférentielle, elle se présente sous forme de tablette monocouche ou multicouches.The "two-in-one" or "three-in-one" washing and rinsing composition may be in the form of a liquid, a gel, a compacted powder or no ; in a preferential manner, it is in the form of a monolayer or multilayer tablet.

Un mode de réalisation particulièrement intéressant consiste en l'utilisation, selon l'invention, desdits copolymères amphotères hydrosolubles ou hydrodispersables sous forme d'une préformulation solide, notamment sous forme de granulés, comprenant ledit copolymère amphotère adsorbé et/ou absorbé sur un support inorganique solide hydrosoluble.A particularly advantageous embodiment consists in the use, according to the invention, of said amphoteric water-soluble or water-dispersible copolymers in the form of a solid preformulation, in particular in the form of granules, comprising said amphoteric copolymer adsorbed and / or absorbed on an inorganic support water-soluble solid.

Un deuxième objet de l'invention, consiste, à titre de produit industriel nouveau, en une préformulation solide sèche destinée à une composition « deux en un » ou « trois en un» lavante et rinçante pour machine automatique à laver la vaisselle, ladite préformulation consistant essentiellement en une solution ou une dispersion dudit copolymère amphotère adsorbé et/ou absorbé sur un support solide particulaire en au moins un matériau inorganique hydrosoluble.A second subject of the invention consists, as a new industrial product, in a dry solid preformulation intended for a "two-in-one" or "three-in-one" washing and rinsing composition for an automatic dishwashing machine, said preformulation consisting essentially of a solution or dispersion of said amphoteric copolymer adsorbed and / or absorbed on a particulate solid support into at least one water-soluble inorganic material.

Parmi les supports inorganiques hydrosolubles, on peut mentionner les sulfates, tripolyphosphates, carbonates, bicarbonates, sesquicarbonates de métaux alcalins, de sodium de préférence.
D'une manière toute préférentielle, ledit support est du tripolyphosphate de sodium, de préférence sous forme anhydride obtenu par atomisation.Among the water-soluble inorganic carriers, there may be mentioned sulphates, tripolyphosphates, carbonates, bicarbonates, sesquicarbonates of alkali metals, preferably sodium.
In a very preferential manner, said support is sodium tripolyphosphate, preferably in anhydride form obtained by atomization.

Le rapport pondéral, exprimé en sec, copolymère amphotère/support inorganique est de 5/95 à 50/50, de préférence de 10/90 à 30/70.The weight ratio, expressed as dry, amphoteric copolymer / inorganic support is from 5/95 to 50/50, preferably from 10/90 to 30/70.

D'une manière préférentielle, ladite préformulation se présente sous la forme de cogranulés présentant un diamètre médian de 250 à 1000 µm (mesure par granulométrie tamis).In a preferential manner, said preformulation is in the form of cogranules having a median diameter of 250 to 1000 μm (measurement by sieve size).

Ladite préformulation peut être obtenue par granulation du matériau support sous forme particulaire à l'aide d'une solution ou d'une dispersion aqueuse de copolymère amphotère, ladite solution ou dispersion présentant un extrait sec de 10 à 40%, de préférence de 15 à 35%.
Le matériau support sous forme particulaire peut présenter un diamètre médian de 150 à 700 µm.
L'opération de granulation peut être réalisée d'une manière connue à l'aide d'un appareil de granulation tel que tambour, assiette, lit fluidisé ...
Si nécessaire les cogranulés obtenus sont séchés, en lit fluidisé notamment, pour améliorer leur coulabilité.Said preformulation may be obtained by granulation of the support material in particulate form with the aid of an aqueous solution or dispersion of amphoteric copolymer, said solution or dispersion having a solids content of 10 to 40%, preferably from 15 to 35%.
The support material in particulate form may have a median diameter of 150 to 700 μm.
The granulation operation can be carried out in a known manner using a granulation apparatus such as drum, plate, fluidized bed, etc.
If necessary the cogranules obtained are dried, in fluidized bed in particular, to improve their flowability.

Ladite préformulation peut en outre contenir des constituants autres, notamment des agents tensio-actifs non-ioniques et les cobuilders organiques déjà mentionnés ci-dessus.Said preformulation may further contain other components, including nonionic surfactants and organic cobuilders already mentioned above.

Un troisième objet de l'invention consiste en un procédé pour améliorer les propriétés anti-redéposition des salissures d'une composition lavante et rinçante « deux en un » ou « trois en un » pour le nettoyage de la vaisselle en machine, par addition à ladite composition d'une quantité efficace d'au moins un copolymère amphotère hydrosoluble ou hydrodispersable décrit ci-dessus ou d'une préformulation telle que décrite ci-dessus.
Les quantités de copolymère amphotère, ainsi que la nature et les quantités des autres additifs éventuellement présents ont déjà été mentionnés ci-dessus.A third object of the invention consists in a method for improving the anti-redeposition properties of soils of a "two-in-one" or "three-in-one" washing and rinsing composition for machine dishwashing, by addition to said composition of an effective amount of at least one water-soluble or water-dispersible amphoteric copolymer described above or a preformulation as described above.
The amounts of amphoteric copolymer, as well as the nature and amounts of the other additives possibly present have already been mentioned above.

Un autre objet de l'invention, consiste, à titre de produit industriel nouveau, en une formulation lavante et rinçante « 2 en 1 » ou « 3 en 1 » pour le lavage de la vaisselle en machine à laver la vaisselle, particulièrement performante, comprenant :

  • au moins 20%, de préférence de 25 à 60% en poids de tripolyphosphate de sodium,
  • un silicate de sodium de rapport molaire SiO2Na2O allant de 1 à 4, de préférence de 1,5 à 3,5, tout particulièrement de 1,7 à 2,8, en quantité inférieure à 10%, tout particulièrement inférieure à 5%, plus particulièrement en quantité allant de 1 à moins de 5% en poids
  • de 0,02 à 0,5% en poids de copolymère amphotère ci-dessus décrit
  • de 0,1 à 20%, de préférence de 0,2 à 10%, tout particulièrement de 0,2 à 5% en poids d'agent tensioactif non-ionique.
Les pourcentages mentionnés ci-dessus sont exprimés en terme de matière sèche.Another object of the invention is, as a new industrial product, a washing and rinsing formulation "2 in 1" or "3 in 1" for washing dishes in dishwashing machine, particularly powerful, comprising:
  • at least 20%, preferably 25 to 60% by weight of sodium tripolyphosphate,
  • a sodium silicate having an SiO 2 Na 2 O molar ratio ranging from 1 to 4, preferably from 1.5 to 3.5, very particularly from 1.7 to 2.8, in an amount of less than 10%, and especially lower at 5%, more particularly in an amount ranging from 1 to less than 5% by weight
  • from 0.02 to 0.5% by weight of amphoteric copolymer described above
  • from 0.1 to 20%, preferably from 0.2 to 10%, most preferably from 0.2 to 5% by weight of nonionic surfactant.
The percentages mentioned above are expressed in terms of dry matter.

D'une manière préférentielle, le silicate de sodium est un cogranulé de silicate de sodium hydraté de rapport SiO2/Na2O pouvant aller de 1,5 à 3,5, et de carbonate de sodium, le rapport pondéral du silicate au carbonate pouvant aller de 5/95 à 45/55, de préférence de 15/85 à 35/65, comme le NABION 15 commercialisé par Rhodia.Preferably, the sodium silicate is a cogranulate of sodium silicate hydrated SiO 2 / Na 2 O ratio ranging from 1.5 to 3.5, and sodium carbonate, the weight ratio of silicate to carbonate ranging from 5/95 to 45/55, preferably from 15/85 to 35/65, such as NABION 15 marketed by Rhodia.

Ladite formulation « 2 en 1 »ou « 3 en 1 » peut en outre comprendre des additifs usuels présents dans les compositions pour lave-vaissellle, tels que ceux décrits plus haut et selon des quantités déjà mentionnées ci-dessus.Said "2 in 1" or "3 in 1" formulation may further comprise usual additives present in the dishwashing compositions, such as those described above and in amounts already mentioned above.

Les exemples suivants sont donnés à titre illustratif.The following examples are given for illustrative purposes.

Les abréviations données ont la signification suivante :

  • * AA : acide acrylique
  • * DADMAC : chlorure de dimethyldiallylammonium CH2=CH-CH2-N+(Me)2-CH2-CH=CH2 Cl-
  • * MAPTAC : chlorure de (methacrylamidopropyl)trimethylammonium CH2=C(CH3)-C(O)-NH-(CH2)3-N+(Me)3 Cl-
  • * DiQUAT : monomère cationique deformule CH2=C(CH3)-C(O)-NH-(CH2)3-N+(Me)2-CH2-CH(OH)-CH2- N+(Me)3 Cl-
  • * STPP : tripolyphosphate de sodium
The abbreviations given have the following meaning:
  • * AA: acrylic acid
  • * DADMAC: dimethyldiallylammonium chloride CH 2 = CH-CH 2 -N + (Me) 2 -CH 2 -CH = CH 2 Cl -
  • * MAPTAC: (methacrylamidopropyl) trimethylammonium chloride CH 2 = C (CH 3 ) -C (O) -NH- (CH 2 ) 3 -N + (Me) 3 Cl -
  • * DiQUAT: cationic monomer of the formula CH 2 = C (CH 3 ) -C (O) -NH- (CH 2 ) 3 -N + (Me) 2 -CH 2 -CH (OH) -CH 2 -N + (Me) 3 Cl -
  • * STPP: sodium tripolyphosphate

Protocole du test d'anti-redéposition des salissuresProtocol of the soil anti-redeposition test

La formulation lavante et rinçante est mise en oeuvre dans la machine à laver la vaisselle, par introduction dans le compartiment de la machine prévu à cet effet. 20 g de poudre lavante classique contenant 0,1% ou 0,2% de polymère à tester sont ainsi mises en oeuvre.The washing and rinsing formulation is implemented in the dishwashing machine, by introduction into the compartment of the machine provided for this purpose. 20 g of conventional washing powder containing 0.1% or 0.2% of polymer to be tested are thus used.

Le test est réalisé sur 10 verres à soda disposés régulièrement dans la machine.The test is performed on 10 soda glasses regularly placed in the machine.

On introduit dans le lave-vaisselle 40 g de « salissure ».40 g of "dirt" are introduced into the dishwasher.

La salissure utilisée est un mélange de sauce salade (50%), de Ketchup (5%), de mayonnaise (10%), de lait (25%) et de crème fraîche (10%).The dirt used is a mixture of salad dressing (50%), Ketchup (5%), mayonnaise (10%), milk (25%) and cream (10%).

Trois cycles successifs à 65°C sont réalisés dans les mêmes conditions.Three successive cycles at 65 ° C. are carried out under the same conditions.

Une fois secs, les verres sont évalués (critères de transparence, brillance et absence de traces) par un panel de 15 personnes formées, qui donnent des notes entre -10 et +10 selon le barème suivant :

  • -10 : dépôt de salissures, voile blanc ou traces de salissure beaucoup plus visibles que sur le témoin
  • -5 : dépôt de salissures, voile blanc ou traces de salissures plus visibles que sur le témoin
  • 0 : poudre classique sans polymère (témoin) : voile blanc et traces de salissures bien visibles
  • +3 : 12 à 24 traces de salissures, voile blanc
  • +5 : 4 à 12 traces de salissures, léger voile blanc
  • +7 : moins de 4 traces de salissures, très léger voile blanc
  • +10 : verre propre, sans traces de salissures ni voile blanc
Once dry, the glasses are evaluated (criteria of transparency, brightness and absence of traces) by a panel of 15 people trained, who give notes between -10 and +10 according to the following scale:
  • -10: dirt deposit, white veil or soil marks much more visible than on the witness
  • -5: deposit of dirt, white veil or traces of soiling more visible than on the witness
  • 0: conventional powder without polymer (control): white veil and visible traces of soiling
  • +3: 12 to 24 traces of soiling, white veil
  • +5: 4 to 12 traces of soiling, light white veil
  • +7: less than 4 traces of soiling, very light white veil
  • +10: clean glass, without stains or white veil

Polymères testés : Polymers tested :

  • AA/DADMAC avec une répartition molaire de 85/15AA / DADMAC with a molar distribution of 85/15
  • AA/DADMAC avec une répartition molaire de 70/30AA / DADMAC with a molar distribution of 70/30
  • AA/DADMAC avec une répartition molaire de 60/40AA / DADMAC with a molar distribution of 60/40
  • AA/DADMAC avec une répartition molaire de 50/50AA / DADMAC with a molar distribution of 50/50
  • AA/DIQUAT avec une répartition molaire de 60/40AA / DIQUAT with a molar distribution of 60/40
  • AA/MAPTAC avec une répartition molaire de 60/40AA / MAPTAC with a molar distribution of 60/40
Exemple 1 : Formule Poudre ou tablette « 3 en 1 » Example 1 : Powder or tablet formula "3 in 1"

Le test est réalisé en eau dure (40°TH), sans sels de rinçage ni sel régénérant.The test is performed in hard water (40 ° TH), without rinsing salts or regenerating salt.

La formulation testée est la suivante : NABION 15 (builder, co-granulé Carbonate/silicate de Sodium) 25% Rhodiaphos HD7 (STPP) 52% Antarox B12 DF (tensioactif non-ionique, démoussant) 0,9% Antarox B79R (tensioactif non-ionique) 0,9% Briquest 543-25S (phosphonates) 1,1% Perborate Monohydraté (agent de blanchiment) 8% TAED (catalyseur de l'agent de blanchiment) 2% Rhodoline DP 226 35 (builder polymère) 2% Amylase (enzyme) 1,3% Protease(enzyme) 0,7% Polymère à tester 0,2% Na2SO4 5,9% The tested formulation is as follows: NABION 15 (builder, co-granulated Carbonate / Sodium silicate) 25% Rhodiaphos HD7 (STPP) 52% Antarox B12 DF (non-ionic surfactant, defoamer) 0.9% Antarox B79R (nonionic surfactant) 0.9% Briquest 543-25S (phosphonates) 1.1% Perborate Monohydrate (bleaching agent) 8% TAED (bleach catalyst) 2% Rhodoline DP 226 35 (polymer builder) 2% Amylase (enzyme) 1.3% Protease (enzyme) 0.7% Polymer to test 0.2% Na 2 SO 4 5.9%

La formulation est sous forme de poudre ou bien sous forme de tablette de 44 mm de diamètre et 1 cm d'épaisseur, obtenue par compactage de 20 g de poudre sous une pression de 2 Mpa.The formulation is in powder form or in the form of a tablet of 44 mm in diameter and 1 cm in thickness, obtained by compacting 20 g of powder under a pressure of 2 MPa.

Les résultats sont les suivants : AA/DADMAC
85/15 AA/DADMAC
60/40 AA/DADMAC
50/50 AA/DIQUAT
60/40 AA/MAPTAC
60/40 Témoin sans polymère +6 +9 +4 +2 +2 0 The results are as follows: AA / DADMAC
85/15 AA / DADMAC
60/40 AA / DADMAC
50/50 AA / DIQUAT
60/40 AA / MAPTAC
60/40 Control without polymer 6 9 4 2 2 0

On constate un réel bénéfice antiredéposition des salissures et rinçage apportés par la présence de 0,2% de copolymères AA/DADMAC avec une répartition molaire de 85/15 et 60/40, par rapport au témoin, ainsi que par rapport aux copolymères AA/DIQUAT avec une répartition molaire de 60/40 et 50/50 ou AA/MAPTAC avec une répartition molaire de 60/40.A real anti-redeposition benefit of the stains and rinses brought about by the presence of 0.2% of AA / DADMAC copolymers with a molar distribution of 85/15 and 60/40, compared with the control, as well as with respect to AA / DIQUAT copolymers with a molar distribution of 60/40 and 50/50 or AA / MAPTAC with a molar distribution of 60/40.

Exemple 2 : Formule Poudre ou tablette « 2 en 1 » : Example 2 : Powder or tablet "2 in 1" formula:

Le test est réalisé en eau douce (< 5°TH), sans sel de rinçage.The test is performed in fresh water (<5 ° TH), without rinsing salt.

La formulation testée est la suivante : NABION 15 (builder, co-granulé Carbonate/silicate de Sodium) 34% Rhodiaphos HD7 (STPP) 30% Antarox B12 DF (tensioactif non-ionique, démoussant) 0,8% Antarox B79R (tensioactif non-ionique) 0,8% Briquest 543-45AS (phosphonates) 0,8% Perborate Monohydraté (agent de blanchiment) 8% TAED (catalyseur de l'agent de blanchiment) 2% Rhodoline DP 226 35 (builder polymère) 1,5% Amylase (enzyme) 1,3% Protease(enzyme) 0,7% Na2SO4 20% Polymère à tester 0,1% La formulation est sous forme de poudre ou bien sous forme de tablette de 44 mm de diamètre et 1 cm d'épaisseur, obtenue par compactage de 20 g de poudre sous une pression de 4 Mpa.The tested formulation is as follows: NABION 15 (builder, co-granulated Carbonate / Sodium silicate) 34% Rhodiaphos HD7 (STPP) 30% Antarox B12 DF (non-ionic surfactant, defoamer) 0.8% Antarox B79R (nonionic surfactant) 0.8% Briquest 543-45AS (phosphonates) 0.8% Perborate Monohydrate (bleaching agent) 8% TAED (bleach catalyst) 2% Rhodoline DP 226 35 (polymer builder) 1.5% Amylase (enzyme) 1.3% Protease (enzyme) 0.7% Na 2 SO 4 20% Polymer to test 0.1% The formulation is in powder form or in the form of a tablet of 44 mm in diameter and 1 cm in thickness, obtained by compacting 20 g of powder under a pressure of 4 MPa.

Les résultats sont les suivants : AA/DADMAC
85/15 AA/DADMAC
60/40 AA/DADMAC
50/50 AA/DIQUAT
60/40 AA/MAPTAC
60/40 Témoin sans polymère +5 +7 +3 +1 +1 0 The results are as follows: AA / DADMAC
85/15 AA / DADMAC
60/40 AA / DADMAC
50/50 AA / DIQUAT
60/40 AA / MAPTAC
60/40 Control without polymer 5 +7 3 +1 +1 0

On constate à nouveau un réel bénéfice antiredéposition des salissures et rinçage apportés par la présence de 0,1% de copolymères AA/DADMAC avec une répartition molaire de 85/15 et 60/40 par rapport au témoin, ainsi que par rapport aux copolymères AA/DIQUAT avec une répartition molaire de 60/40 et 50/50 ou AA/MAPTAC avec une répartition molaire de 60/40There is again a real antiredeposition benefit of soiling and rinsing provided by the presence of 0.1% of copolymers AA / DADMAC with a molar distribution of 85/15 and 60/40 relative to the control, as well as compared to AA copolymers / DIQUAT with a molar distribution of 60/40 and 50/50 or AA / MAPTAC with a molar distribution of 60/40

Exemple 3 : Formulation « 3 en 1 » Example 3 : "3 in 1" formulation

On réalise l'opération décrite à l'exemple 1 par mise en oeuvre des formulations données dans le tableau suivant : Formulation Tensioactif Non ionique 0,9% 0,9% STPP anhydre 50% 50% Perborate de sodium Monohydrate 8% 8% Disilicate de sodium 14% * 3,48% ** Carbonate de sodium 6,6% 6,6% ** Sokalan CP5 (builder polymère) 2% 2% Phosphonate 1% 1 % TAED 2% 2% Enzymes (protéase + amylase) 2% 2% Polymère AA/DADMAC 60/40 0,1 % 0,1 % Sulfate de Sodium qsp 100 qsp 100 Résultat du test +5 +9 * apporté par du disilicate de sodium atomisé (80%)
** apportés par 12% de Nabion 15 The operation described in Example 1 is carried out using the formulations given in the following table: Formulation Nonionic surfactant 0.9% 0.9% Anhydrous STPP 50% 50% Sodium perborate monohydrate 8% 8% Sodium disilicate 14% * 3.48% ** Sodium carbonate 6.6% 6.6% ** Sokalan CP5 (polymer builder) 2% 2% phosphonate 1% 1% DAT 2% 2% Enzymes (protease + amylase) 2% 2% AA / DADMAC 60/40 Polymer 0.1% 0.1% Sodium sulphate qs 100 qs 100 Test result 5 9 * supplied by atomized sodium disilicate (80%)
** contributed by 12% of Nabion 15

On constate que le bénéfice antiredéposition des salissures et rinçage est d'autant meilleur que la teneur en disilicate est faible.It is found that the antiredeposition benefit of soiling and rinsing is even better than the disilicate content is low.

Exemple 4 : Formulation « 3 en 1 » Example 4 : "3 in 1" formulation

On réalise l'opération décrite à l'exemple 1 par mise en oeuvre des formulations données dans le tableau suivant : Formulation Tensioactif Non ionique 1,8% 1,8% 1,8% 1,8% STPP anhydre 52% 52% 52% 52% Perborate de sodium Monohydrate 8% 8% 8% 8% Disilicate de sodium 3,48%** 7%* 12%* 18%* Carbonate de sodium 6,6%** 6,6% 6,6% 6,6% Briquest 543-25S (phosphonates) 1,1% 1,1% 1,1% 1,1% Rhodoline DP 226 35 (builder polymère) 2% 2% 2% 2% TAED 2% 2% 2% 2% Enzymes (protéase + amylase) 2% 2% 2% 2% Polymère AA/DADMAC 70/30 0,1% 0,1% 0,1% 0,1% Sulfate de Sodium qsp 100 qsp 100 qsp 100 qsp 100 Résultat du test +9 +8 +5 +3 * apporté par du disilicate de sodium atomisé (80%)
** apportés par 12% de Nabion 15 The operation described in Example 1 is carried out using the formulations given in the following table: Formulation Nonionic surfactant 1.8% 1.8% 1.8% 1.8% Anhydrous STPP 52% 52% 52% 52% Sodium perborate monohydrate 8% 8% 8% 8% Sodium disilicate 3.48% ** 7% * 12% * 18% * Sodium carbonate 6.6% ** 6.6% 6.6% 6.6% Briquest 543-25S (phosphonates) 1.1% 1.1% 1.1% 1.1% Rhodoline DP 226 35 (polymer builder) 2% 2% 2% 2% DAT 2% 2% 2% 2% Enzymes (protease + amylase) 2% 2% 2% 2% Polymer AA / DADMAC 70/30 0.1% 0.1% 0.1% 0.1% Sodium sulphate qs 100 qs 100 qs 100 qs 100 Test result 9 8 5 3 * supplied by atomized sodium disilicate (80%)
** contributed by 12% of Nabion 15

On constate que le bénéfice antiredéposition des salissures et rinçage est d'autant meilleur que la teneur en disilicate est faible.It is found that the antiredeposition benefit of soiling and rinsing is even better than the disilicate content is low.

Claims (18)

  1. Use in a two-in-one or three-in-one washing and rinsing composition for the machine cleaning of kitchen- and tableware of a water-soluble or water-dispersible amphoteric copolymer comprising in the form of polymerized units
    (a) at least one monomeric compound of general formula I
    Figure imgb0005
     in which
    - R1 and R4 represent independently of one another a hydrogen atom or a linear or branched C1-C6 alkyl group;
    - R2 and R3 represent independently of one another an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl group is a linear or branched C1-C6 chain, preferably a methyl group;
    - n and m are integers of between 1 and 3;
    - X represents a counterion compatible with the water-soluble or water-dispersible nature of the polymer;
    (b) at least one hydrophilic monomer which carries an acidic function, is copolymerizable with (a) and is capable of undergoing ionization in the application medium,
    (c) where appropriate, at least one ethylenically unsaturated hydrophilic monomeric compound of neutral charge which carries one or more hydrophilic groups and is copolymerizable with (a) and (b),
    wherein the a/b molar ratio is between 15/85 and less than 50/50, preferably between 25/75 and 45/55,
    as a soil repellent agent.
  2. Use according to claim 1, characterized in that
    R1 represents hydrogen,
    R2 represents methyl,
    R3 represents methyl,
    R4 represents hydrogen, and
    m and n are equal to 1.
  3. Use according to claim 1 or 2, characterized in that the ion X- is selected from halide, preferably chloride, sulphate, hydrogen sulphate, phosphate, citrate, formate and acetate ions.
  4. Use according to any one of claims 1 to 3, characterized in that the monomer (a) is DADMAC of the following structure:
    Figure imgb0006
     where X- represents Cl-.
  5. Use according to any one of claims 1 to 4, characterized in that the monomer (b) is selected from water-soluble monoethylenically unsaturated C3-C8 carboxylic, sulphonic, sulphuric, phosphonic or phosphoric acids, their anhydrides and their water-soluble salts.
  6. Use according to any one of claims 1 to 5, characterized in that the optional monomer (c) is selected from acrylamide, vinyl alcohol, the C1-C4 alkyl esters of acrylic acid and methacrylic acid, the C1-C4 hydroxyalkyl esters of acrylic acid and methacrylic acid, the polyalkoxylated esters of acrylic acid and methacrylic acid.
  7. Use according to any one of claims 1 to 6, characterized in that the said water-soluble or water-dispersible amphoteric copolymer is selected from
    - DADMAC/acrylic acid copolymers;
    - DADMAC/maleic acid copolymers;
    - DADMAC/itaconic acid copolymers;
    the DADMAC/acid monomer molar ratio being between 15/85 and less than 50/50, preferably between 25/75 and 45/55.
  8. Use according to any one of claims 1 to 7, characterized in that the amount of the said water-soluble or water-dispersible amphoteric copolymer in the two-in-one or three-in-one washing and rinsing composition is between 0.01% and 10%, preferably between 0.02% and 0.5%, by weight relative to the total weight of the composition.
  9. Use according to any one of claims 1 to 8, characterized in that the washing and rinsing composition further comprises at least one surfactant.
  10. Use according to claim 9, characterized in that the said surfactant is nonionic.
  11. Use according to any one of claims 1 to 10, characterized in that the said water-soluble or water-dispersible amphoteric copolymer is in the form of a solid preformulation product, preferably in the form of granules, comprising the said amphoteric copolymer adsorbed and/or absorbed on a water-soluble solid inorganic support.
  12. Use according to claim 11, characterized in that the said inorganic support is a sodium tripolyphosphate.
  13. Use according to claim 11 or 12, characterized in that the amphoteric copolymer/ inorganic support weight ratio, expressed in terms of dry matter, is from 5/95 to 50/50, preferably from 10/90 to 30/70.
  14. Use according to any one of Claims 1 to 13, characterized in that the washing and rinsing composition is in liquid, gel, loose or compacted powder form, preferentially in the form of a single-layer or multilayer tablet.
  15. Method of enhancing the soil antiredeposition properties of a two-in-one or three-in-one washing and rinsing composition for the machine cleaning of kitchen- and tableware by adding to the said composition an effective amount of at least one water-soluble or water-dispersible amphoteric copolymer whose use is claimed in any one of claims 1 to 7, if need be in the form of a preformulation product as decribed in any one of claims 11 to 13.
  16. Method according to claim 15, characterized in that the amount of the said water-soluble or water-dispersible amphoteric copolymer in the two-in-one or three-in-one washing and rinsing composition is between 0.01% and 10%, preferably between 0.02% and 0.5%, by weight relative to the total weight of the composition.
  17. 2-in-1 or 3-in-1 washing and rinsing formulation for machine dishwashing, comprising:
    - at least 20%, preferably from 25 to 60%, by weight of sodium tripolyphosphate,
    - a sodium silicate with an SiO2/Na2O molar ratio ranging from 1 to 4, preferably from 1.5 to 3.5, very particularly from 1.7 to 2.8, in an amount less than 10%, very particularly less than 5%, more particularly in an amount ranging from 1 to less than 5% by weight,
    - from 0.02 to 0.5% by weight of amphoteric copolymer whose use is claimed in any one of claims 1 to 7,
    - from 0.1 to 20%, preferably from 0.2 to 10%, very particularly from 0.2 to 5%, by weight of nonionic surfactant.
  18. Formulation according to claim 17, characterized in that the sodium silicate is in the form of cogranules of hydrated sodium silicate with an SiO2/Na2O ratio ranging from 1.5 to 3.5 and sodium carbonate, the weight ratio of silicate to carbonate ranging from 5/95 to 45/55, preferably from 15/85 to 35/65.
EP03755203A 2002-05-27 2003-05-26 Use of an amphoteric copolymer in a dish washing composition Expired - Lifetime EP1507844B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0206434A FR2839977B1 (en) 2002-05-27 2002-05-27 USE IN A WASHING AND RINSING COMPOSITION OF THE MACHINE DISHWASHER OF AN AMPHOTERIC COPOLYMER AS AGENT ANTI-REDEPOSITION OF SOIL
FR0206434 2002-05-27
PCT/FR2003/001582 WO2003099980A1 (en) 2002-05-27 2003-05-26 Use of an amphoteric copolymer in a dish washing composition

Publications (2)

Publication Number Publication Date
EP1507844A1 EP1507844A1 (en) 2005-02-23
EP1507844B1 true EP1507844B1 (en) 2011-05-11

Family

ID=29415106

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03755203A Expired - Lifetime EP1507844B1 (en) 2002-05-27 2003-05-26 Use of an amphoteric copolymer in a dish washing composition

Country Status (10)

Country Link
US (3) US20040005990A1 (en)
EP (1) EP1507844B1 (en)
JP (1) JP4672364B2 (en)
CN (2) CN1656204B (en)
AT (1) ATE509089T1 (en)
AU (1) AU2003255604A1 (en)
BR (1) BR0304924B1 (en)
ES (1) ES2362181T3 (en)
FR (1) FR2839977B1 (en)
WO (1) WO2003099980A1 (en)

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003299230A1 (en) * 2002-12-23 2004-07-14 Ciba Specialty Chemicals Holding Inc. Hydrophobically modified polymers as laundry additives
DE10342632A1 (en) 2003-09-15 2005-04-07 Henkel Kgaa Machine dishwashing detergents with special polymers
DE10342631B4 (en) 2003-09-15 2006-04-13 Henkel Kgaa Machine dishwashing detergent with special polymer mixture
FR2863880A1 (en) * 2003-12-23 2005-06-24 Rhodia Chimie Sa Cosmetic composition especially useful as a shampoo or shower gel comprises water, anionic surfactant and ampholytic copolymer
DE102004015401A1 (en) * 2004-03-26 2005-10-20 Henkel Kgaa Machine dishwashing detergent
US20060118141A1 (en) * 2004-12-08 2006-06-08 The Procter & Gamble Company Method of cleaning a washing machine or a dishwasher
US20090301519A1 (en) * 2005-07-25 2009-12-10 Rhodia Chimie Removal of dirt/make-up form unclean surfaces
JP4907199B2 (en) * 2005-09-30 2012-03-28 花王株式会社 Method for producing powder detergent composition for dishwasher
JP4841919B2 (en) * 2005-09-30 2011-12-21 花王株式会社 Detergent composition for dishwasher
JP4633657B2 (en) * 2005-09-30 2011-02-16 花王株式会社 Detergent composition for automatic dishwasher
JP5031309B2 (en) * 2005-09-30 2012-09-19 花王株式会社 Detergent composition for dishwasher
JP4767658B2 (en) * 2005-11-08 2011-09-07 花王株式会社 Powder cleaning composition for dishwasher
US7310953B2 (en) * 2005-11-09 2007-12-25 Emerson Climate Technologies, Inc. Refrigeration system including thermoelectric module
DE102005060431A1 (en) * 2005-12-15 2007-06-21 Henkel Kgaa Automatic dishwasher detergent contains positively-charged polymer and nonionic surfactant of polyalkylene oxide monoether type for clear rinse aid or detergent with integrated clear rinse function
CN100368452C (en) * 2006-01-25 2008-02-13 四川师范大学 A kind of water-soluble organic amphoteric polymer flocculant and its preparation method
JP4907327B2 (en) * 2006-02-07 2012-03-28 花王株式会社 Detergent composition for dishwasher
FR2898067B1 (en) * 2006-03-03 2008-05-30 Rhodia Recherches & Tech MODIFICATION OF SOLID SURFACES BY POLYMER ASSOCIATIONS
JP4841976B2 (en) * 2006-03-10 2011-12-21 花王株式会社 Detergent composition for dishwasher
JP5000197B2 (en) * 2006-05-29 2012-08-15 花王株式会社 Detergent composition for automatic dishwasher
JP4912859B2 (en) * 2006-12-25 2012-04-11 花王株式会社 Dishwasher finish composition
JP4842119B2 (en) * 2006-12-28 2011-12-21 花王株式会社 Manufacturing method of powder detergent
DE102007019457A1 (en) * 2007-04-25 2008-10-30 Basf Se Machine dishwashing detergent with excellent rinse performance
JP5349783B2 (en) * 2007-10-05 2013-11-20 花王株式会社 Liquid detergent composition
BRPI0913980A2 (en) * 2008-06-30 2015-10-27 Basf Se hard surface cleaning composition, cloudiness preventive film, and method for cleaning a hard surface
US10138587B2 (en) 2008-07-01 2018-11-27 Whirlpool Corporation Household cleaning appliance with a dispensing system operable between a single use dispensing system and a bulk dispensing system
US8196441B2 (en) 2008-07-01 2012-06-12 Whirlpool Corporation Household cleaning appliance with a dispensing system operable between a single use dispensing system and a bulk dispensing system
US8397544B2 (en) 2008-07-01 2013-03-19 Whirlpool Corporation Household cleaning appliance with a single water flow path for both non-bulk and bulk dispensing
US8286288B2 (en) 2008-07-01 2012-10-16 Whirlpool Corporation Method of indicating operational information for a bulk dispensing system
US20100000264A1 (en) 2008-07-01 2010-01-07 Whirlpool Corporation Method for converting a household cleaning appliance with a non-bulk dispensing system to a household cleaning appliance with a bulk dispensing system
FR2935390B1 (en) * 2008-08-26 2012-07-06 Rhodia Operations COPOLYMER FOR TREATING OR MODIFYING SURFACES
US8852353B2 (en) * 2008-12-10 2014-10-07 Michael Oberlander Solid dishmachine detergent not requiring a separate rinse additive
CA2755982A1 (en) * 2009-03-20 2010-09-23 Ciba Corporation Fast drying ampholytic polymers for cleaning compositions
JP5631797B2 (en) * 2011-03-31 2014-11-26 花王株式会社 Detergent composition for automatic dishwasher
DE102011079260A1 (en) * 2011-07-15 2013-01-17 Henkel Ag & Co. Kgaa Rinse aid and cleaning agent
MX2014001098A (en) * 2011-07-27 2014-09-12 Procter & Gamble Multiphase liquid detergent composition.
US9581311B2 (en) * 2012-03-12 2017-02-28 L-3 Communications Corporation Backlight display using photoluminescent material tuned to improve NVIS compatibility
US9068717B2 (en) * 2012-03-12 2015-06-30 L-3 Communications Corporation Backlight display using photoluminescent material tuned to improve NVIS compatibility
WO2016014802A1 (en) 2014-07-23 2016-01-28 The Procter & Gamble Company Fabric and home care treatment compositions
WO2016014742A1 (en) * 2014-07-23 2016-01-28 The Procter & Gamble Company Fabric and home care treatment compositions
EP3172300B1 (en) 2014-07-23 2018-12-26 The Procter and Gamble Company Fabric and home care treatment composition
JP7036508B2 (en) * 2016-03-18 2022-03-15 スリーエム イノベイティブ プロパティズ カンパニー Zwitterionic Polymer-Containing Compositions, Methods, and Articles for Coating Metal Surfaces
JP7091454B2 (en) 2017-11-14 2022-06-27 エコラボ ユーエスエー インコーポレイティド Solid Controlled Release Caustic Detergent Composition
CA3151823A1 (en) 2019-09-27 2021-04-01 Ecolab Usa Inc. Concentrated 2 in 1 dishmachine detergent and rinse aid
US20230106979A1 (en) * 2020-02-28 2023-04-06 Conopco Inc., D/B/A Unilever Dishwash detergent product

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3614336A1 (en) * 1986-04-28 1987-10-29 Henkel Kgaa LIQUID, AQUEOUS CLEANER FOR HARD SURFACES
CA2072319C (en) * 1991-06-28 2005-11-22 Shih-Ruey T. Chen Ampholyte terpolymers providing superior conditioning properties in skin and nail care products
EP0584709B1 (en) * 1992-08-22 1998-10-21 Clariant GmbH Use of water soluble copolymers based on acrylamidoalkylenesulfonic acids as detergent additives
US5686024A (en) * 1995-12-18 1997-11-11 Rhone-Poulenc Surfactants & Specialties, L.P. Aqueous dispersion of a surface active polymer having enhanced performance properties
US6013617A (en) * 1996-01-19 2000-01-11 Rhone-Poulenc Chimie Q2 /Q3 alkali metal silicate/inorganic compound detergent builders
EP0927237B1 (en) * 1996-09-11 2003-11-12 The Procter & Gamble Company Low foaming automatic dishwashing compositions
CA2296719A1 (en) * 1997-07-23 1999-02-04 Joseph Oreste Carnali Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
US5981456A (en) * 1997-07-23 1999-11-09 Lever Brothers Company Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
DE19914353A1 (en) * 1999-03-31 2000-10-05 Henkel Kgaa Detergent formed bodies, which exhibit good hardness and good disintegration properties, include cationic nitrile compounds as bleach activators
FR2796390B1 (en) * 1999-07-15 2001-10-26 Rhodia Chimie Sa USING AN AMPHOTERIC POLYMER TO TREAT A HARD SURFACE
US6924260B2 (en) * 1999-07-15 2005-08-02 Rhodia Chimie Method of reducing and preventing soil redeposition in an automatic dishwashing machine
ATE339493T1 (en) * 2000-05-11 2006-10-15 Unilever Nv MACHINE DISHWASHING DETERGENT COMPOSITIONS CONTAINING BLEACH AND POLYMERS
JP3422978B2 (en) * 2000-08-23 2003-07-07 花王株式会社 Cleaning composition for hard surfaces

Also Published As

Publication number Publication date
JP4672364B2 (en) 2011-04-20
WO2003099980A1 (en) 2003-12-04
US20040005990A1 (en) 2004-01-08
BR0304924A (en) 2004-09-28
CN1656204A (en) 2005-08-17
ATE509089T1 (en) 2011-05-15
CN102936540A (en) 2013-02-20
BR0304924B1 (en) 2014-09-02
CN1656204B (en) 2012-11-07
JP2005527686A (en) 2005-09-15
US20060270579A1 (en) 2006-11-30
AU2003255604A1 (en) 2003-12-12
FR2839977A1 (en) 2003-11-28
EP1507844A1 (en) 2005-02-23
US20070213251A1 (en) 2007-09-13
ES2362181T3 (en) 2011-06-29
FR2839977B1 (en) 2005-08-12

Similar Documents

Publication Publication Date Title
EP1507844B1 (en) Use of an amphoteric copolymer in a dish washing composition
EP1196523B1 (en) Cleansing composition comprising a water soluble or water dispersible polymer
EP1196527B1 (en) Use of an amphoteric polymer for treating selected hard surface
US6924260B2 (en) Method of reducing and preventing soil redeposition in an automatic dishwashing machine
EP2217690B1 (en) Detergent composition
EP2487232B1 (en) Cleaning agent
US6703358B1 (en) Cleaning composition for hard surfaces
EP2350249B1 (en) Dishwasher detergent
EP2212409B1 (en) Copolymer for treatment of laundry or hard surface
CA2734876A1 (en) Polymer composition and process for the production thereof
EP2487231A1 (en) Agent for treating hard surfaces
EP1196528B1 (en) Cleansing composition for hard surfaces
EP2340299B1 (en) Copolymer for surface processing or modification
EP1896563B1 (en) Phosphate-free automatic dishwashing detergent composition
JPH1060485A (en) Detergent
US20100173819A1 (en) Detergent Composition
JP2002105492A (en) Liquid detergent composition

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: 20041029

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

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

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): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK 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

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60337074

Country of ref document: DE

Effective date: 20110622

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2362181

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20110629

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110511

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: 20110511

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: 20110912

BERE Be: lapsed

Owner name: RHODIA CHIMIE

Effective date: 20110531

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

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: 20110511

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: 20110511

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: 20110812

Ref country code: AT

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: 20110511

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: 20110511

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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: 20110511

Ref country code: MC

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

Effective date: 20110531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

Ref country code: LI

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

Effective date: 20110531

Ref country code: CH

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

Effective date: 20110531

Ref country code: IE

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: 20110511

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: 20110511

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: 20110511

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: 20110511

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: 20110511

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: 20110511

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: 20120210

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: 20110531

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 60337074

Country of ref document: DE

Effective date: 20120210

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: DE

Ref legal event code: R082

Ref document number: 60337074

Country of ref document: DE

Representative=s name: VON ROHR PATENTANWAELTE PARTNERSCHAFT MBB, DE

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: 20110526

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

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: 20110811

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

Effective date: 20110511

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

Effective date: 20110511

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

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: 60337074

Country of ref document: DE

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: 20160801

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

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

Ref country code: IT

Payment date: 20220412

Year of fee payment: 20

Ref country code: GB

Payment date: 20220407

Year of fee payment: 20

Ref country code: FR

Payment date: 20220408

Year of fee payment: 20

Ref country code: ES

Payment date: 20220602

Year of fee payment: 20

Ref country code: DE

Payment date: 20220329

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60337074

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20230602

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20230525

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 EXPIRATION OF PROTECTION

Effective date: 20230527

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20230525