EP3469053B1 - Composition détergente polymérique sans phosphate - Google Patents

Composition détergente polymérique sans phosphate Download PDF

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Publication number
EP3469053B1
EP3469053B1 EP17812816.1A EP17812816A EP3469053B1 EP 3469053 B1 EP3469053 B1 EP 3469053B1 EP 17812816 A EP17812816 A EP 17812816A EP 3469053 B1 EP3469053 B1 EP 3469053B1
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compound
integer
mol
decimal number
acid
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EP17812816.1A
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German (de)
English (en)
French (fr)
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EP3469053A2 (fr
Inventor
Yves Kensicher
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Coatex SAS
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Coatex SAS
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/0002—Washing processes, i.e. machine working principles characterised by phases or operational steps
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the invention relates to the field of detergent compositions, in particular detergent compositions for automatic washing, in particular for automatic dishwashing.
  • the invention provides a phosphate-free detergent composition comprising at least one non-sulfonated nonionic surfactant compound and a non-sulfonated water-soluble copolymer prepared in particular by polymerization reaction of acrylic or methacrylic acid, of an ester of a acrylic or methacrylic acid, itaconic acid or maleic acid and a compound of formula (I):
  • the invention also relates to the use of this non-sulfonated water-soluble copolymer as an anti-tartar agent or anti-drip agent, as well as a cleaning method.
  • the document EP 324568 describes a detergent composition comprising a water-soluble polymer.
  • the document EP 995791 also describes a polymer for a detergent composition.
  • the document EP 2468843 discloses a detergent composition comprising a HASE copolymer.
  • the document EP 2935358 describes a thickening HASE copolymer useful as an anti-settling agent for paint compositions.
  • Prior art detergent compositions suffer from a number of problems. In particular, the presence of phosphates in detergent compositions leads to environmental problems.
  • compositions which are phosphate free.
  • Such compositions are known in particular, nevertheless comprising water-soluble copolymers prepared from phosphate monomers.
  • phosphate residues within these copolymers can prove to be problematic.
  • Detergent compositions without phosphate or with a low concentration of phosphates which comprise copolymers with sulfonated residues. Such detergent compositions do not make it possible to provide completely satisfactory performance compared to phosphated detergent compositions.
  • so-called phosphate-free detergent compositions comprising copolymers with sulfonated residues present defects during dishwashing both as regards the washing efficiency and the ability to avoid traces of tartar or traces of drops.
  • a phosphate-free polymeric detergent composition having improved properties.
  • a phosphate-free detergent composition which makes it possible to combat scale deposits and which has good film-forming effectiveness or effectiveness in reducing or eliminating traces of drops during automatic dishwashing.
  • the invention makes it possible to provide a solution to all or part of the problems encountered with the phosphate-free polymeric detergent compositions of the state of the art.
  • the invention makes it possible to fight against nucleation and against crystal growth leading to the formation of tartar.
  • the monomers (a), (b) and (c) used during the preparation of the copolymer and the surfactant compound are non-sulfonated compounds.
  • the non-sulfonated water-soluble copolymer implemented according to the invention results from the implementation of at least three types of monomers, the monomers (a), (b) and (c) which are different from each other.
  • copolymer used according to the invention is water-soluble, in particular in an acid medium.
  • This non-sulfonated water-soluble copolymer can also be characterized by its molecular weight by weight (M W ). Preferably, it has a molecular mass by weight ranging from 2,000 g/mol to 100,000 g/mol or from 5,000 g/mol to 50,000 g/mol or even from 7,000 g/mol to 20,000 g/mol. soft. Such copolymers of M w of 8,000 g/mol, 9,000 g/mol, 10,000 g/mol, 11,000 g/mol or 12,000 g/mol are particularly preferred. According to the invention, the molecular weight of the copolymers is determined by Steric Exclusion Chromatography (CES) or in English “Gel Permeation Chromatography” (GPC).
  • CES Steric Exclusion Chromatography
  • GPC Gel Permeation Chromatography
  • This technique uses a Waters brand liquid chromatography apparatus equipped with a detector.
  • This detector is a Waters brand refractometric concentration detector.
  • This liquid chromatography apparatus is equipped with a steric exclusion column in order to separate the different molecular weights of the copolymers studied.
  • the liquid elution phase is an aqueous phase adjusted to pH 9.00 using 1 N soda containing 0.05 M NaHCO 3 , 0.1 M NaNO 3 , 0.02 M triethanolamine and 0.03% of NaN 3 .
  • the copolymer solution is diluted to 0.9% dryness in the solubilization solvent of the CES, which corresponds to the liquid phase of elution of the CES to which is added 0.04% of dimethylformamide which plays the role of flow marker or internal standard. Then, it is filtered at 0.2 ⁇ m. 100 ⁇ L are then injected into the chromatography apparatus (eluant: an aqueous phase adjusted to pH 9.00 with 1N sodium hydroxide containing 0.05 M NaHCO 3 , 0.1 M NaNO 3 , 0.02 M trietanolamine and 0.03% NaN 3 ).
  • the liquid chromatography apparatus contains an isocratic pump (Waters 515) whose flow rate is set at 0.8 mL/min.
  • the chromatography apparatus also comprises an oven which itself comprises in series the following column system: a guard column of the Guard Column Ulrahydrogel Waters type 6 cm long and 40 mm in internal diameter and a linear column of the Ulrahydrogel Waters type 30 cm in length and 7.8mm inside diameter.
  • the detection system consists of a refractometric detector of the RI Waters 410 type. The oven is brought to a temperature of 60° C. and the refractometer is brought to a temperature of 45° C.
  • the chromatography apparatus is calibrated using powdered sodium polyacrylate standards of different molecular weights certified by the supplier: Polymer Standard Service or American Polymers Standards Corporation.
  • the acid (a) is acrylic acid or a salt of acrylic acid.
  • the copolymer is prepared by reacting 55 to 90 mol%, preferably 60 to 85 mol%, more preferably 65 to 80 mol% of acid (a), in particular of acrylic acid or a salt of acrylic acid.
  • the acid (a) is acrylic acid or a salt of acrylic acid.
  • the copolymer is prepared by reacting 55 to 90% by weight, preferably 60 to 85% by weight, more preferably 65 to 80% by weight of acid (a), in particular acrylic acid or a salt of acrylic acid.
  • the ester (b) can be an anionic ester or a nonionic ester. According to the invention, the ester (b) can also be a hydrophilic ester or a hydrophobic ester, preferably it is a hydrophobic ester.
  • the ester (b) is an ester of acrylic acid, preferably methyl acrylate, ethyl acrylate, butyl acrylate, hydroxypropyl acrylate, ethylene glycol acrylate, propylene glycol acrylate, more preferably ethyl acrylate; or a methacrylic acid ester, preferably methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxypropyl methacrylate, ethylene glycol methacrylate, propylene glycol methacrylate.
  • the copolymer is prepared by reacting 5 to 20 mol%, preferably 7 to 15 mol% of ester (b), in particular methyl acrylate, acrylate ethyl acrylate, hydroxypropyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate.
  • ester (b) in particular methyl acrylate, acrylate ethyl acrylate, hydroxypropyl acrylate or butyl acrylate, preferably ethyl acrylate or hydroxypropyl acrylate.
  • a more preferred compound (c) of formula (I) is a compound for which R 1 and R 2 represent H, L 1 represents a group chosen from C(O) and CH 2 , L 2 represents a group combining (CH 2 -CH 2 O) x and (CH 2 CH(CH 3 )O) y or (CH(CH 3 )CH 2 O) z , x represents an integer or decimal number between 10 and 140, y+ z represents an integer or decimal number between 10 and 140 and x is strictly greater than y+z and the sum x+y+z is between 10 and 150.
  • a more preferred compound (c) of formula (I) is a compound for which R 1 represents CH 3 , R 2 represents H, L 1 represents a C(O) group, L 2 represents a combining group ( CH 2 -CH 2 O) x and (CH 2 CH(CH 3 )O) y or (CH(CH 3 )CH 2 O) z , x represents an integer or decimal number between 10 and 140, y+z represents an integer or decimal number between 10 and 140 and x is strictly greater than y+z and the sum x+y+z is between 10 and 150.
  • a compound (c) of formula (I) which is also more preferred is a compound for which R 1 represents CH 3 , R 2 represents CH 3 , L 1 represents a C(O) group, L 2 represents a group combining (CH 2 -CH 2 O) x and (CH 2 CH(CH 3 )O) y or (CH(CH 3 )CH 2 O) z , x represents an integer or decimal number between 10 and 140, y+ z represents an integer or decimal number between 10 and 140 and x is strictly greater than y+z and the sum x+y+z is between 10 and 150.
  • a compound (c) of formula (I) which is also more preferred is a compound for which R 1 and R 2 represent H, L 1 represents C(O), L 2 represents (CH 2 CH 2 O) x and x represents 1.
  • a compound (c) of formula (I) which is also more preferred is a compound for which R 1 and R 2 represent H, L 1 represents C(O), L 2 represents (CH 2 CH(CH 3 ) O) y or (CH(CH 3 )CH 2 O) z and y+z represents 1.
  • a compound (c) of formula (I) which is also more preferred is a compound for which R 1 represents CH 3 , R 2 represents H, L 1 represents C(O), L 2 represents a group (CH 2 -CH 2 O) x and x represents 1.
  • a compound (c) of formula (I) which is also more preferred is a compound for which R 1 represents CH 3 , R 2 represents H, L 1 represents C(O), L 2 represents a group (CH 2 CH(CH 3 )O) y or (CH(CH 3 )CH 2 O) z and y+z represents 1.
  • a compound (c) of formula (I) which is also more preferred is a compound for which R 1 represents CH 3 , R 2 represents H, L 1 represents CH 2 , L 2 represents a combining group (CH 2 - CH 2 O) x and (CH 2 CH(CH 3 )O) y or (CH(CH 3 )CH 2 O) z , x represents an integer or decimal number between 10 and 140, y+z represents an integer or decimal between 10 and 140 and x is strictly greater than y+z and the sum x+y+z is between 10 and 150.
  • a compound (c) of formula (I) which is also more preferred is a compound for which R 1 represents CH 3 , R 2 represents H, L 1 represents CH 2 , L 2 represents (CH 2 -CH 2 O ) x , x represents an integer or decimal number between 10 and 140.
  • a compound (c) of formula (I) which is also more preferred is a compound for which R 1 and R 2 represent H, L 1 represents O-CH 2 -CH 2 -CH 2 -CH 2 , L 2 represents (CH 2 -CH 2 O) x , x represents an integer or decimal number between 10 and 140.
  • compound (c) is a compound of formula (I) for which x represents an integer or decimal number between 15 and 80 and y+z represents an integer or decimal number between 10 and 65, preferably a compound of formula (I) for which x represents an integer or decimal number between 30 and 65 and y+z represents an integer or decimal number between 15 and 40, in particular a compound of formula (I) for which x represents a whole or decimal number between 40 and 60 and y+z represents a whole or decimal number between 20 and 30, for example a compound of formula (I) for which x represents 50 and y represents 25.
  • the copolymer is prepared by reacting 7 to 18 mol%, preferably 7 to 15 mol%, of compound (c) of formula (I). Also particularly preferably, the copolymer is prepared by reacting 7 to 18% by weight, preferably 7 to 15% by weight, of compound (c) of formula (I).
  • the non-sulfonated water-soluble copolymer implemented according to the invention can also be prepared by polymerization reaction also implementing a monomer (d).
  • the monomer (d) is chosen from maleic acid, itaconic acid, crotonic acid, their mixtures and their salts. Also preferably, the monomer (d) is used in an amount by weight ranging from 1/20 to 1/3, relative to the amount of monomer (a).
  • the copolymer prepared according to the invention is therefore obtained by a polymerization reaction.
  • This reaction can be a radical polymerization reaction, for example an emulsion, dispersion or solution polymerization reaction.
  • the polymerization can be carried out in water or in a solvent, in the presence of at least one initiator compound.
  • initiator compounds persulfate salts are known, in particular ammonium persulfate, sodium persulfate, potassium persulfate.
  • the amounts of non-sulphonated water-soluble copolymer and of non-sulphonated nonionic surfactant compound can vary quite widely.
  • the detergent composition according to the invention comprises from 1 to 15% by weight, preferably from 2 to 10% by weight, of non-sulfonated water-soluble copolymer. More preferentially, it comprises from 4 to 8% by weight, for example 6% by weight, of non-sulfonated water-soluble copolymer.
  • the quantities of monomers in particular the quantities of monomers (a), (b) and (c), implemented are expressed in molar percentage or by weight relative to the total quantity of monomers used during the preparation of the non-sulfonated water-soluble copolymer.
  • the detergent composition according to the invention also comprises at least one non-ionic surfactant compound which is non-sulfonated.
  • the nonionic surfactant compound comprises ethoxylated chains or propoxylated chains or else it combines ethoxylated chains and propoxylated chains. More preferably, it is a block copolymer comprising ethoxylated chains and propoxylated chains.
  • the nonionic surfactant compound present in the detergent composition according to the invention is a block copolymer which is nonionic and non-foaming. This surfactant compound is non-sulfonated.
  • non-sulfonated nonionic surfactant compounds mention may be made of synthetic alcohol ethoxylates, alcohol ethoxylates of natural origin, ethoxylates tributyl phenol, nonyl phenol ethoxylates, block polymers of ethylene oxide and propylene oxide, ethoxylated-propoxylated alcohol adducts, fatty acid ethoxylates, fatty amine ethoxylates, ethoxylates of castor oil, tristyryl phenol ethoxylates, alkyl polyglycosides.
  • a preferred group of non-sulfonated nonionic surfactant compounds comprises block polymers of ethylene oxide and propylene oxide comprising 10% ethylene oxide, ethoxylated-propoxylated fatty alcohol adducts of C 10 -C 12 , ethoxylated-propoxylated C 12 -C 14 fatty alcohol adducts, ethoxylated-propoxylated C 12 -C 15 oxo-alcohol adducts, oxo-adducts C 12 -C 18 ethoxylated-propoxylated alcohols, C 12 -C 14 fatty alcohol ethoxylates comprising 10 ethylene oxide groups and with a terminal butyl function, C 12 -C 18 fatty alcohol ethoxylates comprising 5 oxide groups containing ethylene and terminal butyl function, C 12 -C 18 fatty alcohol ethoxylates comprising 10 ethylene oxide groups and terminal butyl function, C 12 -C 15 oxo
  • the detergent composition according to the invention comprises from 0.3 to 30% by weight of nonionic surfactant compound, more preferably from 0.5 to 20% by weight or from 1 to 8% by weight.
  • a detergency builder combines several properties such as eliminating or chelating the Ca 2+ and Mg 2+ ions present in the washing water and on the articles to be washed, making the medium basic, improving the performance of surfactant compounds, desorb soils and retain them in the cleaning medium.
  • the detergent composition comprises at least one non-phosphate, organic or inorganic detergent builder.
  • NTA nitriloacetic acid
  • sodium aluminosilicates or zeolite A carbonates such as sodium carbonates, citrates such as sodium citrates, in particular sodium tricitrate, silicates such as sodium silicates , gluconic acid and its salts, in particular its sodium salts, glutamic acid and its salts, sodium quadruple salt of N , N -diacetic acid, EDTA (ethylenediaminetetra-acetic acid), MGDA (methylglycindiacetate), EDDS (ethylenediamine- N- , N'-disuccinic acid), IDSA ( iminodisuccinic acid), sodium salt of iminosuccinic acid and mixtures thereof.
  • NTA nitriloacetic acid
  • carbonates such as sodium carbonates
  • citrates such as sodium citrates, in particular sodium tricitrate
  • silicates such as sodium silicates
  • gluconic acid and its salts in particular its
  • detergent composition according to the invention are known as such. They can be chosen according to their known properties and they can be implemented under conditions and in quantities known as such.
  • the detergent composition according to the invention can take different forms. It can be in solid, liquid or gel form. Preferably, it is in a solid form, for example in the form of powder, granules or in the form of tablets, for example multilayer tablets.
  • the automatic dishwashing detergent composition according to the invention is preferably in the form of powder, granules or in the form of tablets, for example multilayer tablets.
  • the invention also relates to the use of at least one non-sulfonated water-soluble copolymer defined for the detergent composition according to the invention as an anti-tartar agent. Also, the invention relates to the use of at least one non-sulfonated water-soluble copolymer defined for the detergent composition according to the invention as an anti-drip agent. It also relates to the use of at least one copolymer water-soluble non-sulphonated defined for the detergent composition according to the invention as an anti-tartar and anti-drip agent.
  • the invention relates to such uses within a detergent composition also comprising at least one non-sulfonated nonionic surfactant compound.
  • the cleaning method according to the invention is implemented for washing or cleaning which is chosen from washing a vehicle, in particular automobiles, detergents, in particular household detergents, laundry washing, in particular automatic laundry washing , dishwashing or cleaning, in particular automatic dishwashing or cleaning, washing aid, surface cleaning.
  • the cleaning method according to the invention is implemented for the automatic washing or cleaning of dishes.
  • a non-sulfonated copolymer P1 according to the invention is prepared.
  • the temperature is maintained at 73°C +/- 2°C.
  • the pumps are then rinsed with 70 g of water and the whole is cooked at 73° C. for 30 min.
  • the solution is then cooled to 60° C. and 8.5 g of 35% hydrogen peroxide are added.
  • the whole is then cooked for 30 minutes and then cooled to room temperature.
  • polymers P3 to P5 being according to the invention and polymer P2 being outside the scope of protection of the invention
  • the reagents, in particular the monomers M1, M2 and M3, used, the reaction conditions and the characteristics of the polymers prepared are presented in Table 1.
  • Table 1 Polymer P2 P3 P4 P5 M1 (g) 416.50 392.00 355.25 379.75 M2 (g) 61.25 61.25 61.25 61.25 M3 (g) 12.25 36.75 73.50 49.00 MW (g/mol) 10,750 11,110 10,560 10,890 IP 3.1 3.2 3.1 3.2
  • polymers according to the invention are prepared by varying the monomers and their proportions.
  • the reactants in particular the monomers M4 (hydroxypropylacrylate), M5 (polyalkylene glycol methacrylate of M w 2,000 g/mol and composed of 85% by mass of units resulting from the cycloaddition of ethylene oxide and 15% by mass of units resulting from the cycloaddition of propylene oxide in aqueous solution at 50% by weight) and M6 (methallylpolyethylene glycol of M w 2,400 g/mol in aqueous solution at 60% by weight), implemented, the reaction conditions and the characteristics of the prepared polymers are shown in Table 2.
  • the first comparative polymer PC1 is a sodium polyacrylate derived from an acrylic homopolymer in the form totally neutralized with sodium (product Acusol 445 NG from Rohm and Haas), its molecular mass by weight (Mw) is 4,500 g/mol.
  • the second comparative polymer PC2 is a sulfonated acrylic copolymer in the form partially neutralized with sodium (product Acusol 588 G from Rohm and Haas), its molecular weight by weight (M W ) is 12,000 g/mol.
  • detergent compositions are prepared in the form of a washing powder for dishwashers comprising sodium citrate, sodium metasilicate, a non-ionic non-foaming surfactant compound and 1 g of the polymer at test in dry and granulated form.
  • the performance of the polymers is evaluated on the basis of dishwashing tests consisting of glass plates, enamelled ceramic plates, bakelite plates and stainless steel glasses and cutlery.
  • the dishwashers used are of the Miele brand, model G4920SC, the intensive washing program at a temperature greater than or equal to 75°C is used.
  • the ion exchange resins used by dishwashers to soften wash and rinse water are saturated with calcium salts to render them ineffective. No resin regeneration salt is used for washing.
  • the dishwasher is filled with the dishes and then the intensive program is selected.
  • the program begins with a cold water rinse for 10 minutes. After this rinsing, a dose of 50 g of standardized dirt is introduced manually into the dishwasher as well as 17 g of washing powder comprising in particular the polymer to be tested. The washing then continues for one hour, after 30 min the temperature reaches 75°C.
  • the water is drained automatically and a first rinse with water at 40° C. is carried out, followed by a second rinse with water at 70° C. for 15 min.
  • the water from the second rinse is then drained and the dishwasher is stopped. The dishes dry naturally for 30 minutes after opening the dishwasher.
  • the polymers are compared by visual examination of the glasses placed next to each other in a black box lit overhead. A score from 0 to 10 is assigned during each examination of the glasses, 0 for a totally opaque glass and 10 for a new, unwashed glass. The results obtained are shown in Table 3.
  • the washes carried out using the compositions according to the invention make it possible to eliminate all the dirt.
  • the absence of a continuous film of tartar is observed on the surface of the washed dishes, in particular on glass dishes, in particular glasses.
  • the washed dishes do not show visible drip marks.
  • compositions according to the invention allow an effectiveness which is much higher than that obtained by means of the known sodium polyacrylate and of the same level as that obtained with the known sulfonated polymer.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP17812816.1A 2016-06-13 2017-06-09 Composition détergente polymérique sans phosphate Active EP3469053B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1655433A FR3052461B1 (fr) 2016-06-13 2016-06-13 Composition detergente polymerique sans phosphate
PCT/FR2017/051457 WO2017216452A2 (fr) 2016-06-13 2017-06-09 Composition détergente polymérique sans phosphate

Publications (2)

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EP3469053A2 EP3469053A2 (fr) 2019-04-17
EP3469053B1 true EP3469053B1 (fr) 2022-05-25

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US (1) US10865365B2 (es)
EP (1) EP3469053B1 (es)
KR (1) KR102377150B1 (es)
CN (1) CN109312269B (es)
BR (1) BR112018074038B1 (es)
CA (1) CA3026011A1 (es)
ES (1) ES2924803T3 (es)
FR (1) FR3052461B1 (es)
MX (1) MX2018014307A (es)
PL (1) PL3469053T3 (es)
RU (1) RU2742092C2 (es)
WO (1) WO2017216452A2 (es)
ZA (1) ZA201807741B (es)

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Publication number Priority date Publication date Assignee Title
FR3067718B1 (fr) * 2017-06-16 2020-08-14 Coatex Sas Composition detergente polymerique sans phosphate
EP3810739A1 (en) * 2018-06-25 2021-04-28 Dow Global Technologies, LLC Automatic dishwashing formulation with dispersant copolymer

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4797223A (en) 1988-01-11 1989-01-10 Rohm And Haas Company Water soluble polymers for detergent compositions
AU5355599A (en) 1998-10-22 2000-05-04 Rohm And Haas Company Polymer compositions and a method of promoting soil release from fabrics using said polymer compositions
US9682256B2 (en) * 2006-07-14 2017-06-20 Colgate-Palmolive Company Methods of making compositions comprising films
JP2012136694A (ja) 2010-12-27 2012-07-19 Rohm & Haas Co 高−界面活性剤配合物のためのポリマー
CN110305265A (zh) * 2012-12-21 2019-10-08 罗地亚经营管理公司 防沉和增稠组合物及使用其的方法

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MX2018014307A (es) 2019-02-25
CN109312269A (zh) 2019-02-05
BR112018074038B1 (pt) 2022-11-16
WO2017216452A3 (fr) 2018-11-29
FR3052461B1 (fr) 2020-01-10
US20190177663A1 (en) 2019-06-13
RU2742092C2 (ru) 2021-02-02
CA3026011A1 (fr) 2017-12-21
KR20190017759A (ko) 2019-02-20
US10865365B2 (en) 2020-12-15
CN109312269B (zh) 2021-03-02
FR3052461A1 (fr) 2017-12-15
EP3469053A2 (fr) 2019-04-17
WO2017216452A2 (fr) 2017-12-21
RU2019100429A (ru) 2020-07-15
KR102377150B1 (ko) 2022-03-22
BR112018074038A2 (pt) 2019-02-26
RU2019100429A3 (es) 2020-08-11
ZA201807741B (en) 2020-05-27
PL3469053T3 (pl) 2022-11-14
ES2924803T3 (es) 2022-10-11

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