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
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds

Definitions

• the invention relates to the field of detergent compositions, in particular detergent compositions for automatic washing, especially for the automatic washing of dishes.
• the invention provides a phosphate-free detergent composition comprising at least one non-sulfonated nonionic surfactant compound and a water-soluble non-sulfonated copolymer prepared in particular by polymerization reaction, in the presence of at least one compound comprising at least one function alcohol, acrylic or methacrylic acid and a compound of formula (I):
• the invention also relates to the use of this water-soluble non-sulfonated copolymer as an anti-scale agent or anti-drip agent, as well as a cleaning method.
• the detergent compositions of the state of the art present a number of problems.
• the presence of phosphates in detergent compositions leads to environmental problems.
• compositions for automatic dishwashing which are phosphate-free.
• such compositions which nevertheless comprise water-soluble copolymers prepared from phosphate monomers.
• phosphate residues within these copolymers can be problematic.
• Phosphate-free or low phosphate detergent compositions which include sulfonated residue copolymers are known. Such detergent compositions do not provide totally satisfactory performance over phosphate detergent compositions. In particular, such so-called phosphate-free detergent compositions comprising sulfonated residue copolymers have defects in dishwashing both with regard to washing efficiency and the ability to avoid scale marks or traces of drops.
• US 4797223 discloses generically a detergent composition comprising a surfactant and a water-soluble polymer but gives no indication of any anti-scale efficiency, particularly in the field of automatic dishwashing.
• EP 1182217 discloses a water-soluble terpolymer based on a dicarboxylic acid and its use as an anti-scale.
• a 2620240 discloses a dishwasher detergent formulation comprising a complexing agent as well as a terpolymer based on acrylic acid, methacrylic acid and a monomer of formula (I).
• 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 crystalline growth leading to the formation of scale.
• the invention provides a phosphate free detergent composition comprising:
• R 1 and R 2 which may be identical or different, independently represent H or CH 3
• L 1 independently represents a group chosen from C (O), CH 2 , CH 2 -CH 2 and O-CH 2 -CH 2 -CH 2 - CH 2 ,
• L 2 independently represents a group selected from (CH 2 -CH 2 O) x , (CH 2 CH (CH 3 ) O) y , (CH (CH 3 ) CH 2 0) z and combinations thereof and
• x, y and z which are identical or different, independently represent an integer or decimal number between 0 and 150, x is strictly greater than y + z and the sum x + y + z is between 10 and 150 and
• At least one non-sulfonated nonionic surfactant compound At least one non-sulfonated nonionic surfactant compound.
• the monomers (a) and (b) used during the preparation of the copolymer and the surfactant compound are non-sulfonated compounds.
• the water-soluble copolymer non-sulfonated implemented according to the invention results from the implementation of two types of monomers, the monomers (a) and (b) which are different from each other. It is a copolymer different from a HASE copolymer.
• the copolymer used according to the invention is water-soluble, especially in acidic medium.
• This non-sulfonated water-soluble copolymer may also be characterized by its weight-average molecular weight (Mw). Preferably, it has a molecular weight in weight ranging from 2,000 g / mol to 100,000 g / mol or from 5,000 g / mol to 50,000 g / mol or from 7,000 g / mol to 20,000 g / mol. mol.
• Mw weight-average molecular weight
• 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.
• the molecular weight of the copolymers is determined by chromatography of Steric Exclusion (CES) or in English "Gel Permeation Chromatography” (GPC).
• This technique uses a Waters liquid chromatography apparatus equipped with a detector.
• This detector is a Waters refractometric concentration detector.
• This liquid chromatography apparatus is provided 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 sodium hydroxide 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% dry in the solubilization solvent of the CES, which corresponds to the liquid phase of elution of the CES, to which 0.04% of dimethylformamide which is added is added. the role of flow marker or internal standard. Then, it is filtered at 0.2 ⁇ . 100 ⁇ ⁇ are then injected into the chromatograph (eluent: an aqueous phase adjusted to pH 9.00 by N sodium hydroxide containing 0.05 M NaHC0, NaN0 0.1M, 0.02M triétanolamine and 0.03% NaN 3 ).
• the liquid chromatography apparatus contains an isocratic pump (Waters 515) with a flow rate of 0.8 mL / min.
• the chromatography apparatus also comprises an oven which itself comprises in series the following column system: a precolumn of the Guard Column Ulrahydrogel Waters type of 6 cm in length and 40 mm in internal diameter and a linear column of the Ulrahydrogel Waters type of 30 cm long and 7.8 mm inside diameter.
• the detection system consists of a type RI Waters 410 refractometric detector. The oven is heated to a temperature of 60 ° C and the refractometer is heated to a temperature of 45 ° C.
• the chromatography apparatus is calibrated using powdered polyacrylate standards of various molecular weights certified by the supplier: Polymer Standards Service or American Polymers Standards Corporation.
• the polymerization reaction uses at least one compound comprising at least one alcohol function.
• a single compound comprising an alcohol function is used.
• the compound comprising at least one alcohol function is a compound comprising a secondary alcohol function. Even more preferably, the compound comprising at least one alcohol function is chosen from propan-2-ol, butan-2-ol and glycerol. The most preferred compound is propan-2-ol.
• the compound comprising at least one alcohol function is used in the absence of other co-solvent.
• it can be used in a mixture with a co-solvent, preferably in a mixture with water.
• the compound comprising at least one alcohol function is carried out in the form of a mixture with water comprising at least 15% by weight or at least 20% by weight of compound comprising an alcohol function.
• the acid (a) is acrylic acid or a salt of acrylic acid.
• the copolymer is prepared by reaction of 70 to 98% by weight, preferably 75 to 98% by weight, more preferably 80 to 98% by weight, of acid (a), especially acrylic acid or a salt of acrylic acid.
• the polymerization reaction is then carried out in the absence of methacrylic acid and in the absence of a salt of methacrylic acid.
• the copolymer is prepared by reaction of 2 to 30% by weight, preferably 2 to 25% by weight or 2 to 20% by weight of compound (b).
• a compound (b) of formula (I) which is preferred for the preparation of the water-soluble non-sulphonated copolymer is a compound for which:
• R 1 and R 2 represent H or CH 3
• R 1 and R 2 represent H or CH 3
• L 1 represents a group chosen from C (O) and CH 2 or
• L 2 represents a combination group (CH 2 -CH 2 O) x and (CH 2 CH (CH 3) O) y or (CH (CH 3 ) CH 2 0) z or
• x represents an integer or decimal number between 10 and 140, preferably x represents an integer or decimal number between 15 and 140 or
• y + z represents an integer or decimal number between 10 and 140, preferably y + z represents an integer or decimal number between 10 and 135 where x is strictly greater than y + z and the sum x + y + z is between 10 and 150.
• a compound (b) of formula (I) also preferred for the preparation of the Water-soluble non-sulfonated copolymer is a compound for which R 2 is H.
• a compound (b) of formula (I) which is more preferred 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 grouping combining (CH 2 -CH 2 0) x and (CH 2 CH (CH 3) O) y or (CH (CH 3) CH 2 0) 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 and the sum x + y + z is between 10 and 150.
• a more preferred compound (b) 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 combination group (CH 2 -CH 2 O) x and (CH 2 CH (CH 3 ) 0 ) y or (CH (CH 3) CH 2 0) z, x represents a whole or decimal number between 10 and 140, y + z is 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 1 50.
• a compound (b) 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 grouping combining (CH 2 -CH 2 O) x and (CH 2 CH (CH 3 ) O) y or (CH (CH 3 ) CH 2 0) 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 (b) 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 0) x and x represents 1.
• a compound (b) 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 ) 0) y or (CH (CH 3 ) CH 2 0) z and y + z represents 1.
• a compound (b) 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 0) x and x represents 1.
• a compound (b) 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 0) z and y + z represents 1.
• a compound (b) of formula (I) which is also more preferred is a compound wherein R 1 represents CH 3 , R 2 represents H, L 1 represents CH 2 , L 2 represents a combination group (CH 2 -CH 2 O) x and (CH 2 CH (CH 3 ) O) y or (CH 2 CH 3 ) CH 2 0) 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 from 10 to 150.
• a compound (b) 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 (b) 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 0) x , x represents an integer or decimal number between 10 and 140.
• the compound (c) of formula (I) is a compound for which:
• x represents an integer or decimal number between 15 and 140
• y represents an integer or decimal number between 10 and 135 and
• z represents an integer or decimal number between 10 and 135 and
• compound (b) is a compound of formula (I) for which x represents an integer or decimal 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 a integer or decimal number between 15 and 40, in particular a compound of formula (I) for which x represents an integer or decimal number between 40 and 60 and y + z represents an integer or decimal number between 20 and 30, for example a compound of formula (I) wherein x is 50 and y is 25.
• the non-sulfonated water-soluble copolymer used according to the invention is prepared by reaction of only monomers (a) and (b) or mixtures of monomers (a) and monomers (b).
• the non-sulfonated water-soluble copolymer used according to the invention may optionally be prepared by polymerization reaction also implementing a monomer (c).
• the monomer (c) is chosen from methacrylic acid, acrylic acid, maleic acid, itaconic acid and crotonic acid. mixtures and their salts. Also preferably, the monomer (c) is used in a quantity by weight ranging from 1/20 to 1/3 relative to the amount of monomer (a).
• the copolymer prepared according to the invention is thus obtained by a polymerization reaction.
• This reaction may be a radical polymerization reaction, for example an emulsion, dispersion or solution polymerization reaction.
• the polymerization may be conducted in the presence of at least one initiator compound.
• initiator compounds are persulfate salts, especially ammonium persulfate, sodium persulfate, potassium persulfate.
• the amounts of non-sulfonated water-soluble copolymer and non-sulfonated 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 preferably, it comprises from 4 to 8% by weight, for example 6% by weight, of non-sulfonated water-soluble copolymer.
• the amounts of monomers are expressed as a percentage by weight relative to the total amount of monomers used in the preparation of the water-soluble copolymer. - sulphonated.
• the detergent composition according to the invention also comprises at least one nonionic surfactant compound which is non-sulfonated.
• the nonionic surfactant compound comprises ethoxylated chains or propoxylated chains or it combines ethoxylated 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 unsulphonated.
• non-sulfonated nonionic surfactant compounds include ethoxylates of synthetic alcohols, ethoxylates of naturally occurring alcohols, tributyl phenol ethoxylates, nonyl phenol ethoxylates, block polymers of ethylene oxide and propylene oxide, ethoxylated-propoxylated alcohol adducts, ethoxylates of fatty acids, fatty amine ethoxylates, castor oil ethoxylates, tristyryl phenol ethoxylates, alkyl polyglycosides.
• a preferred group of non-tallow nonionic surfactant compounds include block polymers of ethylene oxide and propylene oxide comprising 10% ethylene oxide, ethoxylated-propoxylated fatty alcohol adducts of the present invention.
• 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.
• the detergent composition may also comprise at least one builder or one or more substances chosen from:
• At least one filler in particular a solid filler, for example a zeolitic filler,
• 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 the surfactant compounds, desorb the dirt and keep it in the cleaning medium.
• the detergent composition comprises at least one non-phosphate, organic or inorganic detergency 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, four-fold sodium salt of N, N-diacetic acid, EDTA (ethylenediaminetetraacetic acid), MGDA (methylglycindiacetate), EDDS (ethylenediamine-N-acid) , N'-disuccinic), 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 sodium salts, glut
• the invention also provides a detergent composition for automatic dishwashing which comprises at least one detergent composition according to the invention.
• This detergent composition for automatic dishwashing may also include:
• At least one solid charge which is not zeolitic is not zeolitic
• a whitening or bleaching agent optionally combined with a bleaching agent or activator,
• 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 quantities known as such.
• the detergent composition according to the invention can take different forms. It can be in a 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 detergent composition for automatic dishwashing 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 anti-scale agent. Also, the invention relates to the use of at least one water-soluble non-tallow 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 non-sulfonated water-soluble copolymer defined for the detergent composition according to the invention as anti-scaling and anti-drip agent.
• the invention relates to such uses in a detergent composition also comprising at least one non-sulfonated nonionic surfactant compound.
• the invention relates to a cleaning method comprising the implementation of at least one detergent composition according to the invention.
• the cleaning method according to the invention comprises the use of water and at least one detergent composition according to the invention.
• the cleaning method comprises:
• the cleaning method according to the invention is implemented for washing or cleaning which is selected from washing a vehicle, especially automobile, detergency, including household detergency, laundry, including automatic washing of laundry washing or cleaning the dishes, in particular washing or automatic cleaning of the dishes, washing aid, surface cleaning.
• the cleaning method according to the invention is implemented for washing or automatic cleaning of the dishes.
• copolymer of the detergent composition according to the invention make it possible to define particular and advantageous cleaning or washing methods and methods according to the invention.
• a non-sulfonated P1 copolymer according to the invention is prepared.
• the mixture 3 in a third tank, it is a solution consisting of:
• the polymerization reactor is heated to 85 ⁇ 1 ° C and the 3 mixtures are injected for two hours. During injection, the temperature is maintained at 85 ⁇ 1 ° C.
• the pumps are then rinsed with water and the whole is cooked at 85 ⁇ 1 ° C for 30 min.
• the solution is then cooled to 60 ° C. and 3.05 g of 35% hydrogen peroxide are added and then 50% by weight aqueous sodium hydroxide solution is added to give a pH of 4.4.
• the effectiveness of the copolymer according to the invention is compared with known comparative polymers.
• a first comparative polymer PCI is prepared.
• the polymerization reactor is heated to 85 ⁇ 1 ° C and the 3 mixtures are injected for two hours. During injection, the temperature is maintained at 85 ⁇ 1 ° C.
• the pumps are then rinsed with water and the whole is cooked at 85 ⁇ 1 ° C for 30 min.
• the second comparative polymer PC2 is a partially neutralized sodium sulfonated acrylic copolymer (Acusol product 588 G from Rohm and Haas), its weight-average molecular weight (Mw) is 12,000 g / mol.
• detergent compositions are prepared in the form of a dishwashing powder comprising sodium citrate, sodium metasilicate, a non-foaming nonionic surfactant compound and 1 g of the test in dry and granulated form.
• the performance of the polymers is evaluated from dishwashing tests consisting of glass plates, enamelled ceramic plates, bakelite plates, and stainless steel glasses and cutlery.
• the dishwashers used are brand Miele, 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 the wash and rinse water are saturated with calcium salts to render them inoperative. No regeneration salt of the resins is used for the washings.
• the program begins with a rinse with cold water for 10 minutes. After this rinse, a dose of 50 g of standardized soil is manually introduced into the dishwasher and 17 g of washing powder including the polymer to be tested. The washing then continues for one hour, after 30 minutes the temperature reaches 75 ° C.
• the water is drained automatically and a first rinse with water at 40 ° C is performed, followed by a second rinse with water at 70 ° C for 15 min.
• the second rinse water 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 inspection of the glasses placed next to each other in a black box illuminated zenith. A score of 0 to 10 is assigned at 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 1.
• Table 1 The washes made using the compositions according to the invention make it possible to eliminate all the dirt. There is no continuous film of scale on the surface of washed dishes, especially on glassware, especially glasses. Washed dishes do not show any visible drip.
• compositions according to the invention allow an efficiency 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)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Detergent Compositions (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2017
  • 2017-06-16 FR FR1755451A patent/FR3067718B1/fr active Active
• 2018
  • 2018-06-13 US US16/614,658 patent/US11091724B2/en active Active
  • 2018-06-13 WO PCT/FR2018/051390 patent/WO2018229430A1/fr active Application Filing
  • 2018-06-13 CA CA3066070A patent/CA3066070A1/fr not_active Abandoned
  • 2018-06-13 MX MX2019013403A patent/MX2019013403A/es unknown
  • 2018-06-13 BR BR112019022855A patent/BR112019022855A2/pt not_active Application Discontinuation
  • 2018-06-13 EP EP18749427.3A patent/EP3638761A1/fr active Pending
  • 2018-06-13 KR KR1020197036008A patent/KR20200019614A/ko unknown
  • 2018-06-13 CN CN201880037180.7A patent/CN110741070B/zh active Active
  • 2018-06-13 AU AU2018284025A patent/AU2018284025A1/en not_active Abandoned
  • 2018-06-13 RU RU2020101125A patent/RU2020101125A/ru not_active Application Discontinuation

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