EP3177703B1 - Utilisation dans des compositions détergentes de polymères obtenus par polymérisation en émulsion inverse basse concentration avec un faible taux de monomères neutralises - Google Patents

Utilisation dans des compositions détergentes de polymères obtenus par polymérisation en émulsion inverse basse concentration avec un faible taux de monomères neutralises Download PDF

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Publication number
EP3177703B1
EP3177703B1 EP15759892.1A EP15759892A EP3177703B1 EP 3177703 B1 EP3177703 B1 EP 3177703B1 EP 15759892 A EP15759892 A EP 15759892A EP 3177703 B1 EP3177703 B1 EP 3177703B1
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Prior art keywords
monomers
acid
polymer
polymerization
composition
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German (de)
English (en)
French (fr)
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EP3177703A1 (fr
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Frédéric BLONDEL
Lionel Champagnon
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SPCM SA
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SPCM SA
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    • 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
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes

Definitions

  • the invention relates to the technical field of detergent compositions for household or industrial use adapted to the cleaning and washing of various surfaces and more specifically to the use in this field of synthetic acrylic polymers comprising at least one weak acid function, obtained under particular conditions by the inverse emulsion polymerization process from at least one monomer carrying a weak acid function, as well as the corresponding detergent compositions.
  • “Household or industrial detergent compositions” means compositions for the cleaning of various surfaces, in particular of textile fibers, of hard surfaces of any kind such as dishes, floors, windows, wood surfaces, metal surfaces. or composite. Such compositions correspond, for example, to detergents for washing clothes manually or in a washing machine, products for cleaning dishes manually or for dishwashers, detergents for washing house interiors such as kitchen elements. , toilets, furniture, floors, windows, and other cleaning products for general use.
  • the detergent compositions for household or industrial use do not include compositions intended for cleaning keratin materials (skin, hair, etc.) and therefore do not include cosmetic compositions, dermatological compositions, or pharmaceutical compositions with a cleaning component. In the remainder of the description, the "detergent compositions for household or industrial use” may simply be called “detergent compositions”.
  • liquid compositions includes compositions in the form of solution, gel or dispersion.
  • liquid detergent compositions have required complex work of adaptation and formulation.
  • One of the challenges of this adaptation has been and still is the mastery of rheology.
  • Thickeners or rheology modifiers are therefore widely used in these compositions to adapt their viscosity to the requirements of the consumer, who often feels that "thick is better", but also to suspend or stabilize active agents present in the composition.
  • Natural and synthetic polymers are used as thickeners. There may be mentioned, for example, hydroxycelluloses, carboxymethyl celluloses, polysaccharides, polyacrylamides, acrylic polymers, polyvinylalcohols, polyurethanes, polyvinylpyrrolidones, ethylene polyoxides, etc.
  • a problem encountered in thickening detergent compositions is related to the presence of surfactants, which are necessary for their cleaning function, and which degrade the rheological behavior of the compositions thickened with the aid of polymer. This results in a loss of viscosity or a lack of stability over time of this viscosity.
  • the document FR 2 789 395 A1 discloses water-in-oil thickeners for cosmetic or pharmaceutical preparations, comprising a polymer obtained by inverse emulsion polymerization. During polymerization more than 20% of the acid functions are neutralized.
  • liquid detergent compositions The patent EP 0 759 966 B1 from Johnson & Son, Inc. proposes associative polymers for thickening laundry detergents containing large amounts of nonionic surfactant: 5 to 30% by weight.
  • the polymers used such as Acusof® 820 sold by Rohm and Haas Co are obtained by emulsion polymerization and are generally called latex.
  • the patent US 6,274,539 by The Procter & Gambia Company discloses hand dishwashing compositions containing, for example, 20 to 40% by weight of anionic surfactant, 3 to 10% by weight of nonionic surfactant and 0.2 to 2% by weight a thickening agent corresponding to an associative copolymer of ethyl acrylate, steareth-20, and (meth) acrylic acid.
  • Acusol® 820 is referred to as an example of such a thickening polymer.
  • Example 6 relating to a cleaning formulation for household use, uses, as an associative polymer, a polyacetal modified polyether, Aquaflow® XLS500, which is a polymer obtained by the technique of precipitation polymerization.
  • the patent application GB 2,346,891 proposes to thicken cleaning compositions for hard surface cleaning with hydrophobically modified polycarboxylates, such as Polygel® W30 commercial products from 3V UK Ltd and Rheovis CRX and CR from Allied Colloids.
  • the most effective polymers currently in the detergent compositions are therefore either crosslinked polycarboxylates or homopolymers of acrylic acid obtained by precipitation polymerization, such as Carbopol®, or so-called polymers.
  • associative compounds having a hydrophilic major part and hydrophobic parts such as Acusol® 820 obtained by emulsion polymerization. Nevertheless, it has been found in use that these polymers are still sensitive to the presence of surfactants in the detergent compositions.
  • polymers obtained by inverse emulsion polymerization are not used to thicken detergent compositions and are rather considered by the professionals in the field of detergent compositions to be ineffective as a thickening agent in these compositions.
  • the object of the invention is to provide detergent compositions having a rheological behavior for easy use and which are suitable for the incorporation of a wide range of surfactants, and having excellent resistance to surfactants.
  • the Applicant has developed polymers obtained by inverse emulsion polymerization having improved thickening performance, making them compatible with their use in detergent compositions. It has also been found that these polymers have better resistance to surfactants conventionally used in detergent compositions.
  • the object of this invention is therefore to propose, for thickening liquid detergent compositions, the use of an acrylic polymer obtained by implementing particular conditions in an inverse emulsion polymerization process, said polymer thus having a good Thickening efficiency and being compatible with its use in detergent compositions. Moreover, such polymers are resistant to surfactants conventionally used in such detergent compositions.
  • Such a polymer defined by its process of obtaining is named in the following description "thickening polymer”, “acrylic polymer” or “polymer plugged or crosslinked”.
  • the subject of the invention is also the use of such a thickening polymer for thickening an aqueous detergent liquid composition.
  • the thickening polymer comprises a percentage of neutralized acid functions of 30 to 100% with respect to all the acid functions present on the polymer, obtained by a step of at least partial neutralization of the acid functions present on the polymer made after the polymerization, but before or after the preparation of the composition.
  • compositions for household or industrial use will be in particular in the form of a solution, gel or dispersion, and in particular an aqueous solution, an aqueous gel or an aqueous dispersion.
  • composition in particular aqueous solution, gel or dispersion
  • a composition comprising a part of water, and in particular a part of water representing at least 10% by weight of the mass of the composition.
  • compositions suitable and intended for cleaning textile fibers such as washing liquors by hand or in a washing machine; suitable for cleaning hard surfaces of all kinds such as dishes (whether for manual or dishwasher cleaning), floors, windows, wood, metal or composite surfaces, furniture, kitchen elements, toilets; and cleaning products for general use.
  • the detergent compositions for household or industrial use according to the invention do not include compositions intended for the cleaning of keratin materials (skin, hair, etc.) and therefore do not include the cosmetic compositions, the dermatological compositions or the pharmaceutical compositions. with cleaning component.
  • the invention also relates to the use of a composition according to the invention for cleaning textile fibers, in particular for washing clothes manually or in a washing machine, or for cleaning a hard surface such as dishes, furniture, floors, windows, wood or metals, especially for cleaning dishes manually or in dishwashers ...
  • Such use includes the application of the composition on the surface to be cleaned, optionally followed by rinsing with water.
  • the polymers used in the context of the invention are composed of the repetition of one or more monomeric units, with at least one of the monomeric units corresponding to a monomer comprising an acrylic group.
  • they correspond to homopolymers obtained by polymerization of a monomer comprising an acrylic group or copolymers obtained by copolymerization of a mixture of monomers, at least one of which comprises an acrylic group.
  • such polymers may simply be called acrylic polymers.
  • the polymers used in the context of the invention are water-soluble or hydro-swelling.
  • the monomers used for the preparation of these polymers and in particular the level of hydrophilic monomers will be selected so as to obtain such properties.
  • water-soluble polymer a polymer which, dissolved by stirring in water at a temperature of 25 ° C at a concentration of 50 g / l, gives a solution free of insoluble particles.
  • hydro-swelling polymer is meant a polymer which, dissolved in water at a temperature of 25 ° C, swells and thickens the solution.
  • branched polymers in a conventional manner, nonlinear polymers which have side chains.
  • the branched polymers include, in particular, star-shaped and comb-shaped polymers.
  • crosslinked polymer is meant, in a conventional manner, a non-linear polymer which is in the form of a three-dimensional network insoluble in water, but swellable in water.
  • the crosslinking is obtained by using a branching agent during the polymerization which is integrated in the aqueous phase.
  • a branching agent corresponds to a monomer comprising two or more ethylenic unsaturations and is, for example, chosen from methylenebisacrylamide. (MBA), ethylene glycol di-acrylate, polyethylene glycol dimethacrylate, diacrylamide, cyanomethylacrylate, vinyloxyethylacrylate, vinyloxymethacrylate, triallylamine, formaldehyde, glyoxal, glycidyl ethers such as ethylene glycol diglycidyl ether, epoxies and mixtures thereof.
  • the total monomer concentration given in connection with the polymerization process includes the monomers acting as branching agent.
  • the Applicant was interested in the use of corresponding acrylic polymers or obtained from a reverse polymer emulsion prepared by water-in-oil reverse emulsion polymerization with use of a high molar percentage.
  • the inventors have demonstrated that the properties of the polymer obtained were really dependent, on the one hand, on the neutralization rate of the acid functions of the monomers used during the polymerization and on the other hand, the total concentration of the monomers in the aqueous phase.
  • the Applicant has, in the context of the invention, turned towards a process for the polymerization of inverse emulsion of polymers having a low degree of neutralization and, in particular, a degree of neutralization of the acid functions present of at most 20%.
  • the applicant proposes to use such a polymer, obtained by polymerization of an aqueous solution of monomers in water-in-oil inverse emulsion, in which the polymerization is carried out with a concentration of all the monomers belonging to in the range from 1.3 mmol to 3.6 mmol per gram of aqueous solution.
  • the plaintiff has shown that such a range of concentrations, unlike the higher concentrations used in particular in the prior art, was compatible with obtaining polymer with a low neutralization rate weak acid functions present and overcomes stability problems found in the prior art.
  • acid functions present on the monomers used having at least one acid function are in neutralized form, which allows to obtain thickening properties even more advantageous.
  • 100% of the acid functions present on the monomers used are in free acid form, during the polymerization.
  • the polymerization is carried out with a total concentration of monomers present in the aqueous solution belonging to the range from 1.7 to 3.3 mmol per gram of aqueous solution.
  • concentrations of monomers are given in relation to the mass total aqueous solution (also called aqueous phase), that is to say monomer mass included.
  • the molar percentage of monomers carrying at least one weak acid function relative to all the monomers used is preferably at least 50%, preferably at least 70%, very preferably at least 80%. Such molar percentages may be used with any of the above-mentioned monomer concentration / neutralization concentration combinations.
  • the polymerization will preferably be carried out with monomers which all have at least one ethylenic unsaturation.
  • the polymerization is carried out with a single monomer carrying at least one weak acid function whose molar percentage relative to all the monomers used is at least 30%, which in free form is chosen from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid and fumaric acid.
  • the monomer carrying at least one weak acid function is very preferably acrylic acid in free form or with a degree of neutralization according to the invention. It is also possible to use several monomers carrying at least one weak acid function, in particular chosen from those previously listed, whose total molar percentage with respect to all the monomers used is at least 30%. Preferably, one of these monomers is acrylic acid in free form or with a degree of neutralization according to the invention.
  • the polymerization can be carried out with at least one monomer carrying at least one strong acid function.
  • the polymerization is preferably carried out with a concentration of monomers carrying at least one strong acid function relative to all the monomers used by less than 50%, and preferably less than 30%.
  • the polymerization may, for example, be carried out with a monomer carrying at least one strong acid function which in free form is chosen from acrylamidoalkylsulphonic acids, such as 2-acrylamido-2-methylpropanesulphonic acid (ATBS).
  • ATBS 2-acrylamido-2-methylpropanesulphonic acid
  • the polymerization may, for example, be conducted with a combination acrylic acid / ATBS or acrylic adde / ATBS / acrylamide, the acidic monomers may be in free form or with a degree of neutralization according to the invention.
  • monomer carrying at least one acid function is meant a monomer carrying one or more free or neutralized acid function (s) (that is to say salified by action of a base).
  • the acid function (s) may be a weak acid or strong acid function.
  • a monomer used in the context of the invention will comprise only weak acid functions or strong acid functions, and most often monomers carrying a single acid function will be used. The same definitions and preferences apply to the monomeric units present on the polymer obtained.
  • a monomer carrying at least one free acid weak function in the free form of the -COOH type
  • a monomer carrying a strong acid function in free form mention may be made of monomers bearing a phosphonic acid or sulphonic acid function, such as acrylamidoalkylsulphonic acids such as 2-acrylamido-2-methylpropane acid. sulfonic acid.
  • the acidic functions are in anionic form with a counterion or base-dependent cation used for neutralization, for example of the Na + type when the sodium hydroxide is used or NH 4 + when the ammonia is used. .
  • a counterion or base-dependent cation used for neutralization, for example of the Na + type when the sodium hydroxide is used or NH 4 + when the ammonia is used.
  • the control of the number of acid functions in neutralized form is ensured by the choice of the pH of the aqueous monomer solution which will be adjusted according to the pKa of the acid functions present.
  • the polymerization may involve a single type of monomer, then chosen from monomers carrying at least one weak acid function or different types of monomers, at least one of which carries at least one weak acid function, with a proportion of acid functions present on the monomers used, and thus on the copolymer obtained, in a neutralized form which is less than or equal to 20%.
  • the polymer obtained may contain other monomeric units such as monomeric units carrying at least one strong acid function, monomeric units. neutral (or nonionic), cationic monomeric units and / or monomeric units with hydrophobic character.
  • the training conditions of the aqueous phase and polymerization are such that the acid functions of the monomers involved remain predominantly in free form, and are not neutralized by formation of a salified form, or weakly neutralized with a limited neutralization rate of less than or equal to 20% .
  • a neutralization of less than or equal to 20% takes place, it is generally carried out in the aqueous phase, by adding an appropriate amount of base.
  • a base such as sodium hydroxide or ammonia may be used.
  • the polymerization reaction may be carried out with at least one neutral monomer chosen from acrylamide, methacrylamide, N, N-dimethylacrylamide, N-vinylmethylacetamide, N-vinylformamide, vinyl acetate and diacetoneacrylamide.
  • neutral monomer chosen from acrylamide, methacrylamide, N, N-dimethylacrylamide, N-vinylmethylacetamide, N-vinylformamide, vinyl acetate and diacetoneacrylamide.
  • the polymerization can be carried out with from 30 to 99 mol% of at least one monomer having one or more weak acid function (s) and from 1 to 70 mol% of at least one neutral monomer.
  • the polymerization may, for example, be carried out with a combination of acrylic acid / acrylamide, the acrylic acid being in neutral form or with a degree of neutralization according to the invention.
  • diallyldialkyl ammonium salts such as diallyl dimethyl ammonium chloride (DADMAC); acidified or quaternized salts of dialkylaminoalkyl acrylates and methacrylates, in particular dialkylaminoethyl acrylate (ADAME) and dialkylaminoethyl methacrylate (MADAME); acidified or quaternized salts of dialkylaminoalkylacrylamides or methacrylamides, for example methacrylamido-propyl trimethyl ammonium chloride (MAPTAC), acrylamido-propyl trimethyl ammonium chloride (APTAC) and Mannich products such as quaternized dialkylaminomethylacrylamides.
  • DADMAC diallyl dimethyl ammonium chloride
  • ADAME dialkylaminoethyl acrylate
  • MADAME dialkylaminoethyl methacrylate
  • MADAME dialkylaminoethyl methacrylate
  • the acidified salts are obtained by the means known to those skilled in the art, and in particular by protonation.
  • the quaternized salts are also obtained by means known to those skilled in the art, in particular, by reaction with benzyl chloride, methyl chloride (MeCl), aryl chlorides, alkyl, or dimethylsulfate.
  • hydrophobic monomers examples include undecanoic acid acrylamide, undodecyl methyl acrylamide acid, acrylic acid derivatives such as alkyl acrylates or methacrylates, for example ethoxylated behenyl methacrylate.
  • the molar percentage of hydrophobic monomers with respect to all the monomers used is preferably less than 10%, and generally between 0.001% and 7%. Copolymers obtained with such hydrophobic monomers give associative copolymers.
  • all the monomers carrying at least one acid function used to carry out the polymerization are monomers carrying at least one weak acid function.
  • the polymerization is carried out with at least one monomer carrying at least one strong acid function, in addition to at least one monomer carrying at least one weak acid function.
  • the molar percentage of monomers carrying at least one strong acid function relative to all the monomers used is preferably less than 50%, very preferably less than 30%.
  • the copolymers obtained according to the method of the invention may in particular be formed from a combination of at least one unit monomeric carrier carrying at least one weak acid function and at least one monomeric unit carrying at least one strong acid function, and in particular corresponding to an acrylic acid / ATBS copolymer, these acid monomers being in neutral form or with a neutralization according to the invention; a combination of at least one monomeric unit carrying at least one weak acidic function with at least one neutral monomeric unit and optionally at least one monomeric unit carrying at least one strong acid function, and in particular corresponding to a copolymer acrylic acid / acrylamide or an acrylic acid / ATBS / acrylamide copolymer, the acrylic acid and the ATBS being in neutral form or with a degree of neutralization according to the invention; a combination of at least one monomeric unit carrying at least one weak acid function with at least one cationic monomeric unit and optionally at least one monomeric unit carrying at least one strong acid function; or a combination of at least one monomeric unit carrying at least one weak acid
  • the monomers are put in aqueous solution.
  • This aqueous solution corresponds to the aqueous phase of the inverse emulsion.
  • at most 20% of the acid functions present on the monomers having at least one acid function are in neutralized form.
  • transfer agent otherwise known as a chain limiter agent.
  • the use of a transfer agent is particularly advantageous for controlling the molecular weight of the polymer obtained.
  • transfer agent mention may be made of methanol, isopropanol, sodium hypophosphite, 2-mercaptoethanol, sodium methallysulfonate and mixtures thereof.
  • the aqueous solution of step a) has a total concentration of monomers, a molar percentage of monomers carrying at least one weak acid function with respect to all the monomers used and a neutralization rate of the acid functions. present on the monomers having at least one acid function in accordance with the process described in the context of the invention.
  • the emulsification step (b) of the aqueous phase in the oil phase will preferably be carried out by adding the aqueous phase to the oil phase maintained with stirring.
  • the polymerization reaction is carried out in the presence of a water-in-oil emulsifier.
  • a water-in-oil emulsifier is most often introduced into the oil phase in which the aqueous solution is emulsified.
  • emulsifying agent of the water-in-oil (W / O) type is meant an emulsifying agent having a sufficiently low HLB value to provide water-in-oil emulsions, and in particular an HLB value of less than 10.
  • HLB % by weight of the hydrophilic part / 5
  • the weight percentage of the hydrophilic portion is the ratio of the molecular weight of the hydrophilic portion to the total molecular weight of the molecule.
  • surfactant polymers such as polyesters with a molecular weight between 1000 and 3000 g / mol, products of the condensation between a poly (isobutenyl) succinic acid or its anhydride and a polyethylene glycol, block copolymers with a molecular weight between 2500 and 3500 g / mol, for example those marketed under the names HYPERMER®, sorbitan extracts, such as sorbitan monooleate, sorbitan isostearate or sesquioleate sorbitan, certain polyethoxylated sorbitan esters, such as pentaethoxylated sorbitan monooleate or pentaethoxylated sorbitan isostearate, or diethoxylated oleocetyl alcohol, tetraethoxylated lauryl acrylate.
  • surfactant polymers such as polyesters with a molecular weight between 1000 and 3000 g / mol
  • the aqueous solution contains the monomer (s) and optionally the branching agent and the transfer agent. It may also contain complexing agents such as ethylene diamine or ethylene diamine tetraacetic acid.
  • step c) is initiated by introduction into the emulsion formed in step b) of a free radical initiator.
  • a free-radical initiator agent mention may be made of the oxidizing-reducing pairs with, among the oxidants, cumene hydroperoxide or tertiary butythydroxyperoxide, and among the reducing agents, persulfates such as sodium metabisulphite and salt. from Mohr. Azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis hydrochloride (2-aminopropane) can also be used.
  • the polymerization is generally carried out isothermally, adiabatically or at a controlled temperature. That is, the temperature is kept constant generally between 10 and 50 ° C (isothermal), or the temperature is allowed to increase naturally (adiabatic) and in this case the reaction is generally started at a temperature below 10 ° C and the final temperature is generally above 50 ° C, or finally the rise in temperature is controlled to obtain a temperature curve between that of the isotherm and that of adiabatic.
  • oil-in-water emulsifying agents preferably at a temperature below 50 ° C.
  • emulsifying agent of the oil-in-water (O / W) type is meant an emulsifying agent having a sufficiently high HLB value to provide oil-in-water emulsions and in particular an HLB value of greater than 10.
  • oil-in-water emulsifying agents mention may be made of ethoxylated sorbitan esters such as ethoxylated sorbitan oleate with 20 equivalents of ethylene oxide (EO 20), polyethoxylated sorbitan laurate with 20 moles of ethylene oxide, polyethoxylated castor oil with 40 moles of ethylene oxide, decaethoxylated oleodecyl alcohol, heptaethoxylated lauric alcohol, or polyethoxylated sorbitan monostearate with 20 moles of ethylene oxide.
  • EO 20 ethylene oxide
  • polyethoxylated sorbitan laurate with 20 moles of ethylene oxide
  • the quantities of emulsifying agent (s) introduced are such that the inverse emulsion of the polymer obtained will generally contain from 1% to 10% by weight, and preferably from 2.5% to 9% by weight, emulsifiers of the water-in-oil type (W / O) and optionally from 2% to 10% by weight, and preferably from 2.5% to 6% by weight of oil-in-water emulsifiers (H / E).
  • the mass ratio of the aqueous phase to the oil phase is 50/50 to 90/10.
  • the oil phase used in the inverse emulsion polymerization process may be composed, for example, of a mineral oil, in particular a commercial oil, containing saturated hydrocarbons of paraffinic, isoparaffinic, cycloparaffinic and naphthalic type having room temperature (22 ° C), a density between 0.7 and 0.9; a vegetable oil; a synthetic oil such as hydrogenated polydecene or hydrogenated polyisobutene; an ester such as octyl stearate or butyl oleate; a vegetable oil such as squalane of vegetable origin; or a mixture of several of these oils.
  • a mineral oil in particular a commercial oil, containing saturated hydrocarbons of paraffinic, isoparaffinic, cycloparaffinic and naphthalic type having room temperature (22 ° C), a density between 0.7 and 0.9
  • a vegetable oil a synthetic oil such as hydrogenated polydecene or hydrogenated polyisobutene
  • the resulting emulsion is diluted or concentrated.
  • the inverse emulsions thus obtained can be concentrated, for example by distillation. Inverse emulsions are obtained, the polymer concentration of which can be between 30 and 75% by weight, preferably between 40 and 65% by weight.
  • the polymers obtained from the inverse emulsions subsequently subjected to an isolation step may be in the form of a powder.
  • Such an isolation step may, for example, be selected from the techniques of precipitation, azeotropic distillation and spray drying.
  • the polymers obtained after such steps retain their advantageous properties, in terms of thickening capacity and in terms of resistance to surfactants.
  • the polymerization is most often followed by a neutralization step, otherwise called a post-neutralization step, of at least a part, or even all, of the free acid functions present on the polymer.
  • a neutralization step otherwise called a post-neutralization step
  • it leads, preferably, to a percentage of neutralization with respect to all the acid functions present on the polymer from 30 to 100%.
  • the neutralization is carried out using a base, similar to the monomer neutralization previously described in the context of the polymerization process, the nature and amounts of which are selected by those skilled in the art.
  • polymers thus neutralized, offer much better thickening properties and resistance to surfactants, all other conditions being equal, compared to polymers obtained by inverse emulsion polymerization which do not satisfy the concentration and neutralization conditions of the monomers as defined in the process according to the invention. the invention. Particularly after neutralization, the polymers offer advantageous properties over polymers consisting of the same monomers but prepared by inverse emulsion polymerization directly at higher neutralization rates and / or at a different total monomer concentration.
  • the polymers used in the context of the invention allow after complete neutralization of the free acid functions present, or at least greater neutralization, to thicken much more effectively aqueous media present in detergent compositions.
  • the manufacture of detergent compositions is widely known to those skilled in the art. It generally consists of successively adding one or more cleaning surfactants and other ingredients such as additives in an aqueous solution.
  • the addition of the acrylic thickening polymer described above can be done at any stage of the manufacture of the detergent composition.
  • the detergent composition preferably comprises from 0.01% to 10% by weight of thickening acrylic polymer described above, and preferably from 0.1 to 5% by weight, these percentages being given relative to the total mass of the composition.
  • the neutralization step leading to a percentage of neutralized acid functions of 30 to 100% with respect to all the acid functions present on the polymer can be done before or after the incorporation of the polymer in the composition.
  • the advantageous properties of the polymer obtained by inverse emulsion polymerization according to the method described above retain its advantageous properties, whether it is in the form of a more or less concentrated inverse emulsion, a powder or a aqueous solution. Therefore, the thickening polymer according to the invention can be introduced into the detergent composition, in the form of an inverse emulsion, a powder or in solubilized form, for example in water or an organic solvent, or else in aqueous or organic dispersion form. Generally it is a form solubilized polymer in water that is introduced into the composition, obtained either by inversion of an inverse emulsion in water, or by dissolution of a powder in water. Whatever the form in which it is introduced, in the detergent composition at the time of its use, the polymer will be in a solution, or aqueous phase in the case of a multi-phasic composition, in which it plays its role of thickener and stabilizer.
  • the composition according to the invention comprises an so-called aqueous part composed of water and hydrophilic compounds.
  • the composition may be in the form of a single aqueous portion (solution or gel) constituting the entire composition or an aqueous dispersion comprising solid particles such as mineral microparticles improving the cleaning properties.
  • aqueous phase the part of the composition comprising water and the hydrophilic components of the composition, and in particular the components that are soluble or miscible with water, even in the case of single-phase compositions, or even consisting exclusively of such an aqueous phase.
  • the composition may comprise, in addition to water, at least one hydrophilic organic solvent such as alcohols, and especially linear or branched C 1 -C 6 monoalcohols, such as ethanol, tert-butanol and n-butanol. , isopropanol or n-propanol, and polyols such as glycerine, diglycerine, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or alternatively glycols ethers including C 2 and aldehydes C 2 -C 4 hydrophilic.
  • the aqueous phase may contain all the ingredients conventionally used in a detergent composition and, generally, water-soluble.
  • the detergent composition preferably contains from 10 to 99% by weight of water, preferably more than 20% by weight, and very preferably from 30 to 95% by weight, these percentages being given with respect to the total mass of the composition.
  • the detergent composition may contain between 1 and 50% by weight of hydrophilic organic solvent as described above. She can also contain between 0.1 and 20% by mass of solid particles.
  • solid particles include inorganic solid particles such as silica or titanium dioxide, organic solid particles such as certain polymers (polyhydroxybutyric acid, polycaprolactone, polyorthoester, polyanhydride), capsules enclosing additives such as a perfume or a soap , a fabric softener, said particles generally having a micro-particulate or nano-particle size.
  • the detergent compositions correspond to the compositions traditionally used in this field.
  • the documents FR 2 766 838 , FR 2,744,131 , EP 0 759 966 B1 US 6,274,539 , US 2006/0281660 , US 7,973,004 and GB 2,346,891 some relevant parts of which are reproduced below.
  • the composition may also advantageously comprise at least one surfactant.
  • This surfactant may be chosen from anionic, amphoteric, nonionic or cationic surfactants or mixtures thereof.
  • the composition will comprise a surfactant corresponding to a water-in-oil emulsifier and / or an oil-in-water emulsifier, preferably chosen from those previously mentioned in the context of the polymerization process of the acrylic thickening polymer.
  • the composition will comprise one or more cleaning surfactants.
  • the composition contains one or more cleaning surfactants, these typically represent from 0.1% to 50% by weight, and preferably from 1% to 30% by weight, of the total mass of the composition.
  • the cleaning surfactants which may be incorporated in the composition according to the invention include a variety of nonionic, cationic, anionic and zwitterionic surfactants, such as those described in US Pat. Mc Cutcheon 's detergents and Emulsiffers, North American Edition (1996), Allured Publishing Corporation , and in the following documents: FR 2 766 838 , FR 2,744,131 , GB 2,346,891 , US 20060281660 , US 6,274,539 and EP 0 759 966 , especially.
  • compositions according to the invention will comprise one or more cleaning surfactants chosen from anionic or nonionic surfactants.
  • the composition may comprise one or more anionic or nonionic cleaning surfactants.
  • the anionic or nonionic cleaning surfactants may be used in an amount such that the total amount of anionic surfactant (s) and / or nonionic surfactant (s) represents from 0.1% to 50% by weight. mass, and preferably from 1% to 30% by weight, of the total mass of the composition.
  • the nonionic surfactant (s) present in the compositions according to the invention will have, for example, a HLB value ("Hydrophilic-Lipophilic Balance") of 8 to 13, and preferably of 9, 5 to 11.
  • HLB value Hydrophilic-Lipophilic Balance
  • anononic or nonionic cleaning surfactant s
  • hydrophilic part of which contains one or more saccharide units hydrophilic part of which contains one or more saccharide units
  • the detergent compositions may include, instead of or in addition to such anionic or nonionic surfactants, one or more zwitterionic (s) or cationic surfactant (s).
  • zwitterionic s
  • cationic surfactant s
  • zwitterionic cleaning surfactant By way of examples of zwitterionic cleaning surfactant, mention may be made of the aliphatic compounds of quaternary ammonium, of phosphonium and of C 8 -C 18 sulphonium, which carry a substituent containing an anionic group for solubilization in water, such as carboxy, sulfonate, sulfate, phosphate, phosphonate, and the like, alkyl aminosulphonates, alkyl betaines, and alkyl amido betaines (e.g., (cocoamylamidopropylbetaine), stearamidopropyldimethylamine, diethylaminoethylstearamide, dimethylstearamine, dimethylsojamine, soyamine, myristylamine, tridecylamine, ethylstearylamine, N-tallowpropartediamine, ethoxylated stearylamine (5 moles of ethylene oxide
  • quaternary ammonium salts having three lower (C 1 to C 4) alkyl groups (preferably methyl groups) and a long-chain (C 8 to C 20) alkyl group. for example (coconut) trimethylammonium chloride; alkylpyridinium salts and other compounds in which the pyridine nitrogen atom takes a quaternary form, for example as in an alkylpyridinium bromide, preferably with C10-C20 alkyl chains, preferably C12 to C18.
  • the detergent compositions according to the invention will also contain, most often, one or more additives chosen from: detergency builders (also called “builders”), antifouling agents, anti-redeposition agents, bleaching agents, fluorescers (also called optical brighteners), suds suppressors (also called antifoaming agents), enzymes, chelating agents, neutralizing agents and pH adjusting agents.
  • detergency builders also called “builders”
  • antifouling agents anti-redeposition agents
  • bleaching agents also called fluorescers (also called optical brighteners), suds suppressors (also called antifoaming agents)
  • enzymes also called antifoaming agents
  • chelating agents neutralizing agents and pH adjusting agents.
  • Ad j uvants detergency also called “builders”.
  • Such detergents also known as “builders” are complexing agents that make it possible to complex the ions of water that have a detrimental effect during cleaning, in particular in the case of cleaning with hard water.
  • Such an agent will, in particular, be incorporated in compositions for cleaning the dishes, for dishwashers.
  • the composition comprises a single or more bleaching agent (s), it will also preferably comprise a bleach activator generating in situ in the washing medium, a peroxy carboxylic acid; among these activators, mention may be made of tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, glycerol trialkalates such as pentaacetyl glucose and octaacetyl lactose, etc.
  • a bleach activator generating in situ in the washing medium, a peroxy carboxylic acid
  • these activators mention may be made of tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, glycerol trialkalates such as pentaacetyl glucose and
  • the composition may comprise a single or more fluorescent agent (s), particularly when the composition is a laundry detergent. They may be used in an amount such that the total amount of fluorescent agent (s) represents from 0.05 to 1.2% by weight of the total mass of the composition.
  • fluorescent agents mention may be made of: stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methine, cyanines, thiophenes, etc.
  • the composition may comprise one or more enzyme (s), particularly when the composition is a laundry detergent. They may be used in an amount such that the total amount of enzyme (s) represents from 0.005 to 0.5% by weight of the total mass of the composition.
  • enzymes include proteases (for example Alcalase or Savinase, marketed by Novo Nordisk), amylases, lipases, cellulases and peroxidases.
  • chelating agents which may be incorporated into the composition
  • EDTA ethylenediaminetetraacetic acid
  • salts thereof such as disodium EDTA; cyclodextrins; and their analogues.
  • the composition typically represents from 0.001% to 3% by weight, of the total mass of the composition, preferably from 0.01% to 2% by weight, and preferably from 0.01% to 1% by weight, of the total mass of the composition.
  • One or more thickening polymers may also be incorporated in the detergent compositions according to the invention. These polymers may be natural, semi-natural or synthetic polymers.
  • chitin chitosan and their derivatives
  • gum arabic agar, guar gum, locust bean gum, gum gum, karaya gum, xanthan gums and alginates.
  • polymers based on acrylamide, sodium acrylate, vinylpyrrolidone or 2-acrylamido-2-methylpropanesulphonic acid for example obtained by other polymerization processes than that described in the context of the invention, and in particular by precipitation polymerization.
  • neutralizing agents and / or one or more pH adjusting agents may be included in the composition to bring the pH of the composition to the desired levels.
  • neutralizing agents and pH adjusting agents include triethanolamine, aminomethylpropanol, ammonium hydroxide, sodium hydroxide, other alkali hydroxides, alkali metal silicates, such as sodium carbonate, alkali silicates such as sodium silicate, ascorbic acid and salts thereof, sorbic acid and salts thereof, phosphoric acid and salts thereof. it, citric acid and salts thereof, lactic acid and salts thereof, glycolic acid and salts thereof, boric acid and salts thereof. here, acetic acid and salts thereof, and their analogues.
  • the neutralization agent (s) and the pH adjusting agent (s) are used in the composition of the invention in an amount sufficient to provide a pH ranging from 4 to 10.
  • the ) pH adjusting agent (s) is (are) used in an amount sufficient to give the composition a pH ranging from 4.5 to 8, and preferably from 5 to 7.5.
  • the aqueous phase is gradually transferred to the organic phase.
  • the pre-emulsion thus formed is then subjected to high shear for 1 minute (Ultra Turrax, IKA).
  • the inverse emulsion is then degassed for 30 minutes by simply sparging with nitrogen.
  • aqueous solution containing 1.0% by weight of sodium metabisulphite is then added at a flow rate of 2.5 ml / h for a period of 1 hour 30 minutes. Once the maximum temperature is reached, the temperature of the reaction mixture is maintained for 60 minutes before cooling.
  • Example 2 The same procedure as in Example 1 is carried out by adding to the aqueous phase 5.83 g of 50% sodium hydroxide solution, while maintaining the same weight of aqueous phase by adjusting the amount of deionized water.
  • the aqueous phase is gradually transferred to the organic phase.
  • the pre-emulsion thus formed is then subjected to high shear for 1 minute (Ultra Turrax, IKA).
  • the inverse emulsion is then degassed for 30 minutes by simply sparging with nitrogen.
  • the polymers used in the context of the invention obtained by the inverse emulsion polymerization process have a thickening effect which is much greater than the polymers obtained by inverse emulsion processes which do not satisfy the conditions of% neutralization before polymerization and concentration of monomers. .
  • the polymers obtained according to the invention are very effective at very low concentration.
  • ком ⁇ онент to surfactants is evaluated by using these same polymers in deionized water and in the presence of a surfactant: sodium lauryl ether sulphate (LES), marketed by BASF under the Texapon® NSO reference.
  • LES sodium lauryl ether sulphate
  • the polymers are compared with each other and with other commercially available thickening polymers: Acusol®820 (Rhom & Haas), an anionic copolymer based on ethyl acrylate and acrylic acid and containing a hydrophobic monomer, obtained by polymerization in emulsion (not inverse) and Carbopol® 676 (Lubrizol), a crosslinked acrylic acid polymer obtained by precipitation polymerization. These commercial products are typically used in detergent compositions as a thickening agent
  • the polymers of Examples 1 to 5 make it possible to obtain a lower drop in viscosity and therefore good resistance to surfactants compared with the polymers of Comparative Examples 1 to 4 and Carbopol® 676 and Acusol® 820.
  • the polymers of Examples 1 to 5 make it possible to obtain very good resistance to surfactants compared with the polymers of Comparative Examples 1 to 4 and Carbopol® 676 and Acusol® 820, with different surfactants.
  • Laundry detergent is formulated with the inverse emulsion of Example 1 or with the Acusol ® 820, market reference in this type of formulation.
  • a detergent product for dishwashers is formulated with the inverse emulsion of Example 3 and Carbopol® 676, market reference in this type of formulation.
  • compositions numbered 1 and 2 For each of the compositions numbered 1 and 2 below, the preparation protocol applied is as follows:
  • composition N ° 1 Laundry detergent
  • This formulation corresponds to a basic liquid detergent whose viscosity is controlled by the presence of an acrylic polymer.
  • the assay is adjusted to obtain a viscosity of 800 cps +/- 200 cps (Brookfield RVT, 20 rpm, sp 3)
  • the preparation procedure is simple, it consists in adding in the order presented in Table 6 below, all the ingredients of the following formulation in a 400 ml beaker to obtain 250 g of solution in the end: ⁇ b> Table 6 ⁇ / b> ingredients % by weight Remarks Deionized water QCP 100% We start at 70% and adjust at the end of the process.
  • Example 1 makes the laundry formulation containing 23% surfactant much more effective than Acusol® 820.
  • Composition N ° 2 Liquid product for dishwasher
  • This formulation corresponds to an opaque liquid gel "javellisé for washing machine whose viscosity is controlled thanks to the presence an acrylic polymer.
  • the dosage is adjusted to obtain a viscosity of 9000 cps +/- 2000 cps (Brookfield RVT, 20 rpm, sp 6)
  • the preparation procedure is simple, it consists in adding in the order presented in Table 7 below, all the ingredients of the following formulation in a 400 ml beaker, to obtain 250 g of solution in the end: ⁇ b> Table 7 ⁇ / b> ingredients % by weight Remarks Deionized water QCP 100% We start at 50% and adjust at the end of the process. Stirring trip 500 rpm Acrylic polymer * 3.0% Mix about 30 minutes Sodium carbonate 10.0% Add slowly to 250 rpm.
  • Example 3 thickens the laundry formulation much more effectively for laundry containing 3% surfactant compared to Carbopol® 676.

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EP15759892.1A 2014-08-06 2015-08-05 Utilisation dans des compositions détergentes de polymères obtenus par polymérisation en émulsion inverse basse concentration avec un faible taux de monomères neutralises Not-in-force EP3177703B1 (fr)

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PCT/FR2015/052164 WO2016020622A1 (fr) 2014-08-06 2015-08-05 Utilisation dans des compositions détergentes de polymères obtenus par polymérisation en émulsion inverse basse concentration avec un faible taux de monomères neutralises

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CN107018667A (zh) 2017-08-04
MX2017001486A (es) 2017-05-23
FR3024736B1 (fr) 2016-08-26
CN107018667B (zh) 2019-11-05
US20170218308A1 (en) 2017-08-03
FR3024736A1 (fr) 2016-02-12
BR112017002282A2 (pt) 2018-01-16
EP3177703A1 (fr) 2017-06-14
ES2716416T3 (es) 2019-06-12
WO2016020622A1 (fr) 2016-02-11
US10407649B2 (en) 2019-09-10
TR201903816T4 (tr) 2019-04-22

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