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
  • 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
  • C11D17/0013—Liquid compositions with insoluble particles in suspension
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0031—Carpet, upholstery, fur or leather cleansers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • 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
  • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
• • 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
  • 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
  • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3796—Amphoteric polymers or zwitterionic polymers

Definitions

• the present invention relates to a method for increasing the cleaning properties of an aqueous composition intended for cleaning a surface soiled by soiling, by adding, to said aqueous cleaning composition, at least one polymer in insoluble particulate form. It also relates to the use, in an aqueous composition intended for cleaning a surface soiled by a fouling, of at least one polymer in insoluble particulate form, as agent making it possible to improve the elimination of the fouling of the soiled surface. It also relates to a method for cleaning a surface soiled by dirt.
• the polymer used is a copolymer with sulfur functions in ionic form (preferably with sulphonated or sulphated functions).
• Soft surfaces such as various textiles, hair, human skins, and hard surfaces such as cement, ceramics, bricks, metals are contaminated by various soils which are difficult to remove; indeed very often these soils are linked to the support which they soil by strong chemical or electrostatic bonds which it is difficult to remove.
• Various methods of encapsulating this soiling have already been proposed with various encapsulating products, then removing the encapsulated soiling by various means such as sweeping and aspiration. Unfortunately, the known encapsulating agents participate in and even accentuate the phenomenon of attraction of the encapsulated dirt on the soiled support.
• a first object of the invention consists in a method for increasing the cleaning properties of an aqueous cleaning composition comprising at least one surfactant, intended for cleaning a surface soiled by dirt, by addition to said cleaning composition, at least one polymer (P) comprising - hydrophobic monomer units (N) which are uncharged or non-ionizable at the pH of use of the composition of the invention,
• hydrophilic monomer unit (F) chosen from the monomer units * (F1) cationic or potentially cationic at the pH of use of said composition
• the method for cleaning a surface soiled with dirt can comprise the following steps: a) coating the surface to be cleaned with an effective amount of aqueous cleaning composition comprising the polymer (P) which is not soluble under the conditions of use in the medium aqueous of said composition, b) drying the surface to evaporate the water of the composition and generate the polymer (P) of the dispersion which forms a polymer composite product (P)
• said monomer units (N) and (F) are derived from monoethylenically unsaturated ⁇ - ⁇ monomers; preferably, said monomer units (R) are derived from diethylenically unsaturated monomers.
• the average molar mass of said polymer (measured by gel permeation chromatography (GPC) THF and expressed in polystyrene equivalents) may preferably be at least 20,000 g / mol.
• monomers from which the hydrophobic units (N) are derived there may be mentioned: • vinylaromatic monomers such as styrene, vinyltoluene ...
• alkyl esters of monoethylenically unsaturated ⁇ - ⁇ acids such as methyl and ethyl acrylates and methacrylates, etc.
• N, N (dialkylamino ⁇ alkyl) amides of monoethylenically unsaturated ⁇ - ⁇ carboxylic acids such as N, N-dimethylaminomethyl acrylamide or methacrylamide, N, N-dimethylaminoethyl acrylamide or methacrylamide, N, N-dimethylamino-3-propyl acrylamide or methacrylamide, N, N-dimethylaminobutyl acrylamide or methacrylamide
• monoethylenically unsaturated ⁇ - ⁇ aminoesters such as dimethyl aminoethyl methacrylate (DMAM), dimethyl aminopropyl methacrylate, ditertiobutylaminoethylmethacrylate, dipentylaminoethylmethacrylate
• DMAM dimethyl aminoethyl methacrylate
• dimethyl aminopropyl methacrylate dimethyl aminopropyl methacrylate
• ditertiobutylaminoethylmethacrylate dipentylaminoethylmethacrylate
• monomers that are precursors of amino functions such as N-vinyl formamide, N-vinyl acetamide, etc. which generate primary amine functions by simple acid or basic hydrolysis.
• monomers from which the hydrophilic units are derived are monomers that are precursors of amino functions such as N-vinyl formamide, N-vinyl acetamide, etc. which generate primary amine functions by simple acid or basic hydrolysis.
• N N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine (SPE from RASCHIG), N, N-dimethyl-N- (2-methacrylamidoethyl) -N- (3-sulfopropy! ammonium betaine (SPP from RASCHIG), 1-vinyl-3- (3-sulfopropyl) imidazolidium betaine, 1- (3-sulfopropyl) -2-vinylpyridinium betaine (SPV from RASCHIG),
• N (dialkylamino ⁇ alkyl) amides of ethylenically unsaturated ⁇ - ⁇ carboxylic acids such as N, N-dimethylaminomethyl acrylamide or methacrylamide, N, N-dimethylamino-3-propyl acrylamide or methacrylamide, or ethylenically unsaturated aminoesters such as ditertiobutylaminoethylmethacrylate, dipentylaminoethylmethacrylate, with an alkali metal chloroacetate (sodium in particular) or propane sultone.
• monomers from which the anionic or potentially anionic hydrophilic units (F3) are derived there may be mentioned:
• monomers having at least one carboxylic function such as ethylenically unsaturated ⁇ - ⁇ carboxylic acids or anhydrides, acrylic, methacrylic, maleic, fumaric acids or anhydrides, itaconic, N-methacroyl alanine, N-acryloyl-hydroxy-glycine and their water-soluble salts
• monomers having at least one sulfur function preferably sulphate or sulphonate, such as 2-sulphooxyethyl methacrylate, vinylbenzene sulphonic acid, allylsulphonic acid, 2-acrylamido-
• monomers having at least one phosphonate or phosphate function such as vinylphosphonic acid, vinyldiphosphonic acid, esters of ethylenically unsaturated phosphates such as phosphates derived from hydroxyethyl methacrylate (Empicryl 6835 from RHODIA) and those derived from methacrylates of polyoxyalkylenes and their water-soluble salts
• monoethylenically unsaturated ⁇ - ⁇ monomers which are precursors of anionic function (s), such as those whose hydrolysis generates carboxylate functions (tert-butyl acrylate, dimethyl aminoethyl acrylate, maleic anhydride, etc.) examples of monomers from which the hydrophilic units (F4) derived from uncharged or non-ionizable compounds may be mentioned:
• hydroxyalkyl esters of ⁇ - ⁇ ethylenically unsaturated acids such as hydroxyethyl and hydroxypropyl acrylates and methacrylates, etc.
• amides of ⁇ - ⁇ ethylenically unsaturated acids such as acrylamide, N, N-dimethyl methacrylamide, N-methylolacrylamide ...
• Said polymers (P) are in insoluble particulate form; the diameter of said particles can range from 5 to 500 nm, preferably from 5 to 300 nm, very particularly from 5 to 100 nm, even more particularly from 10 to 50 nm.
• Aqueous dispersions (latex) of said polymer (P) can be obtained in a known manner by radical polymerization in aqueous medium of the ethylenically unsaturated monomers. Methods for obtaining nanoparticulate latexes of small diameter are described in Colloid Polym. Sci. 266: 462-469 (1988) and in Journal of Colloid and Interface Science. Flight. 89. No 1, September 1982 pages 185 and following.
• a method of preparing latex of particles of average size less than 100 nm, in particular of average size ranging from 1 to 60 nm, very particularly from 5 to 40 nm is described in EP-A-644 205.
• the choice and the relative amounts of the monomer (s) from which the unit (s) (N), (F) and (R) of the polymer (P) are derived are such that said polymer (P) has a glass transition temperature Tg of the of the order of - 40 ° C to 150 ° C, preferably of the order of 0 to 110 ° C, very particularly of the order of 40 to 110 ° C and remains insoluble under the conditions of use of the composition of l 'invention.
• said polymer (P) is considered to be insoluble when less than 15%, preferably less than 10% of its weight, is soluble in the aqueous or wet medium of use of the composition of the invention, it that is to say in particular under the temperature and pH conditions of said medium.
• the pH of use of the composition of the invention can range from approximately 1 to approximately 12, depending on the desired use. As it's about
• the pH is generally between 3 and 7, preferably 4 and 6;
• the pH of the detergent bath is generally of the order of 7 to 11, preferably of 8 to 10.5;
• the pH of the rinsing and / or softening bath is generally of the order of 2 to 8;
• a washing additive ("prespotter"), the pH to be considered is that of the pH of the washing bath of the following washing operation, namely of the order 7 to 11, preferably from 8 to 10.5;
• the pH of the detergent bath ranges from 1 to 11.
• At least 70% of the total mass of said polymer (P) is formed of hydrophobic unit (s) (N).
• hydrophilic units (F) When hydrophilic units (F) are present, these preferably do not represent more than 30% of the total mass of the polymer (P).
• crosslinking units (R) When crosslinking units (R) are present, these generally do not represent more than 20%, preferably not more than 10%, especially not more than 5% of the total mass of the polymer (P).
• a first embodiment of the invention consists of a method for increasing the cleaning properties of a composition by adding particles of at least one uncharged or non-ionizable polymer (P1) comprising
• said uncharged or non-ionizable polymer (P1) comprises:
• Said uncharged or non-ionizable polymer (P1) can be used in all types of compositions for cleaning the carpets and rugs mentioned above, the use pH of which can range from 2 to 12, namely, formulations detergents, rinse and / or softening formulations, drying additives, foams or washing additives.
• a second embodiment of the invention consists of a process for increasing the cleaning properties of a composition by adding particles of at least one polymer (P2) having anionic or anionizable units and free of cationic or cationizable units, comprising
• hydrophilic monomer units F4 uncharged or non-ionizable.
• Said polymer (P2) can be used in compositions for cleaning carpets and rugs of a non-cationic nature, namely, detergent formulations, foams, drying additives, or washing additives, or in detergent formulations for cleaning hard surfaces.
• a third embodiment of the invention consists of a method for increasing the cleaning properties of a composition by adding particles of at least one polymer (P3) having amphoteric units, comprising
• optionally hydrophilic monomer units (F4) uncharged or non-ionizable • optionally hydrophilic monomer units (F1) cationic or cationizable, all the hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer ( P3), and the molar ratio of cationic charges to anionic charges which can range from 1/99 to 80/20 depending on the desired use of the composition (C3) thus obtained.
• Said polymer (P3) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 can be used in drying additives and aqueous ironing formulations or in detergent formulations for cleaning surfaces hard.
• Said polymer (P3) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 60/40, preferably from 5/95 to 50/50, can also be used in detergent formulations and additives carpets and rugs or in detergent formulations for cleaning hard surfaces.
• a fourth embodiment of the invention consists of a method for increasing the cleaning properties of a composition by adding particles of at least one polymer (P4) having both units cationic or cationizable and anionic or anionizable units, comprising
• hydrophilic monomer units (F4) uncharged or non-ionizable, all the hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer (P4), and the molar ratio of cationic charges to charges anionics which can range from 1/99 to 80/20 depending on the desired use of the composition (C4) thus obtained.
• Said polymer (P4) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 can be used in drying additives and aqueous ironing formulations.
• a fifth embodiment of the invention consists of a method for increasing the cleaning properties of a composition by adding particles of at least one polymer (P5) having cationic or cationizable units and free of anionic or anionizable units, comprising
• Said polymer (P5) can be used in all the types of laundry cleaning compositions mentioned above, the use pH of which can range from 2 to 12, namely, detergent formulations, rinse formulations and / or softeners, drying additives, foams or washing additives.
• said monomer units (F1) are cationizable units derived from at least one cationizable monomer having a pKa of less than 11, preferably less than 10, 5. Mention may in particular be made, as examples of polymer (P) in particulate form, of particles or aqueous dispersions of particles (latex) of polymers or copolymers having units derived from
• the glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer
• the glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer
• the glass transition temperature Tg of which can range from 100 to 140 ° C, depending on the composition of said polymer;
• the glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer
• the glass transition temperature Tg can range from 40 ° C to 110 ° C, depending on the composition of said polymer.
• Said polymers (P) can be introduced in solid form or preferably in the form of aqueous dispersions (latex) having a dry extract of the order of 10 to 50%, preferably from 20 to 40% by weight, in the aqueous composition intended for cleaning to be improved.
• aqueous dispersions (latex) having a dry extract of the order of 10 to 50%, preferably from 20 to 40% by weight, in the aqueous composition intended for cleaning to be improved.
• a second object of the invention relates to an entirely preferred embodiment of the method of the invention.
• the second object of the invention therefore consists of a method for increasing the cleaning properties of an aqueous cleaning composition comprising at least one surfactant, intended for cleaning a surface soiled by dirt, by addition to said cleaning composition, of at least one polymer (P) in an amount effective to improve the removal of soiling from said surface, said polymer (P) being a copolymer (P ')
• hydrophobic monomer units (N) which are uncharged or non-ionizable at the pH of use of said composition and • and at least one hydrophilic sulfur-containing non-carboxylated monomer unit, preferably sulfonated or sulfated, (F ') anionic or amphoteric , derived from monoethylenically unsaturated ⁇ - ⁇ monomers.
• said copolymer (P ′) does not comprise more than 10% of its weight of COO " carboxylated monomer units and / or not more than 10% of its weight of non-amphoteric monomer units carrying a charge cationic.
• Said copolymer (P ') is most preferably free of carboxyl charges and cationic charges (not amphoteric). Examples of monomers from which the hydrophobic units (N) are derived have already been mentioned above.
• monomers having at least one sulfate or sulfonate function such as 2-sulfooxyethyl methacrylate, vinylbenzene sulfonic acid, allylsulfonic acid, 2-acrylamido-2methylpropane sulfonic, acrylate or sulfoethyl methacrylate, acrylate or sulfopropyl methacrylate and their water-soluble salts;
• N N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine
• SPE N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine
• SPP N-methacrylamidoethyl
• SPP 1-vinyI-3- (3-sulfopropyl) imidazolidium betaine
• 1- (3-sulfopropyl) -2-vinylpyridinium betaine SPV from RASCHIG).
• Said copolymer (P ′) can also comprise units derived from other ethylenically unsaturated ⁇ - ⁇ monomers which are non-carboxylated and non-cationic or non-potentially cationic at the pH of use of the composition.
• said copolymer can optionally further comprise:
• Said copolymer (P ') may also comprise units derived from ethylenically unsaturated ⁇ - ⁇ carboxylated and / or non-amphoteric cationic or potentially cationic monomers at the pH of use of the composition, and this in an amount corresponding to not more than 10 % by weight of units derived from carboxylated ethylenically unsaturated ⁇ - ⁇ monomers and containing not more than 10% of units derived from cationic or potentially cationic non-amphoteric ⁇ - ⁇ ethylenically unsaturated monomers.
• the monomer units with phosphonate or phosphate functions do not represent more than 10% of the total mass of the said copolymer (P ').
• All the hydrophilic units namely the units (F '), those with phosphonate or phosphate functions and the uncharged hydrophilic units) preferably represent not more than 30% of the total mass of the copolymer
• crosslinking units (R) When crosslinking units (R) are present, these generally do not represent more than 20%, preferably not more than 10%, especially not more than 5% of the total mass of the copolymer (P ').
• a preferred embodiment of the second subject of the invention consists in using in an aqueous cleaning composition, a copolymer (P ") comprising • at least 70% of its weight of hydrophobic monomer units (N)
• Said polymer (P ) can be used in all types of compositions for cleaning carpets and rugs of a non-cationic nature, the pH of use of which can range from 2 to 12, namely, detergent formulations, foams, washing additives ("prespotter”) or for cleaning hard surfaces (ceramic glass, formica ).
• said copolymer (P ") does not comprise more than 10% of its weight of carboxylated monomer units COO " and / or not more than 10% of its weight of non-monomeric units amphoteric carrying a cationic or potentially cationic charge.
• Said copolymer (P ") is most preferably free of carboxyl charges and cationic charges (not amphoteric).
• copolymers (P), (P ') and (P ") there may be mentioned the polymers or copolymers of: * methyl methacrylate / butyl acrylate / hydroxyethylmethacrylate / methacrylic acid / N, N-dimethyl- N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine (SPE from RASCHIG), whose glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said copolymer;
• SPE N-dimethyl- N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine
• the glass transition temperature Tg can range from 40 ° C to 130 ° C, depending on the composition of said copolymer
• the glass transition temperature Tg can range from 40 ° C to 110 ° C, depending on the composition of said copolymer.
• the amount of polymer (P) or of copolymers (P ') and (P ") present in particulate form in dispersion in the cleaning composition according to the invention can range from 0.05 to 50% by dry weight of the weight of said composition , depending on the desired application.
• polymer (P) or copolymers (P ') and (P ") can be used as follows:
• the aqueous cleaning composition in which said polymer (P) or copolymer (P ') and (P ") is dispersed comprises at least one anionic, nonionic, amphoteric, zwitterionic or cationic surfactant.
• surfactant expressed as dry can represent from 0.1 to 50% of the weight of the composition, and this depending on the type of composition.
• constituents may be present, alongside the particles of polymer (P) or copolymer (P ') and (P ") dispersed in the aqueous cleaning composition.
• P polymer
• P ' copolymer
• P a detergent formulation for washing laundry
• the detergent formulation may include surfactants in an amount corresponding to about 3 to 40% by weight based on the detergent formulation, surfactants such as anionic surfactants.
• methyl ester sulfonates the radical R of which is C 1 -C 4 -g; . alkyl sulfates of formula ROSO3M, where R represents a C5-C24, preferably C-
• OE ethoxylenated
• OP propoxylenated
• RCONHROSO3M sulfated alkylamides of formula RCONHROSO3M where R represents a C2-C22 alkyl radical. preferably in CQ-C20.
• alkylsulfonates secondary in C8-C22, alkylglycerol sulfonates, sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or sulfosuccinate diesters, N-acyl sarcosinates, alkyl glycoside sulfates, polyethoxycarboxylates; the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...
• polyoxyalkylenated polyoxyethylenated, polyoxypropylenated, polyoxybutylenated alkylphenols in which the alkyl substituent is CQ-C- ⁇ 2 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the Triton X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy. ; . glucosamide, glucamide, glycerolamide;
• polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units oxyethylene, oxypropylene
• amine oxides such as alkyl oxides C10-C18 dimethylamines, alkoxy oxides C8-C22 ethyl dihydroxy ethylamines; . the alkylpolyglycosides described in US-A-4,565,647; . amides of C8-C20 fatty acids; . ethoxylated fatty acids; . ethoxylated fatty amides; . ethoxylated amines.
• Amphoteric and zwitterionic surfactants alkyldimethylbetaines, alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, condensation products of fatty acids and protein hydrolysates; alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms.
• Bleaching agent to improve the removal of oxidizable dirt type oxidizing agents: sources of peroxides, such as hydrogen peroxide, organic peroxides, preformed peracids and mixtures of the above compounds.
• the potential bleaching agents are described in patent EP 0629694 B1 published on December 21, 1994.
• the concentration of the bleaching agent can vary from 0.01% to 50%, preferably from 0.1 to 20% by mass of the formulation.
• the detergency builders improving the properties of the surfactants can be used in amounts corresponding to approximately 5-50%, preferably approximately 5-30% by weight for the liquid detergent formulas or approximately 10 -80%, preferably 15-50% by weight for detergent formulas in powders, detergency builders such as: Inorganic detergency builders
• polyphosphates tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates
• alkali metals ammonium or alkanolamines.
• tetraborates or borate precursors tetraborates or borate precursors
• silicates in particular those having an Si ⁇ 2 / Na2 ⁇ ratio of the order of 1.6 / 1 to 3.2 / 1 and the lamellar silicates described in US-A-4,664,839;
• alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates); . cogranules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868; . crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X ...; Zeolite A with a particle size of the order of 0.1-10 micrometers is preferred.
• Organic detergency builders water-soluble polyphosphonates (1-hydroxy-1 ethane, 1-diphosphonates, methylene salts diphosphonates ...); the water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as: polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts); - hydroxypolycarboxylate ethers; citric acid and its salts, mellitic acid, succinic acid and their salts; the salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N- (2 hydroxyethyl) -nitrilodiacetates); succinic C5-C20 alkyl acids and their salts (2-dodecenylsuccinates, lauryl succinates); - polyacetal carboxylic esters; polyaspartic
• the detergent formulation may further comprise at least one oxygen-releasing bleaching agent comprising a per-compound, preferably a persalt.
• Said bleaching agent can be present in an amount corresponding to approximately 1 to 30%, preferably from 4 to 20% by weight relative to the detergent formulation.
• per-compounds capable of being used as bleaching agents mention should be made in particular of perborates such as sodium perborate monohydrate or tetrahydrate; peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate.
• perborates such as sodium perborate monohydrate or tetrahydrate
• peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate.
• Preferred bleaching agents are sodium perborate, mono- or tetrahydrate and / or sodium carbonate peroxyhydrate. Said agents are generally combined with a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid, in an amount corresponding to approximately 0.1 to 12%, preferably from 0.5 to 8% by weight relative to the detergent formulation.
• a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid, in an amount corresponding to approximately 0.1 to 12%, preferably from 0.5 to 8% by weight relative to the detergent formulation.
• these activators there may be mentioned, tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluryl, sodium p-acetoxybenzenesulfonate, pentaacetylglucose, Toctaacetyllactose.
• Non-oxygenated bleaching agents acting by photoactivation in the presence of oxygen, agents such as sulfonated aluminum and / or zinc phthalocyanines.
• the detergent formulation may further comprise anti-fouling agents ("soil release"), anti-redeposition, chelating agents, dispersants, fluorescence, foam suppressants, softeners, enzymes and other various additives.
• Anti-fouling agents oil release
• agents such as:
• cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose;
• polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048);
• polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethyl terephthalate and 1,2-propylene diol, having from 1 to 4 sulfonated groups (US Pat. No. 4,968,451);
• polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated by ethyl or methyl units (US-A-4,711,730) or polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or groups anionic sulfopolyethoxy
• sulfonated polyester copolymers derived from terephthalic, isophthalic and sulfoisophthalic acid, anhydride or diester and a diol FR-A-2 720 399.
• Anti-redeposition agents FR-A-2 720 399.
• agents such as:. ethoxylated monoamines or polyamines, polymers of ethoxylated amines
• the iron and magnesium chelating agents can be present in amounts of the order of 0.1-10%, preferably of the order of 0.1-3% by weight. Among others, we can mention:
• aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethylethylenediaminetriacetates, nitrilotriacetates;
• aminophosphonates such as nitrilotris- (methylenephosphonates);
• polyfunctional aromatic compounds such as dihydroxy-disulfobenzenes.
• Polymeric dispersing agents They can be present in an amount of the order of 0.1-7% by weight, to control the hardness of calcium and magnesium, agents such as
• the water-soluble salts of polycarboxylic acids of molecular mass of the order of 2000 to 100,000 obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and in particular polyacrylates with a molecular mass of the order of 2,000 to 10
• agents such as: stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanins, thiophenes ...
• agents such as:. C10-C24 monocarboxylic fatty acids or their alkali, ammonium or alkanolamine salts, fatty acid triglycerides;
• aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons such as paraffins, waxes; . N-alkylaminotriazines;
• agents such as clays.
• enzymes can be present in amounts of about 0.5-10% by weight, agents such as clays.
• enzymes such as:
• proteases amylases, lipases, cellulases, peroxidases (US-A-3,553,139, US-A-4,101,457, US-A-4,507,219, US-A-4,261,868).
• Other additives We can cite among others:
• the detergent composition can be used by any means, in particular by spraying, leaching, coating, impregnation, soaking, padding, at a rate of 0.1 g / l to 400 g / l, preferably from 1g / l to 50g / l to carry out spraying operations at a temperature of the order of 25 to 90 ° C.
• the cleaning composition can be an aqueous rinse-off formulation capable of facilitating the following cleaning.
• alcohols methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin
• aqueous cleaning composition is a washing additive
• Prespotter this can be in the form of an aqueous dispersion, a solid (stick), or a foam.
• - anionic surfactants such as those already mentioned above, in an amount of at least 5% the weight of the composition;
• - type oxidizing agents sources of peroxides, such as hydrogen peroxide, organic peroxides, preformed peracids and mixtures of the above compounds.
• sources of peroxides such as hydrogen peroxide, organic peroxides, preformed peracids and mixtures of the above compounds.
• the potential bleaching agents are described in patent EP 0629694 B1 published on December 21, 1994.
• the concentration of the bleaching agent can vary from 0.01% to 50%, preferably from 0.1 to 20% by mass of the formulation.
• aqueous cleaning composition is a composition for cleaning hard surfaces, this may comprise, alongside said polymer
• - surfactants from 0.1 to 50% by dry weight of the aqueous composition
• non-ionic surfactants of the C 6 -C 12 alkylphenol type, polyoxyethylenated, polyoxyethylenated and / or polyoxypropylene C8-C22 aliphatic alcohols , ethylene oxide - propylene oxide block copolymers, optionally polyoxyethylenated carboxylic amides, anionic or amphoteric surfactants such as those of the alkali metal soap type (alkaline salts of C8-C24 fatty acids), alkali sulfonates (alkylbenzene sulfonates C8-C-13, C12-C16 alkylsulfonates), oxyethylenated and sulfated C6-C-I6 fatty alcohols, oxyethylenated and sulfated C8-C13 alkylphenol
• biocides or bacteriostats capable of bringing a biocidal nature to the dispersions, such as cationic surfactants (alkyldimethylammonium halides ...), biocides quaternary ammonium or phosphonium halides, amphoteric biocides derived from glycines, biocides phenolics, biocides derived from chlorhexidine, hypochlorites, biocides or film-forming polymers, quaternary polyammonium ...
• - film-forming anti-fouling agents such as terephthalic polyesters which may be sulfonated ... - alcohols (ethanol, isopropanol, glycols)
• the cleaning operation consists in applying said cleaning composition, optionally diluted from 1 to 1000 times, preferably from 1 to 100 times, on the hard surface to be cleaned.
• the application of the dispersion to the soiled surface can be carried out for example by soaking, fine spraying, coating by application using a sponge, a mop or using a prepreg cellulosic material.
• the amount of cleaning composition which can be favorably used is that corresponding to a deposit of 0.0001 to 1 g, preferably from 0.0005 to 0.1 g of copolymer (P) per m 2 of hard surface to be treated.
• the particles are formed from polymer chains.
• the most hydrophilic chains are preferably located on the surface of the particle, thus forming the shell.
• the most hydrophobic chains are located inside the particle, thus forming the heart of the particle.
• the advantages of the process using the polymers (P) or copolymer (P ') and (P ") are in particular the following: - after application or copolymer (P') and (P") in dispersion, on the surface to be cleaned , the continuous liquid phase typically of water evaporates naturally or by heating or by penetration into the support and forms a stack / aggregate of particles or a continuous film or both simultaneously in contact with the dirt to be removed.
• the “stain-polymer” composite thus formed is then removed by any means known to those skilled in the art (sweeping, vacuuming, brushing, combing, rinsing, delamination, etc.);
• the shell of the polymer particle (P) or copolymer (P ') and (P ") is chosen according to the physicochemical nature of the support to be treated in order to minimize the interaction between the aggregate / polymer film and the surface to be treated after elimination of the continuous phase.
• the problem solved by the invention is precisely to avoid adhesion of the soil particle encapsulated by the polymer (P) or copolymer (P ') and (P ") to the surface of the support by a judicious choice of the nature and content of the constituent monomers of the latex.
• the method according to the invention is particularly advantageous for improving the cleaning properties of the compositions for cleaning polyamide carpets; polymers (P) are preferably used, the particles of which have sulfonate and or sulfate units (copolymers P 'and P ") on the surface and whose overall composition is such that the Tg at the pH of application of the cleaning composition is between 60 and 110 ° C.
• the particle size is then between 5 and 50 nm.
• a third object of the invention consists in the use, in an aqueous cleaning composition comprising at least one surfactant intended for cleaning a surface soiled by a fouling, of a polymer (P) or of a copolymer (P ') or (P ") as described above, as an agent making it possible to improve the removal of soiling from said surface.
• the soils that can be thus removed are in particular fatty soils (oils for example), inorganic soils (carbon black, insoluble metal salts), protein soils (stains from coffee, milk, fruit juice) oxidizable in in most cases or decomposable by the presence of enzymes, natural soiling of the cellulosic type.
• the detergent formulation used is adjusted to pH 4.
• the polymers and copolymers tested were used in the form of an aqueous dispersion (latex); they were obtained by emulsion polymerization and have the following characteristics:
• Latex L 1 a Styrene, 100%, Tg of 108 ° C at pH4, particle size of 40 nm.
• Latex L 1 b Styrene / Styrene Sulfonate, 95/5, Tg of 104 ° C at pH4, particle size of 21 nm
• Latex L 1c Styrene / AMPS, 95/5, Tg of 108 ° C at pH 4, particle size of 43 nm
• Latex L 1d styrene / ABu / AMPS 72/23/5, Tg of 65 ° C at pH 4, particle size of 48 nm
• Latex L 1e styrene / M MA / styrene sulfonate 71/24/5 Tg of 110 ° C, particle size of 13nm
• Latex L 2a MMM / MAA 95/5 Tg of 115 ° C at pH 4, particle size of 88nm
• Latex L 2b MMA / ABu / MAA 95/0/5 Tg of 129 ° C at pH 4, particle size of 32 nm
• Latex L 2c MMA / ABu / MAA 83/12/5 Tg of 83 ° C, particle size of 26 nm
• Latex L 2d MMA / ABu / MAA 70/25/5 Tg of 54 ° C, particle size of 26 nm
• MMA methyl methacrylate MAA methacrylic acid The size of the latex particles was determined by light scattering using a Zetasizer from Malvern Instruments.
• a polyamide carpet cleaning operation is carried out using a sprayer by spraying the carpet with the aqueous base composition shown in the table above.
• 15 to 25 ml of formulation / m 2 of surface to be treated are used.
• the carpet is presaluted according to the protocol of standard ISO / DIS 11378 well known to those skilled in the art with a model soiling such as soiling B5 described in annex B of iso standard DIS 11378. (reference "AATCC soil") which is evenly distributed on the carpet.
• 15 ml of formulation (A) / m 2 are then sprayed.
• the carpet is then allowed to dry for at least half an hour at room temperature.
• the carpet thus treated is vacuumed with a conventional Hoover type household vacuum cleaner.
• the carpet can be brushed beforehand.
• the carpet is vacuumed without brushing, but the vacuum cleaner has an integrated brush system.
• the powder which has been aspirated is analyzed by electron microscopy. We also measure the removal of dirt by a surface analysis technique, we only note in the table the difference with the vacuum (simple suction).
• Latexes with low Tg (2d) give less good results because they plasticize the carpet and do not properly remove dirt.
• Carboxylated latexes (which contain acrylates on the surface) remove dirt well but are difficult to remove from the carpet, unless their size is optimized (2a versus 2b, 2c).
• Polystyrene-based latexes give interesting results but by adding sulfonate units on the surface, their performance is considerably increased (comparison 1a and 1b / 1c / 1d / 1e).
• Latex sulfonates of type 1b, 1c, 1d and 1e are excellent candidates because they do not accumulate (or little) on the carpet and do not modify the surface appearance or the touch. By optimizing their glass transition temperature (Tg), good efficiency is obtained (comparison of 1b, 1c and 1d). Nanolatex 1c and 1d therefore give good results. The result is optimal with the hardest and smallest latex, i.e. with latex 1e.
• the aim of this experiment is to show that the quantity of polymer particles deposited on the surface to be cleaned manages the size of the final chips and therefore the capacity to coat or trap dirt.
• use is made of nanolatex produced from synthesis (dry extract of 30% on average), these are coated on polyamide surfaces previously soiled with coffee; the coating is made with a threaded rod of different thicknesses.
• the edges of the samples dry faster than the center due to the spike effect.
• relatively heterogeneous chips are obtained.
• the latexes 2b, 2c and 2d have almost the same size and a variable Tg. According to Figure 2/2, it is clear that the lower the Tg, the larger the chips; in the extreme, no more chips are formed with the 2d latex which forms an adhesive film.
• the effect on the coffee stain is as follows: in the case of 2d latex, the stain has not been eliminated, it is brighter. In the case of latex 2c, the elimination is satisfactory, it is not so in the case of latex 2b, the removal is appreciably improved by the latex 2a. It is concluded that there is a maximum glass transition temperature Tg below which the latex has no effect on the task. This temperature is, according to the above experience, reasonably between 54 and 82 ° C.
• the best cleaning agents have a Tg around 60 ° C. and a size close to 100 nm.
• the latexes L 1 b, L 1d and L 1e have almost the same size and a variable Tg. According to Figure 2/2, it is clear that the lower the Tg, the smaller the chips; interestingly, even the weak Tg forms larger chips than their carboxylated counterparts.
• the effect on the coffee stain is as follows: in all cases, the coffee stain is clearly removed. However, increasing the Tg of the latex (by 1d, then 1b then 1e leads to an improvement in removal. It is concluded that the higher the Tg of the sulfur latex, the better its anti-stain activity. preferably, the latex has a higher Tg at 100 ° C.

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