EP1684894A1 - Emulsion zur beförderung eines hydrophoben wirkstoffs zu einem substrat in einem wässrigen medium - Google Patents

Emulsion zur beförderung eines hydrophoben wirkstoffs zu einem substrat in einem wässrigen medium

Info

Publication number
EP1684894A1
EP1684894A1 EP04805319A EP04805319A EP1684894A1 EP 1684894 A1 EP1684894 A1 EP 1684894A1 EP 04805319 A EP04805319 A EP 04805319A EP 04805319 A EP04805319 A EP 04805319A EP 1684894 A1 EP1684894 A1 EP 1684894A1
Authority
EP
European Patent Office
Prior art keywords
emulsion
phase
water
hydrophobic
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP04805319A
Other languages
English (en)
French (fr)
Inventor
Ian Harrison
Evelyne Prat
Hélène LANNIBOIS
Anne-Gaëlle DRENO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR0313284A external-priority patent/FR2862234B1/fr
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1684894A1 publication Critical patent/EP1684894A1/de
Ceased legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/066—Multiple emulsions, e.g. water-in-oil-in-water
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/54—Silicon compounds
    • 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
    • C11D17/0017—Multi-phase 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners

Definitions

  • the present invention relates to an emulsion (E), in the form of a multiple emulsion (Em), the reverse internal emulsion of which comprises a hydrophobic active substance, or in the form of an emulsion (E).
  • This emulsion can be used to convey said hydrophobic active material to a substrate in an aqueous medium.
  • a detergent or rinsing composition or as a detergent or rinsing composition for washing or rinsing articles of textile fibers, with the aim of conveying and promoting the deposition of a hydrophobic active material such as a perfume, an agent hydrophobic care ..., on a textile article, in cotton in particular.
  • a hydrophobic active material such as a perfume, an agent hydrophobic care ...
  • W / OW water-in-oil-in-water
  • EP-930 933-A- claims a process for the controlled release of an active principle contained in a multiple emulsion of water-in-oil-in-water type, characterized in that: - said multiple emulsion comprises a reverse emulsion Ei with an aqueous phase A1 which contains at least one hydrophilic active principle, said emulsion Ei being dispersed in the form of droplets of direct emulsion Ed, in an aqueous continuous phase A2, with the two emulsions Ed and Ei stabilized by at least one surfactant, present at level of their respective continuous phases and in that said multiple emulsion is brought into contact with a sufficient amount of an agent, so as to transform it into a direct emulsion and to induce the release of the active principle, contained in the aqueous phase A1 of the emulsion Ei, in the aqueous phase A2.
  • the surfactant present in the aqueous continuous phase A2 of the Ed emulsion is preferably chosen from water-soluble lecithins, sucrose esters, esters of fatty acids, polyoxyethylenated alkylamides, triglyceride sulfates, alkyl sulfates, alkyl ether sulfates, alkyls sulfonates, alkylamine salts, fatty amines, lipoamino acids, alkylbetaines, alkylpolyglycol ethers, copolymers of alkylene oxides, modified polyesters, silicone polymeric surfactants.
  • the surfactant present in the continuous phase of the Ei emulsion is preferably chosen from liposoluble lecithins, esters of sorbitan and of fatty acids, polyalkylene dipolyhydroxystearates, fatty acids, monoglycerides, polyglycerol esters, polyglycerol polyricinoleate, lactic and tartaric acid esters.
  • the continuous phase of the Ei emulsion is an oily phase composed of at least one oil chosen from mineral, vegetable or animal oils.
  • the direct emulsion Ed preferably comprises by volume from 50 to 99% of an aqueous continuous phase A2 for i to 50% of reverse emulsion Ei
  • the reverse emulsion Ei is preferably composed by volume of 50 to 99% d '' a continuous phase for 1 to 50% of aqueous phase A1.
  • W / O / W oil in water
  • the reverse emulsion comprising an internal aqueous phase, comprising at least one hydrophilic active material, dispersed in an internal oily phase, said internal oily phase comprising at least one nonionic or cationic surfactant and / or at least nonionic amphiphilic polymer or cationic,
  • the external aqueous phase comprising: - at least one nonionic polyoxyalkylenated surfactant and / or at least one nonionic polyoxyalkylenated amphiphilic polymer, - and at least one water-soluble or water-dispersible compound chosen from (i) the polymers obtained by polymerization of at least one carboxylic acid monomer, and at least one ethylenically unsaturated monomer, and / or at least one polyoxyalkylenated ester of ethylenically unsaturated carboxylic acid; (ii) polymers resulting from the polymerization of at least one carboxylic acid monomer and optionally comprising at least one hydrophobic graft; (iii) polypeptides of natural or synthetic origin, optionally comprising at least one hydrophobic graft; (iv) highly depolymerized polysaccharides optionally comprising at least one hydrophobic graft.
  • the object of the invention is an emulsion in the form of a multiple emulsion or in a dry form redispersible in a multiple emulsion, the oil phase of which consists of or comprises a hydrophobic active material, emulsion which, after being used in an aqueous medium is capable of carrying said hydrophobic active material towards a substrate present in or in contact with said aqueous medium.
  • a first object of the invention consists of an emulsion (E) comprising a liquid or fusible hydrophobic phase (O) containing and / or consisting of at least one hydrophobic active material (A), said emulsion (E) having: in the form of a multiple emulsion (Em) comprising: - an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, at the interface of the two phases, at least one water-soluble or water-dispersible stabilizing agent (Di) - an aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed, using at least one dispersing agent and / or stabilizer (De) • or in solid form (Es), water-dispersible in a multiple emulsion (Em) in which the external phase (We) is aqueous, comprising - the reverse e
  • the hydrophobic phase (O) contains and / or consists of at least one hydrophobic active material (A).
  • the hydrophobic phase (O) and / or the active material (A) are made of at least one organic or organosilicon material or a mixture of at least one organic material and at least one organosilicon, liquid or fusible material which is insoluble in a aqueous phase.
  • the active material (A) is contained in the hydrophobic phase (O), it can also be in at least one solid or liquid inorganic material insoluble in an aqueous phase or in a mixture of at least one inorganic material and at least one organic material and / or at least one organosilicon material.
  • the material constituting the hydrophobic phase (O) or the active material (A) is considered to be insoluble when less than 15%, preferably less than 10% of its weight, is soluble in the internal aqueous phase (Wi) and the external phase (We) if the latter is present, and this in a temperature range between 20 ° C. and the preparation temperature of the inverse emulsion (Ei) and of the multiple emulsion (Em) or of the emulsion in a solid form (Es).
  • Said hydrophobic phase (O) preferably has a melting point less than or equal to 100 ° C., more particularly less than or equal to 80 ° C.
  • Said material constituting the hydrophobic phase (O) may be made of an organosilicon material (01).
  • Said polyorganosiloxane preferably has a dynamic viscosity measured at 25 ° C. and at a shear rate of 0.01 Hz for a stress of 1500 Pa (carried out on a Carrimed® of the CSL2-500 type) of between 10 4 and 10 9 cP.
  • an amphoteric polyorganosiloxane having at least one cationic or potentially cationic function and at least one anionic or potentially anionic function
  • polyorganosiloxanes there may be mentioned: > linear, cyclic or crosslinked polyorganosiloxanes formed from nonionic organosiloxane units of general formula (R) a (X) bSKO) [4 - (a + b)] / 2 (0 formula in which • the symbols R are identical or different and represent an alkyl hydrocarbon radical, linear or branched, having from 1 to 4 carbon atoms, aryl, phenyl in particular;
  • X are identical or different and represent a hydroxyl group, an alkoxy radical, linear or branched, having from 1 to 12 carbon atoms, an OCOR 'function, where R' represents an alkyl group containing from 1 to 12 atoms carbon, preferably 1 carbon atom;
  • said polyorganosiloxane is at least substantially linear, and very preferably linear.
  • X are identical or different and represent a hydroxyl group, an alkoxy radical, linear or branched, having from 1 to 12 carbon atoms, an OCOR 1 function, where R ′ represents an alkyl group containing from 1 to 12 atoms carbon, preferably 1 carbon atom;
  • the symbols B are identical or different and represent an aliphatic and / or aromatic and / or cyclic hydrocarbon radical containing up to 30 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen and / or nitrogen and / or sulfur, optionally carrying one or more ether, ester, thiol, hydroxyl, optionally quaternized amine, carboxylate functions, the symbol B being bonded to silicon preferably via an Si-C- bond; • a is 0, 1 or 2
  • R 1 represents an alkylene group containing 2 to 6 carbon atoms, optionally substituted or interrupted by one or more nitrogen atoms or oxygen atoms,
  • R 2 and R 3 represent. H,. an alkyl or hydroxyalkyl group containing from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms,. an amino alkyl group, preferably primary, the alkyl group of which contains from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, optionally substituted and / or interrupted by at least one nitrogen atom and / or d oxygen, said amino group being optionally quaternized, for example by a hydrohalic acid or an alkyl or aryl halide.
  • the polyorganosiloxanes carrying amino functions present in their chain, per 100 total silicon atoms, from 0.1 to
  • OR * o R4 is a divalent hydrocarbon radical chosen from: * linear or branched alkylene radicals, having 2 to 18 carbon atoms; * alkylene-carbonyl radicals, the linear or branched alkylene part of which contains 2 to 20 carbon atoms; * alkylene-cyclohexylene radicals, the linear or branched alkylene part of which contains 2 to 12 carbon atoms and the cyclo-hexylene part comprises an OH group and optionally 1 or 2 alkyl radicals having 1 to 4 carbon atoms; * the radicals of formula -R 7 - O - R 7 in which the identical or different radicals R 7 represent alkylene radicals having 1 to 12 carbon atoms; * the radicals of formula -R 7 - O - R 7 in which the radicals R 7 have the meanings indicated above and one of them or both are substituted by one or two group (s) -OH; * the radicals of formula -R 7 - COO - R 7 in which the
  • R 4 has the meaning indicated above
  • R 5 and R 6 have the meanings indicated below and
  • R 11 represents a divalent alkylene radical, linear or branched, having from 1 to 12 carbon atoms, one of the valential bonds (that of R 11 ) being connected to the atom of -NR 10 -, the other (that of R 4 ) being connected to a atom of silicon;
  • the radicals R 5 are identical or different, chosen from linear or branched alkyl radicals having 1 to 3 carbon atoms and the phenyl radical;
  • the radical R 6 represents a hydrogen radical or the radical R 5 or Ov or the sterically hindered piperidinyl groups of formula IV
  • R ' 4 is chosen from a trivalent radical of formula: - (CH 2 ) CH 'm ⁇ co— O ⁇ m represents a number from 2 to 20, and a trivalent radical of formula: where p represents a number from 2 to 20; * U 'represents -O- or NR 12 " , R 12 being a radical chosen from a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms; * R 5 and R 6 have the same meanings as those given above with regard to formula III.
  • said polyorganosiloxane with a sterically hindered amino function is a linear, cyclic or three-dimensional polyorganosiloxane of formula (V):
  • the symbols Z identical or different, represent R 1 below and or the symbol B below;
  • the symbols R 1 , R 2 and R 3 which are identical and / or different, represent a monovalent hydrocarbon radical chosen from linear or branched alkyl radicals having from 1 to 4 carbon atoms, linear or branched alkoxy radicals having from 1 to 4 carbon atoms, a phenyl radical and preferably a hydroxy radical, an ethoxy radical, a methoxy radical or a methyl radical;
  • the symbols B identical and / or different functional groups, represent a group with sterically hindered piperidinyl function (s) chosen from those mentioned above; and
  • the number of organosiloxy units without group B ranges from 10 to 450, preferably from 50 to 250;
  • the number of organosiloxy units with a group B ranges from 1 to 5, preferably from 1 to 3; - 0 ⁇ w ⁇ 10 and 8 ⁇ x ⁇ 448.
  • said polyorganosiloxane is linear.
  • hydrophobic phase (A) there may be mentioned in particular the oils RHODORSIL® 21645, RHODORSIL® Extrasoft marketed by Rhodia.
  • Said material constituting the hydrophobic phase (O) may be made of an organic material (02).
  • organic material such as vegetable oils (rapeseed, castor oil, sunflower oil, rapeseed oil erucic, linen ).
  • mineral oils such as naphthenic, paraffinic (petrolatum) oils, polybutenes
  • waxes comprising alkyl chains containing from 4 to 40 carbon atoms.
  • animal waxes beeswax, lanolin, whale oil
  • vegetable waxes carnauba, candellila, sugar cane wax, jojoba
  • fossil mineral waxes montane, ozokerite, Utah wax
  • hydrocarbon waxes comprising from 4 to 35 carbon atoms (mineral oils, paraffins, microcrystalline waxes)
  • synthetic waxes such as polyolefins (polyethylene, polypropylene), sterone, carbowax.
  • the active ingredient (A) can constitute the hydrophobic phase (O) or be contained in the hydrophobic phase (O); when it is contained in the hydrophobic phase (O), it can be soluble, partially soluble or insoluble in said hydrophobic phase (O). Mention may be made, as active materials (A) contained in the hydrophobic phase (O), of other hydrophobic materials such as in particular the perfume molecules, the organic or organosilicon anti-UV agents, the hydrophobic bactericidal agents, solid polyamide capsules, particles of silica or other oxides or inorganic compounds ...
  • the stabilizing agent (Di) is made of a material chosen from water-soluble or water-dispersible polysaccharides (PSA): - whose average degree of polymerization (DP) is at least 1.5, preferably at least 20, very particularly at least 100 - whose Brookfield viscosity at 25 ° C in solution at 1% by mass in water is less than 20,000 mPa.s., preferably less than 5,000 mPa.s., very particularly ranging from 30 at 4500 mPa.s., said polysaccharides (PSA) being also free of lipophilic polyorganosiloxane substituent groups.
  • PSA water-soluble or water-dispersible polysaccharides
  • water-soluble or water-dispersible means here that said polysaccharide (PSA) is not capable of forming a macroscopic two-phase solution at 25 ° C. in the internal aqueous phase (Wi).
  • lipophilic is used here as antonym of the term “hydrophilic”; that is, has no affinity for water; this means that the polyorganosiloxane groups, of which the polysaccharide (PSA) is free, would form, taken alone, at a concentration of 10% by weight, a macroscopic two-phase solution in distilled water at 25 ° C. According to the invention, the Brookfield viscosity at 25 ° C.
  • Said polysaccharide (PSA) is a homopolysaccharide or a heteropolysaccharide; it can be linear or branched, non-ionic or ionic; it can optionally be substituted and / or modified by nonionic or ionic groups, other than lipophilic polyorganosiloxane groups.
  • said polysaccharide (PSA), or its backbone comprises similar or different glycosyl units joined by ⁇ (1-4) bonds.
  • ⁇ (1-4) bonds it can also comprise other bonds, in particular ⁇ (1-3) and / or ⁇ (1-6).
  • Said glycosyl units, similar or different, can in particular be hexose and / or pentose units.
  • hexose units (similar or different), mention may in particular be made of D-glucose, D- or L-galactose, D-mannose, D- or L-fucose, L-rhamnose units
  • pentose units there may be mentioned in particular the D-xylose, L- or D-arabinose units, etc.
  • the hydroxyl functions or functions of the glycosyl units can be modified and / or substituted by nonionic groups. , ionic or ionizable.
  • non-ionic modifying groups when concerned, these can in particular be linked to the carbon atoms of the sugar skeleton either directly or via —O— bonds.
  • nonionic groups mention may be made of: • The alkyl groups comprising from 1 to 22 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen and / or nitrogen,
  • Aryl or arylalkyl groups comprising from 6 to 12 carbon atoms • Hydroxyalkyl or cyanoalkyl groups comprising from 1 to 6 carbon atoms
  • esters obtained by replacing hydrogen with a hydroxyl function -OH of the polysaccharide skeleton by a group comprising at least one acid unit containing in particular carbon, sulfur or phosphorus, such as in particular the carbonyl groups R- (CO) -, sulfonyl R-SO 2 -, phosphorylated R 2 P (O) -, hydroxyphosphorylated R- P (O) (OH) -, acid groups forming "ester” units with the residual oxygen atoms of the skeleton polysaccharide.
  • alkyl, alkenyl, aryl can comprise from 1 to 20 carbon atoms; it can also comprise a heteroatom, of nitrogen for example, linked directly to a carbonyl, sulfonyl unit, etc., and thus form urethane type bonds, etc.
  • a heteroatom of nitrogen for example, linked directly to a carbonyl, sulfonyl unit, etc., and thus form urethane type bonds, etc.
  • esters chosen from the acetate, propanoate, trifluoroacetate, 2- (2-hydroxy-1-oxopropoxy) propanoate, lactate, glycolate, pyruvate, crotonate, isovalerate, cinnamate, formate, salicylate, carbamate groups methylcarbamate, benzoate, gluconate, methanesulfonate, toluenesulfonate; the hemiesters groups of fumaric, malonic, itaconic, oxalic, maleic, succinic, tartaric, aspartic, glutamic, malic acids; there may be mentioned more particularly the substituent groups acetate, hemiacetate and 2- (2-hydroxy-1-oxopropoxy) propanoate.
  • the rate of MS modification of a polysaccharide by a nonionic modifying group corresponds to the average number of moles of precursor of the nonionic modifying group which has reacted per glycosyl unit.
  • the rate of modification MS can vary according to the nature of the precursor of said modifying group.
  • the rate of modification by nonionic groups is less than 3 by definition. If said precursor is capable of forming new reactive hydroxyl groups (hydroxyalkylation precursor for example), the rate of modification MS is theoretically not limited; it can for example go up to 6, preferably up to 2. This rate is generally at least 0.001, preferably at least 0.01.
  • anionic or anionizable groups mention may be made of those containing one or more carboxylate, sulfonate, sulfate, phosphate, phosphonate functions, etc.
  • R is a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms.
  • X is an integer ranging from 0 to 5.
  • y is an integer ranging from 0 to 5.
  • R ' is an alkylene radical containing from 1 to 12 carbon atoms, optionally bearing one or more OH substituents.
  • the radicals R " which are similar or different, represent a hydrogen atom, an alkyl radical containing from 1 to 18 carbon atoms.
  • the radicals R ' which are similar or different, represent an alkyl radical containing from 1 to 18 carbon atoms.
  • R" is a linear, branched or cyclic alkylene radical containing from 1 to 6 carbon atoms.
  • A represents O or NH.
  • Y is a heterocyclic aliphatic group comprising from 5 to 20 carbon atoms and a nitrogen heteroatom X 'is a counterion, preferably halide (chloride, bromide, iodide in particular), as well as the N-alkylpyridinium-yl groups whose alkyl radical contains from 1 to 18 carbon atoms, with a counterion, preferably halide (chloride, bromide, iodide in particular).
  • halide chloride, bromide, iodide in particular
  • cationic or potentially cationic groups there may be mentioned very particularly: - those of formula • -NH 2
  • hindered amino groups such as those derived from HALS amines, of general formula:
  • R represents CH3 or H.
  • the degree of substitution DS corresponds to the average number of hydroxyl functions of the glycosyl units substituted by the said ionic or ionizable group or groups, per glycosyl unit. It is generally less than 3, preferably less than 2.
  • PSA polysaccharides
  • PSA polysaccharides
  • Galactomannans especially guar gum depolymerized. in particular by an oxidative route, optionally modified or substituted by non-ionic groups (hydroxypropyl in particular), anionic (carboxymethyl in particular), cationic (hydroxypropyltrimethylammonium chloride for example), having a Brookfield viscosity (1% solution in water) which can range from 30 to 4500 mPa.s., preferably from 60 to 3500 mPa.s. We can cite in particular:
  • alkylpolvglvcosides having a C4-C20 alkyl group > preferably CS-C-JS. as well as an average number of glucose units of the order of 1.5 to 10, preferably of the order of 1.5 to 4, more generally of the order of 1.6 to 2.7 per mole of alkylpolyglycoside (APG), such as those mentioned in US 4,565,647.
  • the average size of the aqueous droplets (Wi) of the internal inverse emulsion (Ei) can range up to 10 ⁇ m, preferably from 0.05 ⁇ m to 5 ⁇ m, and more preferably from 0.1 to 1 ⁇ m.
  • the average size corresponds to the median diameter in volume (d50), which represents the diameter of the particle equal to 50% of the distribution cumulative; it can for example be measured with a Horiba granulometer or optical microscope.
  • the dispersed aqueous phase (Wi) has a pH which can range from 0 to 14, preferably from 2 to 11, more preferably from 5 to 11. It can contain additives making it possible to adjust the osmotic pressure, such as salts (chloride or sulfate sodium, calcium chloride %) or sugars (glucose) or polysaccharides (dextran ). It can also contain buffering agents, hydrophilic active materials, in particular antibacterial agents such as methyl chloro isothiazolinone and methyl isothiazolinone (KATHON® CG marketed by
  • the mass ratio of the dispersed aqueous phase (Wi) to the hydrophobic phase (O) can range from 5/95 to 95/5, preferably from 3070 to 80/20.
  • the ratio of the mass of stabilizer (Di) to the mass of hydrophobic phase (O) can range from 0.1 / 100 to 500/100, preferably from 0.5 / 100 to 100/100, very particularly from 0, 5/100 to 50/100.
  • the inverse emulsion (Ei) can be obtained in a conventional manner. For example, it can be obtained by dissolving and / or dispersing the polysaccharide (PSA) in water and then adding the aqueous solution and / or dispersion obtained to the hydrophobic phase (O), with stirring.
  • the stirring can advantageously be carried out by means of a frame blade, a planetary type mixer, a mixer having a scraping mobile and a blade rotating in opposite directions (counter-stirring).
  • the preparation of the reverse emulsion is generally carried out at a temperature higher than the melting temperature of the material used as the hydrophobic phase, but lower than that of degradation of the elements entering into the composition of the reverse emulsion. More particularly, this temperature is between 10 and 80 ° C.
  • the duration of the agitation can be determined without difficulty by those skilled in the art.
  • the multiple emulsion (Em) comprises the reverse emulsion above (Ei), as internal emulsion, dispersed in an external phase (We) aqueous or miscible with water, comprising at least one dispersing agent and / or stabilizer (De).
  • Said dispersing and / or stabilizing agent (De) has a hydrophilic tendency.
  • said dispersing and / or stabilizing agent (De) is chosen from hydrophilic surfactants and / or hydrophilic polymers and / or hydrophilic amphiphilic polymers.
  • the term "hydrophilic” is used in its usual sense of “who has an affinity for water”; this means that the dispersing and / or stabilizing agent (De) is not capable of forming a macroscopic two-phase solution in distilled water at 25 ° C.
  • the external phase (We) is an aqueous phase.
  • the surfactants and / or polymers (De) satisfy the Bancroft rule and are preferably chosen from compounds which satisfy both of the two conditions below: - when they are mixed with the external aqueous phase at a concentration between 0.1 and 10% by weight of said phase and between 20 and 30 ° C, they are in the form of a solution in all or part of the concentration range indicated.
  • said dispersing and / or stabilizing agent (De) can be formed (a) of at least one nonionic hydrophilic surfactant (b) of at least one anionic hydrophilic surfactant (c ) at least one cationic hydrophilic surfactant (d) at least one nonionic hydrophilic polymer (e) at least one nonionic hydrophilic amphiphilic polymer (f) at least one anionic hydrophilic polymer (g ) of at least one anionic hydrophilic amphiphilic polymer (h) of at least one cationic hydrophilic polymer (i) of at least one cationic hydrophilic amphiphilic polymer G) or of a mixture of at least two of said surfactants and / or polymers (a)
  • the total content of surfactant (s) and / or polymer (s) (De) present (s) in the external phase (We) can be between 0.01 and 50% by weight, preferably between 0.1 and 10%, more particularly between 0.5 and 5% by weight, relative to the inverse emulsion (Ei).
  • the nonionic hydrophilic surfactants have an HLB value at least equal to the required HLB of the hydrophobic phase (O); as an indication, this minimum value of HLB is most often at least 10. These are preferably polyalkoxylated.
  • the polyalkoxylated nonionic surfactant can be chosen from the following surfactants, alone or as a mixture:
  • Alkoxylated alkyl phenols more particularly ethoxylated and / or propoxylated.
  • the total number of ethoxylated and optionally propoxylated units is between 10 and 100.
  • anionic hydrophilic surfactants that may be mentioned:
  • - sulphate alkylamides as well as their polyalkoxylated derivatives (ethoxylated (OE), propoxylated (OP), or their combinations); - salts of saturated or unsaturated fatty acids, and
  • cationic hydrophilic surfactants which may also be present in the dispersing and / or stabilizing agent (De), it is possible to mention the quaternary ammonium salts of formula R 1 R 2 R 3 R 4 N + X " where the groups R are long or short hydrocarbon chains, alkyl, hydroalkyl or alkyl ethoxylated, X being a counterion (R 1 is a group C 8 -C 22 , preferably C ⁇ -C-10 or C12-C14 alkyl, R 2 is a methyl group, R 3 and R 4 being similar or different being a methyl or hydroxy methyl group); as well as Cationic esters, such as choline esters.
  • nonionic hydrophilic polymers which can be used, mention may be made of the water-soluble or water-dispersible nonionic polysaccharides (PSA)
  • nonionic hydrophilic amphiphilic polymers are preferably polyalkoxylated compounds, comprising at least two blocks, one of them being hydrophilic, the other hydrophobic, at least one of the blocks comprising polyalkoxylated, more particularly polyethoxylated and / or polypropoxylated patterns.
  • said nonionic polyalkoxylated hydrophilic amphiphilic polymers are chosen from polymers whose molar mass by weight is less than or equal to 100,000 g / mol (measured by GPC, polyethylene glycol standard), preferably between 1,000 and 50,000 g / mol, preferably between 1,000 and 20,000 g / mol.
  • polymers of this type mention may be made, inter alia, of polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polymers.
  • Such polymers are well known and are in particular marketed under the brands Pluronic (marketed by BASF), Arlatone (marketed by ICI).
  • Said hydrophilic nonionic amphiphilic polymer can also be is a hydrophilic amphiphilic block polymer, obtained by polymerization of at least one hydrophilic nonionic monomer and at least one hydrophobic monomer, the proportion and nature of said monomers being such that the polymer resulting checks the conditions previously stated (Bancroft rule - two conditions). They comprise at least one hydrophobic block and at least one neutral (nonionic) hydrophilic block.
  • the polymer comprises at least three blocks, and more particularly three blocks, the polymer is advantageously linear.
  • the hydrophilic blocks are more particularly at the ends.
  • the polymers comprise more than three blocks, the latter are preferably in the form of grafted or combed polymers.
  • hydrophobic monomers from which the hydrophobic block (s) of the hydrophilic amphiphilic polymer may be mentioned, in particular:
  • esters of mono- or polycarboxylic acids linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation
  • esters of saturated carboxylic acids comprising 8 to 30 carbon atoms, optionally carrying a hydroxyl group
  • esters of (meth) acrylic acid with an alcohol comprising 1 to 12 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) n-butyl acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl acrylate;
  • the vinyl nitriles more particularly include those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile;
  • the preferred monomers are the esters of acrylic acid with linear or branched C ⁇ -C 4 alcohols such as methyl, ethyl, propyl acrylate and butyl, vinyl esters such as vinyl acetate, styrene, ⁇ -methylstyrene.
  • nonionic hydrophilic monomers from which the hydrophilic amphiphilic block polymers can be obtained mention may be made of ethylene oxide; amides of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation, or derivatives, such as (meth) acrylamide, N-methyloI (meth) acrylamide; hydrophilic esters derived from (meth) acrylic acid such as for example 2-hydroxyethyl (meth) acrylate; vinyl esters making it possible to obtain polyvinyl alcohol blocks after hydrolysis, such as vinyl acetate, vinyl Versatate®, vinyl propionate.
  • These monomers can be used alone, in combination, as well as in the form of macromonomers. It is recalled that the term macromonomer designates a macromolecule carrying one or more functions which can be polymerized by the method used.
  • the preferred hydrophilic monomers are acrylamide and methacrylamide, alone or as a mixture, or in the form of macromonomers.
  • the nonionic hydrophilic amphiphilic polymers have an HLB value at least equal to the required HLB of the hydrophobic phase (O); As an indication, this minimum value of HLB is most often at least 10.
  • the anionic hydrophilic polymers which may be used, mention may be made of the water-soluble or water-dispersible anionic polysaccharides (PSA) already mentioned above as stabilizing agent ( Di), such as
  • Oxidically depolymerized guars (with some COOH + functions resulting from depolymerization in an oxidizing medium), such as MEYPRO-GAT 7, MEYPRO-GAT 20, MEYPRO-GAT 30 sold by Rhodia • Depolymerized hydroxypropylated guars with a change in the order of 0.01 to 0.8, such as Rhodia's HMP-CON
  • Carboxymethylated depolymerized guars having a degree of substitution of the order of 0.05 to 1.6 such as MEYPRO-GUM R 600 sold by Rhodia.
  • anionic hydrophilic amphiphilic polymers which may be used, mention may be made particularly of block polymers, preferably diblocks or triblocks, obtained by polymerization of at least one anionic hydrophilic monomer, optionally at least one nonionic hydrophilic monomer, and at least one hydrophobic monomer. Again, the choice of monomers and their respective proportions are such that the resulting polymer satisfies the two conditions set out above (Bancroft rule).
  • anionic hydrophilic monomers from which the hydrophilic amphiphilic block polymers can be obtained mention may be made.
  • vinyl sulfonic acid vinylbenzene sulfonic acid, vinyl phosphonic acid, vinylidene phosphoric acid, vinyl benzoic acid, as well as alkali metal salts, such as sodium, potassium, or ammonium ;
  • nonionic hydrophilic monomers and hydrophobic monomers have already been mentioned above.
  • cationic hydrophilic polymers which can be used, mention may be made of water-soluble polysaccharides (PSA) or cationic water dispersants already mentioned above as stabilizing agent (Di), such as for example
  • the dispersing and / or stabilizing agent (De) is chosen from nonionic hydrophilic surfactants and / or nonionic hydrophilic (amphiphilic) polymers; more preferably, said nonionic hydrophilic surfactants and / or nonionic hydrophilic (amphiphilic) polymers have an HLB value at least equal to the required HLB of the hydrophobic phase (O); as an indication, this minimum value of HLB is most often at least 10.
  • the hydrophilic amphiphilic hydrophilic agent (De) is very particularly a non-ionic hydrophilic amphiphilic polymer.
  • the dispersing and / or stabilizing agent (De) is in a mixture of at least one nonionic hydrophilic surfactant and at least one anionic hydrophilic surfactant, optionally combined at least one nonionic hydrophilic (amphiphilic) polymer.
  • the dispersing and / or stabilizing agent (De) is chosen from cationic hydrophilic surfactants and / or cationic hydrophilic (amphiphilic) polymers, optionally mixed with at least one surfactant nonionic hydrophilic and / or at least one nonionic hydrophilic (amphiphilic) polymer.
  • a nonionic surfactant and / or a nonionic polymer is present, this can represent up to 50% of the weight of the cationic / nonionic mixture.
  • the dispersing and / or stabilizing agent (De) is chosen from stabilizing agents (Di) in at least one non-ionic, anionic or cationic water-soluble or water-dispersible polysaccharide (PSA), or their compatible mixtures . It may optionally be added with at least one other dispersing and / or stabilizing agent (De) other, compatible; preferably, the mass quantity of dispersing and / or stabilizing agent (De) other than water-soluble or water-dispersible polysaccharide (PSA), if any, is at most equal to the mass of water-soluble or water-dispersible polysaccharide (PSA) used as as a dispersing and / or stabilizing agent (De).
  • the amount of external phase (We) of the multiple emulsion (Em) is a function of the desired concentration for the multiple emulsion (Em).
  • the internal inverse emulsion mass ratio (external EiVphase (We) comprising the dispersing and / or stabilizing agent (De) can range from 50/50 to 99/1, preferably from 70/30 to 98/2, very particularly from 70 / 30 to 80/20.
  • the mass ratio, expressed in sec, of dispersing and / or stabilizing agent (De) / mass of the internal inverse emulsion (Ei), can range from 0.01 / 100 to 50/100, preferably 0.1 / 100 to 10/100, especially 0.5 / 100 to 5/100.
  • the concentration of the external phase (We) in dispersing and / or stabilizing agent (De) can range from 1 to 50%.
  • the emulsion (E) is a multiple emulsion (Em) comprising at least 70% by weight of internal emulsion (Ei).
  • the average size of the internal inverse emulsion globules (Ei) dispersed in the external phase (We) is preferably less than 200 ⁇ m; preferably it can range from 1 to 20 ⁇ m, more preferably from 5 to 15 ⁇ m.
  • the average size of the internal inverse emulsion globules (Ei) dispersed in the external phase (We) is at least twice, preferably at least 5 times, very particularly d '' at least 10 times that of the average size of the droplets of the internal aqueous phase (Wi) dispersed in the hydrophobic phase.
  • the external phase (We) can be aqueous or non-aqueous miscible with water.
  • miscible with water means is not likely to form a macroscopic diphasic solution at 25 ° C.
  • the external phase (We) is a non-aqueous phase miscible with water, it is in particular an alcoholic or hydroalcoholic phase, in particular a phase based on isopropyl alcohol, ethanol. .
  • the external phase (We) is an aqueous phase.
  • the pH of the external aqueous phase is not limiting; it depends on the intended application of the invention.
  • the pH can range from 0 to 14, preferably from 2 to 11, more preferably from 5 to 11.
  • the pH of the external aqueous phase (We) of the concentrated multiple emulsion (Em) can range from 5 to 11, preferably from 6 to 8.
  • the external phase (We), preferably aqueous, can also contain hydrophilic active materials, in particular antibacterial agents such as methyl chloro isothiazolinone and methyl isothiazolinone (KATHON® CG marketed by Rohm and Haas), as well as buffering agents for adjust the pH, additives to adjust the osmotic pressure, such as salts (sodium chloride or sulfate, calcium chloride %) or sugars (glucose) or polysaccharides (dextran ”).
  • hydrophilic active materials in particular antibacterial agents such as methyl chloro isothiazolinone and methyl isothiazolinone (KATHON® CG marketed by Rohm and Haas), as well as buffering agents for adjust the pH, additives to adjust the osmotic pressure, such as salts (sodium chloride or sulfate, calcium chloride %) or sugars (glucose) or polysaccharides (dextran ”).
  • the active material (A) contained in or constituting the hydrophobic phase (O) is a hydrophobic active material useful in the field of care or detergency of articles made of textile fibers
  • the external phase (We) an aqueous liquid detergent formulation containing the dispersing and / or stabilizing agent (De) formed from a mixture of at least one nonionic hydrophilic surfactant and at least one anionic hydrophilic surfactant , optionally combined with at least one non-ionic hydrophilic (amphiphilic) polymer.
  • the concentration of the aqueous external phase (We) in hydrophilic compound (De) can range from 10 to 60% by weight, preferably from 15 to 50% by weight; its pH can range from 6 to 8.
  • the mass ratio, expressed in sec, of nonionic surfactant / anionic surfactant can range from 3/1 to 1/1.
  • the active material (A) is a hydrophobic active material useful in the field of care or detergency of articles made of textile fibers
  • the external phase (We) a liquid detergent formulation non-aqueous miscible with water, containing the dispersing and / or stabilizing agent (De) formed from a mixture of at least one nonionic hydrophilic surfactant and at least one anionic hydrophilic surfactant, optionally combined with at least one nonionic hydrophilic (amphiphilic) polymer.
  • the concentration of the non-aqueous external phase (We) in hydrophilic compound (De) can range from 10 to 60% by weight, preferably from 15 to 50% by weight.
  • the active material (A) is a hydrophobic active material useful in the field of caring for articles made of textile fibers
  • the external phase (We) an aqueous liquid rinsing formulation, containing the dispersing and / or stabilizing agent (De) formed from at least one cationic hydrophilic surfactant and / or from at least one cationic hydrophilic (amphiphilic) polymer, optionally in admixture with at least one nonionic hydrophilic surfactant and / or at least one nonionic hydrophilic (amphiphilic) polymer.
  • the active material (A) is a hydrophobic active material useful in the field of paints, and the external phase (We) an aqueous formulation for paint.
  • the active material (A) is a hydrophobic active material useful in the field of paints, and the external phase (We) an aqueous formulation for paint.
  • the multiple emulsion (Em) according to the invention can be obtained by implementing techniques involving a single reactor or two reactors.
  • a technique in a single reactor can be carried out by implementing the following steps: (a) preparing the reverse emulsion (Ei) (b) preparing the external phase containing the agent and / or stabilizer (De) ( c) the external phase is introduced into the reverse emulsion (Ei) without stirring (d) the whole is stirred.
  • Step (a) of preparation of the reverse emulsion (Ei) can be carried out as described above.
  • Step (b) of preparation of the external phase (We) can be carried out by mixing the constituent of the external phase (We) (preferably water) and the dispersing and / or stabilizing agent (De ).
  • the external phase (We) can also include adjuvants such as preservatives and additives regulating the osmotic pressure.
  • the preparation of the external phase can be carried out at room temperature.
  • the external phase (We) is prepared at a temperature close to that at which the reverse emulsion (Ei) is prepared. Once the external phase (We) is obtained, it is added to the inverse emulsion
  • step (d) After having introduced all of the external phase (We) into the reverse emulsion (Ei), the whole is agitated (step (d).
  • the stirring is carried out by means of moderately shearing mixers, as are, for example, the agitators provided with a frame blade, the planetary type mixers, or those having a scraping mobile and a blade rotating in opposite directions. (cons-stirring).
  • This stirring operation preferably takes place at a temperature at which the hydrophobic phase (O) is in a liquid form, and more particularly is between 10 and 80 ° C.
  • the average size of the internal inverse emulsion (Ei) globules advantageously varies between 1 and 100 ⁇ m, more particularly between 1 and 20 ⁇ m, advantageously between 5 and 15 ⁇ m.
  • the average size of the globules corresponding to the median diameter in volume (d50) which represents the diameter of the globule equal to 50% of the cumulative distribution, is measured with a Horiba device and, or with an optical microscope.
  • the various constituents of the emulsion (Em) can be used according to the quantities mentioned above.
  • the inverse emulsion / external phase weight ratio (We) can range from 50/50 to 99/1, preferably 70 / 30 to 98/2, especially from
  • a technique in two reactors can be carried out by implementing the following steps: (a) preparing the external phase (We) containing the dispersing and / or stabilizing agent (De) as above (b) preparing l reverse emulsion (Ei) as above (c) gradually introducing the reverse emulsion (Ei) into the external phase (We), with stirring
  • Step (c) of preparation of the actual multiple emulsion is carried out with stirring; stirring can be done by means of a paddle frame.
  • the stirring speed is relatively slow, of the order of 400 revolutions / minute.
  • the multiple emulsion (Em) obtained is analogous to that obtained by the technique known as a single reactor.
  • Another technique in two reactors, making it possible to prepare a similar multiple emulsion (Em) implements the following steps: (a) the reverse emulsion (Ei) is prepared as above; the amount of reverse emulsion (Ei) prepared is divided into two parts (b) the external phase (We) is prepared containing the dispersing and / or stabilizing agent (De) (c) the external phase (We) is introduced into the first part of the reverse emulsion (Ei) without stirring (d ) the whole is stirred (e) little by little the remaining part of the inverse emulsion (Ei) is introduced into the multiple emulsion obtained in step (d), with stirring When the dispersing and / or stabilizing agent (De) is in at least water-soluble or water-dispersible polysaccharide (PSA) constituting the stabilizing agent (Di), the multiple emulsion (Em)
  • the emulsion in solid form (Es), according to the invention can be obtained by addition, to the external phase of the multiple emulsion (Em), of a matrix (M) - in a water-soluble or water-dispersible compound, capable of form, in the presence of the external phase of the multiple emulsion (Em), a solid shell, after drying and optionally crystallization - into a solid water-soluble or water-dispersible material capable of adsorbing and / or absorbing the multiple emulsion (Em) and / or to hydrate, while remaining in a solid form - or in an insoluble solid material, capable of adsorbing and / or absorbing the multiple emulsion (Em).
  • the external phase (We) of the multiple emulsion (Em) is aqueous.
  • the materials capable of forming the matrix (M) there may be mentioned: • the following water-soluble or water-dispersible organic and inorganic compounds: - polyethylene qlvcols (PEG) having a molecular weight of between 2,000 and 100,000 g / mole - co-polymers of ethylenically unsaturated carboxylic acid or anhydride and of non-ionic ethylenically unsaturated monomer - water-soluble or water-dispersible polypeptides (PP) of natural or synthetic origin - the polyelectrolytes (PE) in acid form, belonging to the family of weak polyacids, having a molecular mass of less than 20,000 g / mole, preferably between 1,000 and 5,000 g / mole - the polvvinylpyrrolidones (PVP) having a molecular weight less than 20,000 g / mole, preferably between 1,000 and 10,000 g / mole - polyvinyl alcohols (PEG
  • the water-soluble or water-dispersible salts of alkali metals like silicates (Sil). carbonates (Carb). phosphates (Phos). sulphates. phosphonates. acetates, citrates, salts of saturated or unsaturated fatty acids (stearates) of alkali metals, mixtures of sodium acetate and citric acid - or mixtures thereof.
  • copolymers of ethylenically unsaturated carboxylic acid or anhydride and of ethylenically unsaturated nonionic monomer mention may be made of copolymers of linear or branched aliphatic, cycloaliphatic or aromatic aliphatic or monocarboxylic or polycarboxylic acid and of monoolefinic ⁇ containing from 2 to 20 carbon atoms.
  • ⁇ monoolefin monomers mention may especially be made of ethylene, propylene, butene-1, isobutylene, n-pentene-1, 2-methyl butene-1, n-hexene-1, methyl -2 pentene-1, methyl-4 pentene-1, ethyl-2 butene-1, diisobutylene (or -trimethyl-2,4,4 pentene-1), methyl-2 dimethyl-3,3 pentene -1.
  • the molar ratio between the two types of monomers can range from 30/70 to 70/30.
  • the copolymer of formula (i) results from the polymerization of maleic anhydride and 2,4,4-trimethyl 1-pentene.
  • copolymer is well known to those skilled in the art. Mention may be made, as polymer of this type, of that marketed under the name Geropon® EGPM and T36 (maleic anhydride / diisobutylene), marketed by Rhodia Chimie, as well as Sokalan® CP9 (maleic anhydride / olefin) marketed by BASF.
  • Geropon® EGPM and T36 maleic anhydride / diisobutylene
  • Sokalan® CP9 maleic anhydride / olefin
  • BASF water-soluble or water-dispersible synthetic polymers
  • polymers can be homopolymers derived from aspartic or glutamic acid as well as copolymers derived from aspartic acid and glutamic acid in any proportions, or copolymers derived from aspartic and / or glutamic acid and d other amino acids.
  • copolymerizable amino acids there may be mentioned glycine, alanine, leucine, isoleucine, phenyl alanine, methionine, histidine, proline, lysine, serine, threonine, cysteine ...
  • proteins of plant origin are preferably hydrolyzed, with a degree of hydrolysis less than or equal to 40%, for example from 5 to less than 40%.
  • proteins of vegetable origin mention may be made, by way of indication, of the proteins originating from protein seeds, in particular those of peas, faba beans, lupins, beans, and lentils; proteins from cereal grains, especially those from wheat, barley, rye, corn, rice, oats, and millet; proteins from oil seeds, especially those from soybeans, peanuts, sunflowers, rapeseed, and coconuts; proteins from the leaves, especially alfalfa, and nettles; and proteins from plant organs from buried reserves, notably that of potatoes and beets.
  • proteins of animal origin mention may be made, for example, of muscle proteins, in particular stroma proteins, and gelatin; proteins originating from milk, in particular casein, lactoglobulin; and fish protein.
  • the protein is preferably of vegetable origin, and more particularly comes from soybeans or wheat.
  • a radical -R-COOH where R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene residue containing 1 or 2 carbon atoms, methylene in particular.
  • R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene residue containing 1 or 2 carbon atoms, methylene in particular.
  • R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene residue containing 1 or 2 carbon atoms, methylene in particular.
  • copolymers obtained from the monomers corresponding to the preceding general formula and those obtained using these monomers and other monomers in particular vinyl derivatives such as vinyl alcohols and copolymerizable amides such as acrylamide or methacrylamide.
  • the preferred polyelectrolytes have a low degree of polymerization.
  • the molecular weight by weight of the polyelectrolytes is more particularly less than 20,000 g / mole. Preferably, it is between 1,000 and 5,000 g / mole.
  • An ampholyte polymer is a polymer which comprises anionic or potentially anionic charges depending on the pH and cationic or potentially cationic charges depending on the pH, the potentially anionic or potentially cationic charges being taken into account for the calculation of the ratio of total number of anionic charges to the total number of cationic charges.
  • the film-forming ampholytic polymer (PA) generally has a molecular mass of less than 500,000 g / mol, determined by aqueous gel permeation chromatography (GPC).
  • the film-forming ampholytic polymer (PA) can be obtained from anionic and cationic ethylenically unsaturated monomers. It can also be obtained from a mixture of monomers additionally containing neutral monomers.
  • the anionic ethylenically unsaturated monomers can be chosen from acrylic, methacrylic, fumaric, maleic, itaconic acids or anhydrides, N-methacroyl alanine, N-acryloyl-hydroxy-glycine ...
  • water-soluble, sulfonated or phosphonated ethylenically unsaturated monomers such as sulfopropyl acrylate or its water-soluble salts, water-soluble styrene sulfonates, vinylsulfonic acid and its water-soluble salts or vinylphosphonic acid and its water-soluble salts.
  • the cationic ethylenically unsaturated monomers can be chosen from
  • aminoacryloyl or acryloyloxy monomers such as trimethylaminopropylmethacrylate chloride, trimethylaminoethylacrylamide or methacrylamide chloride or bromide, trimethylaminobutylacrylamide or methacrylamide, trimethylaminopropylmethacrylamide () (3-acrylamidopropyl) trimethylammonium chloride (APTAC), methacryloyloxyethyl trimethylammonium chloride or methyl sulfate, acryloyloxyethyl trimethylammonium chloride;
  • N N-dialkyldiallylamine monomers such as N, N-dimethyldiallylammonium chloride (DADMAC);
  • polyquaternary monomers such as dimethylaminopropylmethacrylamide chloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium (DIQUAT) ...
  • the neutral ethylenically unsaturated monomers can be chosen from acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, dimethylaminoethylmethacrylate (DMAEMA), dimethylaminopropyl methacrylamide, vinyl alcohol, alkyl or hydroxyalkyl acrylates or methacrylates, polyoxyalkylene glycol acrylates or methacrylates ... Mention may very particularly be made, as ampholyte polymer ( PA), copolymers or terpolymers
  • MAPTAC acrylic or methacrylic acid
  • DIQUAT acrylic or methacrylic acid
  • DADMAC acrylic or methacrylic acid
  • MES acrylic or methacrylic acid / DMAEMA
  • Osides are compounds which result from the condensation, with elimination of water, of daring molecules between them or even of daring molecules with non-carbohydrate molecules.
  • the holosides which are formed by the combination of exclusively carbohydrate units are preferred, and more particularly the oligoholosides (or oligosaccharides) which contain only a limited number of these units, that is to say a number which is generally lower. or equal to 10.
  • oligoholosides mention may be made of sucrose, lactose, cellobiose, maltose, sucrose and trehalose.
  • the water-soluble or water-dispersible polyholosides are highly depolymerized; they are described for example in the work of P. ARNAUD entitled “organic chemistry course", Gaultier-Villars sky, 1987. More particularly, these polyholosides have a molecular mass by weight of less than 500,000 g / mole, preferably less at 20,000 g / mole.
  • polyholosides By way of nonlimiting example of polyholosides, mention may be made of celluloses and cellulose derivatives (carboxy methyl cellulose), carrageenans; among the highly depolymerized polyholosides, mention may be made of dextran, starch, xanthan gum and galactomannans such as guar or carob, these polysaccharides preferably having a melting point above 100 ° C. and a solubility in water between 5 and 500 g / l.
  • amino acids (AA) there may be mentioned monocarboxylated or dicarboxylated monoamine acids, monocarboxylated diamine acids and their water-soluble derivatives.
  • Amino acids preferably have a side chain with acid-base properties; they are chosen in particular from arginine, lysine, histidine, aspartic, glutamic and hydroxyglutamic acids; they can also be in the form of derivatives, preferably water-soluble; it can be, for example, sodium, potassium or ammonium salts, such as sodium glutamate, aspartate or hydroxyglutamate.
  • surfactants likely to constitute the matrix (M)
  • the description of the fluid isotropic phases and rigid liquid crystal of hexagonal or cubic type is given in the work of RG LAUGHLIN entitled "The AQUEOUS PHASE BEHAVIOR OF SURFACTANTS "- ACADEMIC PRESS - 1994.
  • phase rigid liquid crystal is stable up to a temperature at least equal to 55 ° C.
  • the fluid isotropic phase can be poured, while the rigid liquid crystal phase cannot.
  • ionic glycolipid surfactants in particular derivatives of uronic acids (galacturonic, glucuronic acids, D-mannuronic, L-iduronic, L-guluronic 10), having a substituted hydrocarbon chain or unsaturated or unsaturated comprising from 6 to 24 carbon atoms and preferably from 8 to 16 carbon atoms, or their salts.
  • uronic acids galacturonic, glucuronic acids, D-mannuronic, L-iduronic, L-guluronic
  • L-iduronic glucuronic acids
  • surfactant examples include amphoteric surfactants such as amphoteric derivatives of alkyl polyamines such as amphionic XL®, Mirataine H2C-HA® marketed by Rhône-Poulenc as well as Ampholac 7T / X® and Ampholac 7C / X® sold by Berol Nobel.
  • amphoteric surfactants such as amphoteric derivatives of alkyl polyamines such as amphionic XL®, Mirataine H2C-HA® marketed by Rhône-Poulenc as well as Ampholac 7T / X® and Ampholac 7C / X® sold by Berol Nobel.
  • alkali metal silicates mention may in particular be made of those having a SiO 2 / M 2 O molar ratio of 1.6 to 3.5 with M representing a sodium or potassium atom.
  • the amount of matrix (M) used is such that it represents from 20 to 80%, preferably from 30 to 70% of the weight of the emulsion in solid form (Es) expressed in dry form.
  • the solid emulsion (Es) of the multiple emulsion (Em) can be carried out in different ways, depending on the nature of the matrix. When it is a meltable matrix at a temperature below 80 ° C.
  • the solid emulsion of the multiple emulsion (Em) can be produced by adding to said multiple emulsion (Em) polyethylene glycol in the molten state at a temperature of the order of 60 to 80 ° C., or in solution aqueous, then crystallization by drying / cooling in thin film in a ventilated oven, and flaking.
  • a variant of this process consists in producing the multiple emulsion (Em) by dispersing the reverse emulsion (Ei) at a temperature of 60 to 80 ° C in molten polyethylene glycol added with (De) and then crystallization by drying. / thin film cooling in a ventilated oven, and flaking.
  • the solid form can be achieved by placing on a support on said material and optionally moderate drying.
  • the external aqueous phase of the multiple emulsion (Em) comprises at least one water-soluble or water-dispersible compound (M) which cannot be melted at a temperature below 100 ° C, as a drying additive for the multiple emulsion.
  • M water-soluble or water-dispersible compound
  • the multiple emulsion (Em) is diluted with water preferably comprising dispersing and / or stabilizing agent (De) and introduced into the matrix (M), then dried.
  • the drying operation (consisting in removing water from the external aqueous phase) can be carried out by any means known to those skilled in the art.
  • the drying is carried out so that at least 90% by weight of the external aqueous phase is eliminated.
  • Drying can be carried out in an oven, preferably in a thin layer.
  • the drying temperature is less than or equal to 100 ° C. More particularly, temperatures between 50 and 90 ° C are suitable for the implementation of this method.
  • Another method of drying the emulsion is a so-called rapid method.
  • spray drying drying by using Duprat® drums, or lyophilization (freezing-sublimation) are suitable.
  • Spray drying can be carried out in the usual manner in any known device such as for example an atomization tower associating a spraying carried out by a nozzle or a turbine with a stream of hot gas.
  • the inlet temperature of the gases is of the order of 100 ° C. to 200 ° C. and that of the outlet of the atomizing gases is preferably between 55 and 100 ° C. These temperatures are given for information only, and depend on the thermal stability of the various elements.
  • it is defined according to the desired final water content in the granule.
  • the desired average size of the granules (d50) is between 100 ⁇ m and a few millimeters (Sympatec), preferably between 100 and 800 ⁇ m.
  • Such granules can be obtained directly using a double-effect atomizer (drying / granulation). They can also be obtained using a single-effect atomizer (drying) associated with a granulation device (fluidized bed) with spraying of water, optionally additive with matrix material (M).
  • the average size of the granules (d50) obtained directly after drying is between 100 ⁇ m and a few millimeters (Sympatec), preferably between 100 and 800 ⁇ m.
  • a second object of the invention consists in the use of an emulsion (E) comprising a hydrophobic liquid or fusible phase (O) containing and / or consisting of at least one hydrophobic active material (A), said emulsion (E ) being: • in the form of a multiple emulsion (Em) comprising: - an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, with interface of the two phases, at least one water-soluble or water-dispersible stabilizing agent (Di) - an aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed, using at
  • Said substrate (S) can be of any material, in particular a metal or any natural, artificial or synthetic material, or a mixture of these materials.
  • Said hydrophobic phase (O) is preferably made of an active material capable of bringing its intrinsic properties or the benefits which result therefrom, to said substrate.
  • the aqueous external phase (We) can itself constitute the aqueous medium (B), with release of the hydrophobic phase and of the hydrophobic active material by deposition or application and drying of the emulsion on the substrate (S).
  • the emulsion according to the invention can be used in paints, preferably aqueous, or itself constitute a preferably aqueous paint, and be used to transport in particular a hydrophobicizing agent on a surface of the building material, plaster, cement, wood ..., with release of the hydrophobicizing agent by depositing and drying the paint on the surface. It can also be used for the treatment of metals. Likewise, it can be used in cosmetic compositions or itself constitute an aqueous cosmetic composition (moisturizing creams, sun creams, make-up products, styling gels, etc.); the hydrophobic phase can be or contain any hydrophobic active care material (such as conditioning agents, detangling agents, etc.), anti-UV agents, pigments, dyes, etc.
  • any hydrophobic active care material such as conditioning agents, detangling agents, etc.
  • the second object of the invention consists in particular in use of an emulsion (E) comprising a liquid or fusible hydrophobic phase (O) containing and / or consisting of at least one hydrophobic active material (A), said emulsion (E) being: • in the form of a multiple emulsion (Em) comprising: - an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, at the interface of the two phases, at least one water-soluble stabilizing agent or water-dispersible (Di) - an aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed, using at least one dispersing and / or stabilizing agent (De)
  • Brookfield viscosity at 25 ° C in solution at 1% by mass in water is less than 20,000 mPa.s., preferably less than 5,000 mPa .s., particularly ranging from 1 to 4500 mPa.s., to transport, in mili eu aqueous (B) brought into contact with a substrate (S), the hydrophobic phase (O) containing and / or consisting of at least one hydrophobic active material (A), towards said substrate (S), the volume of said aqueous medium being sufficient to cause destabilization and / or rupture of the emulsion
  • the emulsion (E) by dilution of said emulsion (E) and / or drying subsequent to dilution of said emulsion (E), and the provision and / or release of the material active (A) contained or constituent of the hydrophobic phase (O), on the substrate (S).
  • the emulsion (E) is a multiple emulsion
  • emulsion (Em) comprising at least 70% by weight of internal emulsion (Ei).
  • relative amounts of emulsion (Em) and aqueous medium (B) equivalent to a dilution of 2 to 100 times the volume of said emulsion (Em) can be used.
  • the emulsion according to the invention is particularly advantageous for conveying and depositing a hydrophobic active material on a hydroxyapatite surface (tooth), a keratin surface (skin, hair, leather) or a textile surface.
  • the hydrophobic phase can contain hydrophobic agents having refreshing properties, agents making it possible to fight against dental plaque, antiseptic agents, etc.
  • the emulsion (E) can be included or itself form a composition for dental or oral hygiene, composition intended to be rinsed or diluted. It may be toothpaste, mouthwash, etc.
  • Said substrate (S) may in particular be a keratinous surface, such as the skin and the hair.
  • the hydrophobic phase can be or contain any hydrophobic active care material (such as conditioning agents, detangling agents, etc.), anti-UV agents, pigments, dyes, etc .; the emulsion (E) can be included in or itself form a cosmetic composition intended to be rinsed or diluted; it may in particular be a shampoo, a conditioner, a shower gel, etc.
  • Said substrate (S) may be leather; the hydrophobic phase can be or contain any hydrophobic active material capable of providing the hydrophobic substrate, softness, flexibility, protection with respect to external agents, etc.
  • said substrate (S) is made of a textile material.
  • the textile substrate may be in the form of textile fibers or of articles made from natural textile fibers (cotton, linen or other natural cellulosic material, wool ...), artificial (viscose, rayon %) or synthetic ( polyamide, polyester ...) or mixtures thereof.
  • said substrate is a textile surface made of a cellulosic material, in particular cotton.
  • Said hydrophobic phase (O) is preferably made of a material for textile care ("textile care agent").
  • the particular examples of organosilicon (01) and organic (02) materials mentioned above are particularly well suited, very particularly organosilicon materials, especially amines.
  • the benefits brought by a hydrophobic lubricating phase (01) or (02) to a textile substrate are in particular the contribution of properties of softness (softness), anti-creasing (anti-wrinkling), ease of ironing (easy- ironing), abrasion resistance (especially protection against aging when wearing the garment or repeated washing operations), elasticity, color protection, retention of perfumes ...
  • perfumes preferably, these are dissolved in the hydrophobic phase (O), in particular in organosilicon (01) or organic (02) materials.
  • the aqueous bath (B) in which the textile substrate is present to acquire benefits can be very varied. It may be, without limitation, a soaking bath, washing, rinsing, padding ...
  • the emulsion (E) according to the invention can in particular be used as an additive in a detergent composition for washing or rinsing articles made of textile fibers, or as a detergent or rinsing composition for washing or rinsing articles made of textile fibers, with the aim of conveying a hydrophobic care agent ("textile care agent") and / or any other useful hydrophobic active material, and to promote the deposition thereof and / or thereof on an article made of textile fibers, in particular cotton, during the rinsing operation and / or during the subsequent drying (s) to the main washing operation in the case of a detergent composition for washing, or in the subsequent drying operation in the case of a rinsing composition.
  • textile care agent hydrophobic care agent
  • s subsequent drying
  • the use of the emulsion (E) in the form of a multiple emulsion (Em) or in the form of a water-dispersible solid (Es) containing a hydrophobic phase (O) of care, as composition of rinsing or in a composition for rinsing the laundry, made it possible to bring to the laundry, after drying, properties of softness, flexibility, anti-wrinkling (anti-wrinkling), ease of ironing (easy-ironing), abrasion resistance, elasticity, color protection, fragrance retention ...
  • the deposition of the hydrophobic phase (O) containing or consisting of the active material (A) on the substrate can be a deposition by adsorption , co-crystallization, trapping and / or adhesion.
  • the amount of emulsion (E) in the form of a multiple emulsion (Em) or in the form of a water-dispersible solid (Es) which may be present in a composition for washing textile fiber articles, according to the third object of the invention, corresponds to an amount of hydrophobic phase (O) representing from 0.0001% to 25%, preferably from 0.0001% to 5% of the total weight of the composition, with relative amounts of emulsion, expressed as an emulsion multiple (Em), and aqueous medium (B) equivalent to a dilution of 2 to 100 times the volume of said emulsion (Em).
  • the amount of emulsion (E) in the form of a multiple emulsion (Em) which may be present in a composition for rinsing articles of textile fibers, according to the third object of the invention, corresponds to an amount of hydrophobic phase (O ) representing from 0.0001% to 25%, preferably from 0.0001% to 5% of the total weight of the composition, with relative amounts of emulsion, expressed in multiple emulsion (Em), and of aqueous medium (B ) equivalent to a dilution of 2 to 100 times the volume of said emulsion (Em).
  • O hydrophobic phase
  • a washing composition, whether or not compacted or liquid powder, of articles made of textile fibers may contain at least one surfactant preferably chosen from anionic surfactants and nonionics or mixtures thereof.
  • anionic surfactants mention may be made of alkyl (C 8 -C ⁇ 5 ) benzene sulfonates (at a rate of 0-30%, preferably 1-25%, more preferably 2-15% by weight).
  • primary or secondary alkyl sulfates can be mentioned, in particular primary (C 8 -C ⁇ 5 ) alkyl sulfates; alkyl ether sulfates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; fatty acid esters sulfonates; sodium salts are generally preferred.
  • nonionic surfactants there may be mentioned the ethoxylates of primary or secondary alcohols, in particular the ethoxylates of alcohols aliphatic C 8 -C 2 o having from 1 to 20 moles of ethylene oxide per mole of alcohol, and more particularly the ethoxylates of primary or secondary aliphatic alcohols C 1 0-C 15 having from 1 to 10 moles of ethylene oxide per mole of alcohol; may also be mentioned non-ionic non-ethoxylated surfactants such as alkylpolyglucosides, glycerol monoethers, and polyhydroxyamides (glucamides).
  • non-ionic non-ethoxylated surfactants such as alkylpolyglucosides, glycerol monoethers, and polyhydroxyamides (glucamides).
  • the level of nonionic surfactants is 0-30%, preferably 1-25%, more preferably 2-15% by weight.
  • the choice and amount of the surfactant depends on the desired use of the detergent composition.
  • the surfactant systems to be chosen for washing textiles by hand or in the machine are well known to formulators. Amounts of surfactants as high as 60% by weight may be present in the compositions for hand washing. Amounts of 5-40% by weight are generally suitable for washing textiles in the machine.
  • these compositions comprise at least 2% by weight, preferably from 2-60%, more preferably 15-40% and particularly 25-35% by weight.
  • cationic mono-alkyl surfactants Mention may be made of the quaternary ammonium salts of formula R 1 R 2 R 3 R 4 N + X " where the groups R are long or short, alkyl, hydroalkyl or alkyl ethoxylated chains, X being a counterion (R 1 is a C 8 -C 22 , preferably C 8 -C 10, or C1 2 -C 1 4 alkyl group, R 2 is a methyl group, R 3 and R 4 being similar or different being a methyl or hydroxymethyl group); as well as cationic esters, such as choline esters.
  • Detergent compositions for most washing machines generally contain an anionic surfactant other than soaps, or a nonionic surfactant, or mixtures thereof, and optionally a soap.
  • Detergent compositions for washing textiles generally contain at least one builder, the total amount of builder is typically 5-80%, preferably 10-60% by weight.
  • inorganic adjuvants such as sodium carbonate, crystalline or amorphous aluminosilicates (10-70%, preferably 25-50% dry), lamellar silicates, inorganic phosphates (Na orthophosphate, pyrophosphate and tripolyphosphate). Further details relating to particularly suitable aluminosilicates and zeolites are given in WO 03/020819.
  • organic detergency builders such as polymers of polyacrylate type, acrylic / maleic copolymers and acrylic phosphinates; polycarboxylate monomers such as citrates, gluconates, oxidisuccinates, mono-, di- and tri-succinates of glycerol, dipicolinates, hydroxyethyliminodiacetates, malonates or succinates of alkyl or alkenyl; fatty acid sulfonate salts ....
  • organic detergency builders such as polymers of polyacrylate type, acrylic / maleic copolymers and acrylic phosphinates; polycarboxylate monomers such as citrates, gluconates, oxidisuccinates, mono-, di- and tri-succinates of glycerol, dipicolinates, hydroxyethyliminodiacetates, malonates or succinates of alkyl or alkenyl; fatty acid sulfonate salts ....
  • the organic detergency builders are citrates (5-30%, preferably 10-25% by weight), acrylic polymers, more particularly acrylic / maleic copolymers (0.5-10%, preferably 1- 10% by weight).
  • the compositions may favorably contain a bleaching system, in particular peroxide compounds such as inorganic persalts (perborates, percarbonates, perphosphates, persilicates and persulfates, preferably sodium perborate monohydrate or tetrahydrate, and sodium percarbonate) or organic peroxyacids (urea peroxide), capable of releasing oxygen in solution.
  • the bleaching peroxide compound is favorably present at 0.1-35%, preferably 0.5-25% by weight.
  • the preferred activators are peroxycarboxylic acids, in particular peracetic and pernonanoic acids. Mention may very particularly be made of N, N, N ', N', - tetracetyl ethylenediamine (TAED) and sodium nonanoyloxybenzene sulfonate (SNOBS).
  • TAED peracetic and pernonanoic acids.
  • SNOBS sodium nonanoyloxybenzene sulfonate
  • compositions also generally comprise one or more enzymes, in particular proteases, amylases, cellulases , oxidases, peroxidases and lipases (0.1-3% by weight), perfumes, anti-redeposition agents, anti-fouling, anti-color transfer, non-ionic softening agents ...
  • Detergent compositions for washing textiles may also be in the form of nonaqueous liquid tablets in an envelope made of a material dispersing in the washing medium such as polyvinyl alcohol for example. They comprise at least one water-miscible alcohol, such as in particular isopropyl alcohol, in an amount which can range from 5 to 20% by weight. .
  • compositions for rinsing articles of textile fibers can contain cationic or non-ionic softening agents. They can represent from 0.5 to 35%, preferably from 1-30%, more preferably from 3 to 25% by weight of the rinsing composition.
  • Cationic softeners are substantially non-water-soluble quaternary ammonium compounds comprising a single alkyl or alkenyl chain containing at least 20 carbon atoms, or preferably compounds having two polar heads and two alkyl or alkenyl chains containing at least 14 carbon atoms .
  • the softening compounds have two alkyl or alkenyl chains containing at least 16 carbon atoms, and particularly at least 50% of the alkyl or alkenyl groups have 18 or more carbon atoms.
  • the linear alkyl or alkenyl chains are predominant.
  • quaternary ammonium compounds having two long aliphatic chains are very commonly used, such as distearyl dimethyl ammonium chlorides; ditallow alkyl dimethyl ammonium.
  • the rinse compositions may further include nonionic softeners such as lanolin; lecithins and other phospholipids are also suitable.
  • the rinsing compositions may also contain nonionic stabilizing agents such as linear C 8 -C 22 alkoxylated alcohols containing from 10 to 20 moles of alkylene oxide, C 10 -C 20 alcohols and their mixtures.
  • the amount of non-ionic stabilizing agent represents 0.1-10%, preferably 0.5-5%, very particularly 1-4% by weight of the composition.
  • the molar ratio of the quaternary ammonium compound and / or other softening cationic agent to the stabilizing agent is favorably 40 / 1-1 / 1, preferably 18 / 1-3 / 1.
  • the composition may also comprise fatty acids, in particular monocarboxylated (C 8 -C 2 ) alkyl or alkenyl acids or their polymers; preferably they are saturated and non-saponified, like oleic, lauric or tallow acids. They can be used in an amount of at least 0.1%, preferably at least 0.2% by weight. In concentrated compositions, they can be present in an amount of 0.5-20%, preferably 1-10% by weight.
  • the molar ratio of the quaternary ammonium compound and / or other fatty acid softening cationic agent is favorably 10 / 1-1 / 10.
  • a final object of the invention consists in a method for conveying, to a substrate (S) in contact with an aqueous medium (B), at least one active material contained in or constituting a hydrophobic phase (O) liquid or fusible of an emulsion (E), said emulsion being • in the form of a multiple emulsion (Em) comprising: - an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, at the interface of the two phases, at least one water-soluble or water-dispersible stabilizing agent (Di) - an aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed , using at least one dispersing and / or stabilizing agent (De) • or in solid form (Es), water-dispersible in a multiple emulsion (Em), comprising - the reverse emul
  • the last object of the invention relates in particular to a method for conveying, to a substrate (S) in contact with an aqueous medium (B), at least one active material contained in or constituting a hydrophobic phase (O) liquid or fuse of an emulsion (E), said emulsion being in the form of a multiple emulsion (Em) comprising: an internal inverse emulsion (Ei) comprising said continuous hydrophobic liquid or fusible phase (O), an aqueous dispersed phase (Wi) and, at the interface of the two phases, at least one water-soluble or water-dispersible stabilizing agent (Di) - a aqueous or water-miscible external phase (We), in which the internal emulsion (Ei) is dispersed, using at least one dispersed, using at least one dis
  • Arlatone® F 127G of formula HO (CH 2 CH2 ⁇ ) ⁇ (CH (CH3) CH 2 ⁇ ) y (CH 2 CH 2 O) z H marketed by ICI -Uniquema
  • Example 1 Multiple emulsion Composition of the inverse emulsion (Ei):
  • Preparation of the internal aqueous phase Water is introduced into a 1 I reactor fitted with a paddle-type stirring.
  • the Meyprogat® 7 powder is then gradually introduced with stirring at room temperature.
  • the mixture is stirred for two hours at ambient temperature so as to disperse the gel particles of Meyprogat® 7 in a homogeneous manner.
  • the dispersion is sheared using a rotor-stator type tool
  • the pH of the internal aqueous solution / dispersion is 5 to 7.5
  • the internal aqueous phase is then introduced over 45 minutes at room temperature. Stirring is continued for 15 minutes to refine the emulsion.
  • An inverse emulsion (Ei) is obtained, the drops of dispersed aqueous phase (Wi) having a particle size of 1 ⁇ m (observation made under optical microscopy on a sample without and with prior dilution in Extrasoft oil).
  • composition of the multiple emulsion
  • a concentrated multiple emulsion (Em) is obtained, which is in the form of a viscous non-pourable cream; the average droplet size (d50) of internal reverse emulsion is close to 10 ⁇ m, with a low polydispersity index.
  • Example 2 multiple emulsion A multiple emulsion is prepared according to the procedure of Example 1, replacing the 10 parts by weight of Meyprogat® 7 with 10 parts of cellulose monoacetate.
  • EXAMPLE 3 Depositing Rhodorsil® Extrasoft Oil on Detergent Bath on Cotton
  • Test is carried out in a Tergotometer laboratory apparatus, well known to formulators of detergent compositions.
  • the device simulates the mechanical and thermal effects of washing machines of the American type with pulsator; thanks to the presence of 6 washing pots, it makes it possible to carry out series of simultaneous tests with appreciable time savings.
  • the pots are heated to 40 ° C.
  • Example 1 A quantity of double emulsion prepared in Example 1 or in Example 2 corresponding to 0.5 g of Rhodorsil® Extrasoft oil is introduced into each pot.
  • Rinsing cycle The tissue squares are then rinsed 3 times for 5 minutes (each time) with cold water.
  • the fabric squares are taken out and allowed to air dry. An assessment of softness performance is given by a jury of trained experts, in a blind test.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Veterinary Medicine (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Wood Science & Technology (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Dermatology (AREA)
  • Materials Engineering (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP04805319A 2003-11-13 2004-10-27 Emulsion zur beförderung eines hydrophoben wirkstoffs zu einem substrat in einem wässrigen medium Ceased EP1684894A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0313284A FR2862234B1 (fr) 2003-11-13 2003-11-13 Emulsion pour vehiculer une matiere active hydrophobe vers un substrat en milieu aqueux
FR0400665A FR2862235B1 (fr) 2003-11-13 2004-01-23 Emulsion pour vehiculer une matiere active hydrophobe vers un substrat en milieu aqueux
PCT/FR2004/002762 WO2005049189A1 (fr) 2003-11-13 2004-10-27 Emulsion pour vehiculer une matiere active hydrophobe vers un substrat en milieu aqueux

Publications (1)

Publication Number Publication Date
EP1684894A1 true EP1684894A1 (de) 2006-08-02

Family

ID=34524997

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04805319A Ceased EP1684894A1 (de) 2003-11-13 2004-10-27 Emulsion zur beförderung eines hydrophoben wirkstoffs zu einem substrat in einem wässrigen medium

Country Status (5)

Country Link
US (1) US20070128142A1 (de)
EP (1) EP1684894A1 (de)
JP (1) JP2007519506A (de)
FR (1) FR2862235B1 (de)
WO (1) WO2005049189A1 (de)

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2887448B1 (fr) * 2005-06-23 2009-04-17 Rhodia Chimie Sa Composition cosmetique comprenant un copolymere ampholyte
FR2887450B1 (fr) * 2005-06-23 2007-08-24 Rhodia Chimie Sa Ingredient concentre pour le traitement et/ou la modification de surfaces, et son utilisation dans des compositions cosmetiques
US7807766B2 (en) * 2005-09-21 2010-10-05 Cognis Ip Management Gmbh Polymers for use in cleaning compositions
DE102005047833A1 (de) * 2005-10-05 2007-04-19 Basf Ag Verfahren zur Herstellung von granulären oder pulverförmigen Waschmittelzusammensetzungen
EP1972326B1 (de) * 2005-12-28 2017-09-13 Kao Corporation Haut- oder haarwaschzusammensetzung
JP4886505B2 (ja) 2006-12-28 2012-02-29 花王株式会社 洗浄剤用組成物
DE102007013141A1 (de) * 2007-03-15 2008-09-18 Cognis Ip Management Gmbh Amphotere Polymere als Soil Release Additive in Wasch- und Reinigungsmitteln
GB0818473D0 (en) * 2008-10-08 2008-11-12 Probio Nutraceuticals As Composition
JP2011121871A (ja) * 2009-12-08 2011-06-23 Kao Corp 皮膚化粧料
ITVA20110009A1 (it) * 2011-03-25 2012-09-26 Lamberti Spa Composizione cosmetica per la pelle
FR2977801B1 (fr) * 2011-07-11 2013-08-16 Fabre Pierre Dermo Cosmetique Dispositif et procede pour la sterilisation a ultra-haute temperature d'une emulsion, notamment dermo-cosmetique, instable a la temperature de sterilisation
US9217094B2 (en) 2011-07-28 2015-12-22 The Board Of Trustees Of The University Of Illinois Superhydrophobic compositions
US9364859B2 (en) 2011-07-28 2016-06-14 Kimberly-Clark Worldwide, Inc. Superhydrophobic surfaces
TWI541025B (zh) 2012-02-28 2016-07-11 Suntory Holdings Ltd W / O / W type emulsion with time stability and its manufacturing method
US9452135B2 (en) 2012-03-20 2016-09-27 Particle Dynamics International, Llc Gelling agent-based dosage form
US10005917B2 (en) 2013-04-30 2018-06-26 Kimberly-Clark Worldwide, Inc. Non-fluorinated water-based superhydrophobic compositions
US9803100B2 (en) * 2013-04-30 2017-10-31 Kimberly-Clark Worldwide, Inc. Non-fluorinated water-based superhydrophobic surfaces
US10653738B2 (en) * 2014-07-22 2020-05-19 Meridian Research and Development Inc. Topical medications for bruises and burns
WO2016138272A1 (en) 2015-02-27 2016-09-01 Kimberly-Clark Worldwide, Inc. Non-fluorinated water-based superhydrophobic compositions
WO2018145895A1 (en) 2017-02-10 2018-08-16 Unilever Plc Ancillary laundry composition
WO2018146260A1 (en) * 2017-02-13 2018-08-16 Unilever Plc Use of laundry serum
PL3580318T3 (pl) * 2017-02-13 2023-10-02 Unilever Ip Holdings B.V. Sposób dostarczania kompozycji do prania
US11180721B2 (en) 2017-02-13 2021-11-23 Conopco, Inc. Ancillary laundry composition

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4565647B1 (en) * 1982-04-26 1994-04-05 Procter & Gamble Foaming surfactant compositions
FR2679563B1 (fr) * 1991-07-22 1995-06-09 Agro Ind Recherc Dev Alkylgalactosides uronates d'alkyle, leur procede de preparation et leurs applications, notamment comme agents tensio-actifs non ioniques.
CA2294988C (en) * 1997-07-01 2015-11-24 Isis Pharmaceuticals Inc. Compositions and methods for the delivery of oligonucleotides via the alimentary canal
FR2767064B1 (fr) * 1997-08-07 1999-11-12 Centre Nat Rech Scient Procede de liberation d'un principe actif contenu dans une emulsion multiple
EP1137396B1 (de) * 1998-12-05 2004-09-29 Imperial Chemical Industries PLC Emulgiersystem und emulsionen
FR2798601B1 (fr) * 1999-09-20 2001-12-21 Centre Nat Rech Scient Emulsion double polydisperse, emulsion double monodisperse correspondante et procede de preparation de l'emulsion monodisperse
JP4478264B2 (ja) * 1999-11-29 2010-06-09 ライオン株式会社 Ｗ／ｏ／ｗ型複合エマルション
AU784642B2 (en) * 2000-05-26 2006-05-18 Color Access, Inc. Low emulsifier multiple emulsions
JP2001354820A (ja) * 2000-06-14 2001-12-25 Shiseido Co Ltd 複合エマルジョン及びこれを配合した化粧料
FR2815550B1 (fr) * 2000-10-20 2003-08-29 Rhodia Chimie Sa Granules obtenus par sechage d'une emulsion multiple
FR2815637B1 (fr) * 2000-10-20 2006-08-04 Rhodia Chimie Sa Procede de preparation d'une emulsion dont la phase huileuse est de forte viscosite
KR100435921B1 (ko) * 2000-12-29 2004-06-12 주식회사 태평양 동수역학적 이중 안정화에 의한 안정한 수-유-수 다중에멀젼 시스템 및 이의 제조방법
JP4858664B2 (ja) * 2001-07-23 2012-01-18 ライオン株式会社 Ｗ／ｏ／ｗ型複合エマルション
DE60220297T2 (de) * 2001-08-31 2007-09-06 Unilever N.V. Wäschebehandlungsmittel
FR2833184B1 (fr) * 2001-12-11 2004-01-23 Rhodia Chimie Sa Procede de preparation d'une emulsion multiple de type eau/huile/eau
FR2833186B1 (fr) * 2001-12-12 2004-01-23 Rhodia Chimie Sa Utilisation de copolymeres cationiques a blocs comme aide au depot d'emulsions simples ou multiples
ATE323462T1 (de) * 2002-01-04 2006-05-15 Oreal Ein silikon-copolymer und entweder ein polymer aus einem ethylenisch ungesättigten monomer mit sulfongruppen oder ein organisches pulver enthaltende zusammensetzung; deren verwendungen, insbesondere in der kosmetik
US7094842B2 (en) * 2002-01-04 2006-08-22 L'oreal Composition containing a silicone copolymer and an AMPS-like polymer and/or organic powder
JP2007520555A (ja) * 2004-02-05 2007-07-26 バクスター・インターナショナル・インコーポレイテッド 自己安定化剤の使用により調製された分散剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005049189A1 *

Also Published As

Publication number Publication date
US20070128142A1 (en) 2007-06-07
WO2005049189A1 (fr) 2005-06-02
JP2007519506A (ja) 2007-07-19
FR2862235B1 (fr) 2007-12-28
FR2862235A1 (fr) 2005-05-20

Similar Documents

Publication Publication Date Title
EP1684894A1 (de) Emulsion zur beförderung eines hydrophoben wirkstoffs zu einem substrat in einem wässrigen medium
EP1453597B1 (de) Verwendung von kationischen blockcopolymeren als beschichtigungshilfsmittel von einfachen und multiplen emulsionen
EP1345970B1 (de) Verwendung von amphoteren polysacchariden zur behandlung von gegenständen aus textilfasern
WO2016020622A1 (fr) Utilisation dans des compositions détergentes de polymères obtenus par polymérisation en émulsion inverse basse concentration avec un faible taux de monomères neutralises
EP2069471A1 (de) Wasch- oder reinigungsmittelabgabesystem
FR2529907A1 (fr) Composition detergente non-ionique favorisant la separation des salissures, son procede de preparation et son application au lavage des matieres fibreuses synthetiques
FR2829693A1 (fr) Creme cosmetique moussante
FR3016288A1 (fr) Article de conditionnement comportant une enveloppe et une composition anhydre comprenant un agent oxydant
FR2913896A1 (fr) Nouvelles compositions a base de glycosides d'alkyle, procede pour leur preparation et utilisation comme agent tensioactifs
JP2019206521A (ja) カルボキシメチル化セルロースナノファイバーを含む添加剤
JP6980801B2 (ja) マイクロカプセルを含む消費者製品組成物
FR2537596A1 (fr) Detergent liquide puissant assouplissant les textiles
LU85927A1 (fr) Composition detergente assouplissant les tissus,renforcee par un adjuvant de detergence et procede de lavage
EP2366012A1 (de) Verbesserungen bei textilbehandlungsmitteln
WO2005003270A1 (fr) Emulsion inverse ou multiple eau/huile ou eau/huile/eau, comprenant une phase hydrophobe et un polysaccharide substitue hydrosoluble ou hydrodispersable
FR3117024A1 (fr) Composition solide anhydre comprenant une association de tensioactifs anioniques particuliers et au moins un polysaccharide cationique
EP1257599A1 (de) Verwendung von zusammensetzungen enthaltend proteine, polysaccharide und ethylenoxidderivate als tensidmittel
WO2005032497A2 (fr) Emulsions comprenant un polymere dendritique et utilisation d'un polymere dendritique comme agent d'emulsification
FR2575177A1 (fr) Detergent et composition detergente liquides assouplissant les tissus pour gros lavages contenant de la bentonite
FR3117027A1 (fr) Composition solide anhydre comprenant une association de tensioactifs anioniques de types sulfonate et carboxylate
FR3117019A1 (fr) Composition solide anhydre comprenant une association de tensioactifs anioniques carboxylates et sulfonates, de tensioactifs cationiques et éventuellement de tensioactifs amphotères ou zwittérioniques
FR2581992A1 (fr) Polyamides antistatiques d'acides trialkylacetiques et de polyamines, composition detergente les contenant et procedes pour laver et/ou traiter le linge les utilisant
EP1419231B1 (de) Additiv für eine zusammensetzung zur behandlung von textilien sowie seine verwendung als pflegemittel
FR2862234A1 (fr) Emulsion pour vehiculer une matiere active hydrophobe vers un substrat en milieu aqueux
EP1188816A1 (de) Wasch- und Reinigungsmittel auf Basis von Alkyl- und/oder Alkenyloligoglycosiden und Fettalkoholen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060501

AK Designated contracting states

Kind code of ref document: A1

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

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20070709

REG Reference to a national code

Ref country code: DE

Ref legal event code: R003

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20110423