EP1667636A2 - Emulsions comprising a dendritic polymer and use of a dendritic polymer as an emulsification agent - Google Patents

Emulsions comprising a dendritic polymer and use of a dendritic polymer as an emulsification agent

Info

Publication number
EP1667636A2
EP1667636A2 EP20040787480 EP04787480A EP1667636A2 EP 1667636 A2 EP1667636 A2 EP 1667636A2 EP 20040787480 EP20040787480 EP 20040787480 EP 04787480 A EP04787480 A EP 04787480A EP 1667636 A2 EP1667636 A2 EP 1667636A2
Authority
EP
Grant status
Application
Patent type
Prior art keywords
emulsion
phase
function
formula
preferably
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.)
Withdrawn
Application number
EP20040787480
Other languages
German (de)
French (fr)
Inventor
Mikel Morvan
Alain Senechal
Olivier Anthony
Franck Hameau de Normandie TOURAUD
Jean-François SASSI
Katerina Karagianni
René Les Hauts du Golf ROSSIN
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

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/02Cosmetics or similar toilet preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/066Multiple emulsions, e.g. water-in-oil-in-water
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/442Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/72Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toilet preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88Polyamides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0008Detergent materials characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017Multi-phase liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715Polyesters; Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719Polyamides; Polyimides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines, polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/004Preparations used to protect coloured hair

Abstract

The invention relates to novel emulsions comprising a dendritic polymer. The invention also relates to the use of a dendritic polymer as an emulsification agent. The inventive emulsions are suitable for use in the cosmetics, detergents, paint and coatings industries.

Description

Emulsions comprising a dendritic polymer and use of a dendritic polymer as emulsifier

The present invention relates to novel emulsions, comprising a dendritic polymer. It also relates to the use of a dendritic polymer as emulsifying agent. The emulsions are structures, or systems, physicochemical finding applications in many fields. Also known formulations in the form of emulsions. The application areas include cosmetic formulations, detergent formulations, formulations for coatings

(Painting ...), certain polymerization processes (latex preparation, preparation of polymers or polyacrylamide-based copolymers), plant protection formulations. Emulsions are also means vectorization or protection of a compound (internal phase or compound included in the internal phase). An emulsion comprises at least two immiscible liquid phases, an outer phase and an inner phase dispersed in droplet form in the external phase. Often one of the two phases is an aqueous phase. If the external aqueous phase, often referred to as direct emulsion, or "oil in water" emulsion. If the internal aqueous phase, often referred to as inverse emulsion, or "water in oil" emulsion. An emulsion generally comprises also an emulsifying agent, playing a role at the interfaces of the droplets. An emulsion is generally prepared by mixing more or less vigorous the two phases and, if appropriate the emulsification agent. If the resulting mixture is at thermodynamic equilibrium is generally referred microemulsion. If the resulting mixture is out of thermodynamic equilibrium, energy being imparted to the system by mixing, generally referred to simply emulsion. In this application, the term "emulsion" of course covers emulsions, and also microemulsions. The droplet size, and their stability over time, depend in particular on the nature and quantity of the various phases and of the emulsifier. They also generally depend on the strength of the mixture implemented for obtaining them (amount of energy imparted to the system). Thus, an emulsifying agent, and its amount may be chosen according to the phase to be emulsified. Many emulsifying agents are known. Among the most used include surfactants. This is often molecules of relatively low molecular weight comprising a hydrophilic portion and a hydrophobic portion. These agents can be disadvantageous in some applications. They are often irritating, which has a major disadvantage, for example in the fields of cosmetics and pharmaceuticals. They can further have a negative impact on the environment. Their presence in certain formulations, especially in coating formulations such as paints, can induce migration phenomena at interfaces, and thus induce appearance problems or cohesion with the coated object. Finally, they are often high foaming, which is not always desired for the formulation and can lead to difficulties in the preparation of a formulation. Polymeric emulsifying agents are also known. There may be mentioned for example the copolymers in poly blocks (ethylene oxide) -poly (propylene oxide) - poly (ethylene oxide) used for the execution of direct emulsions. Also exemplary copolymers polyhydroxystearate-PEG-polyhydroxystearate type, for example marketed under the name Arlacel or Superonic by Uniqema, used for making inverse emulsions. Also known is the use of polysaccharides and polysaccharide derivatives. These polymeric agents provide solutions for emulsification of particular systems for which there is no known effective enough surfactant (amount introduced, stability over time ...), where where a surfactant have disadvantages, such as that were mentioned above. However, the potential use of these polymeric compounds are limited. For example, they can present high temperature low resistance, or a substantial degradability in formulations comprising enzymes. The present invention relates to novel emulsions, including new by the emulsifier, as an alternative to the known emulsions. It thus provides the news of a polymeric compound used as emulsifying agent. The emulsions according to the invention and the use according to the invention, in particular the advantage of a low-foaming, and / or high temperature resistance, and / or a low degradability in formulations comprising enzymes and / or heavy use of versatility. The emulsions according to the invention and the use according to the invention have the advantage, for inverse emulsions, allow obtaining small dispersions stable. In addition, the emulsions according to the invention have the advantage of being stable in a wide variety of backgrounds. They are also stable when the external phase is an aqueous phase which may contain a wide variety of products. They can be implemented in the presence of a significant quantity of such a That a detergent surfactant, eg an anionic surfactant. Under certain conditions and formulations, the emulsifying agent may be adsorbed on surfaces, and thus serve as a vector of filing of the internal phase to a surface. In particular such vectorization by the emulsifying agent is not screened by the presence of anionic surfactants. This is particularly useful for detergents or shampoos.

Thus, the invention provides an emulsion comprising an internal phase, an external phase, and an emulsifier polymer, one phase being an aqueous phase, characterized in that the emulsifying polymer is a dendritic polymer. Similarly, the invention provides the use of a dendritic polymer as emulsifying agent. the emulsions according to the invention it is specified that comprise the dendritic polymer as an emulsifying agent, but it is not excluded that they additionally comprise one or more other emulsifying agents. Sometimes referred to as co-emulsifiers or emulsifier toning, e.g. toning surfactant ( "surfactant booster"). As part of inverse emulsions, the dendritic polymer is advantageously used as the sole emulsifying agent.

Emulsion The emulsion phase comprises at least two immiscible liquid phases, an internal phase and an external phase, one of which is aqueous. It is not excluded that the emulsion comprises three immiscible phases, the emulsions then with an aqueous phase, a first group of droplets (first internal phase) dispersed in the external phase, and a second group of droplets (second phase internal) dispersed in the external phase. It is not excluded that a phase (aqueous phase or not) is not miscible with the internal phase is dispersed as droplets within droplets of the internal phase. In this case we often speak of multiple emulsions, emulsion comprising an internal and an external emulsion. For example, there may be water in oil emulsions in water, comprising an inner phase (water), an intermediate (oil) phase and an outer phase. The dispersion of the internal phase in the intermediate phase is an internal reverse emulsion, the dispersion of the intermediate phase in the external phase is an external direct emulsion. Likewise, in this application, we can speak of internal or external emulsifying agent. In the present application the inverse emulsion concept covers both a simple inverse emulsion an internal inverse emulsion of a multiple emulsion. The concept of direct emulsion covers both a simple direct emulsion and an external direct emulsion of a multiple emulsion. Aqueous Phase The aqueous phase can be an external phase, if applicable an outer phase of a multiple emulsion. There is talk of direct emulsions. The aqueous phase to be an internal phase, if appropriate the outer phase of a multiple emulsion. There is talk of inverse emulsions. The aqueous phase comprises water course, and possibly other compounds. Other compounds may be solvents or co-solvents, dissolved or solid compounds dispersed in water, such as active materials. By "other compounds" of the aqueous phase, does not refer to the liquid inner phase or intermediate phase of a multiple emulsion. The dendritic polymer is preferably dispersible or soluble in water. The aqueous phase may also include compounds to give the solution a pH and / or salts having substantially no influence on the pH. It was noted that the pH may affect the water solubility of the dendritic polymer and the hydrophilicity of groups within the dendritic polymer. This is particularly the case for the carboxylic acid groups, and amino groups. It is preferable to be in pH and concentration conditions such that the dendritic polymer is dispersible or soluble in water, and / or such as pH sensitive groups are in ionic form. If there is a pH limit beyond or below which the dendritic polymer is soluble or dispersible, the pH is preferably within a range from the limit to 2 units above or below the limit, in domain dispersibility or solubility. Such conditions and such groups are detailed below, in connection with the description of the dendritic polymers. The aqueous phase may also comprise compounds conventionally used in the field of formulations comprising emulsions and emulsions, for example in the fields of household care (detergents, washing, hard surface cleaning, dishwashing), in the areas of cosmetics (hair care, shampoo, shower gels, creams, milks, lotions, gels, deodorants), in the industrial (emulsion polymerization, surface treatment in industrial processes, lubrication ..), the areas of coatings eg in paints. It may for example be surfactants, anionic, cationic, amphoteric, zwitte onic, or nonionic surfactants, detergency adjuvants (builders), of hydrophilic active agents, salts, viscosifying agents. The non-aqueous phase emulsion comprises an immiscible phase with the aqueous phase. For simplicity, we will designate this phase by "non-aqueous phase" or "oil phase" or "hydrophobic phase". By immiscible phases, is meant that a phase is not soluble to more than 10% in the other phase, at a temperature of 20 ° C. The nonaqueous phase can be the internal phase (direct emulsions), or the external phase (reverse emulsions). It can in particular be an intermediate phase of a multiple emulsion. Examples of compounds constituting the non-aqueous phase, or included in the nonaqueous phase include: - oils / fats / waxes of animal or vegetable origin;

- mineral oils / waxes, for example paraffin hydrocarbon;

- the products resulting from the alcoholysis of the aforementioned oils and optionally subsequent esterification;

- the product from the transesterification of the aforementioned oils; - essential oils;

- mono-, di- and tri- glycerides;

- fatty acids, saturated or unsaturated, comprising 10 to 40 carbon atoms; esters of such acids and alcohol having 1 to 6 carbon atoms;

- monohydric saturated or unsaturated, containing 2 to 40 carbon atoms; - polyols containing 2 to 10 carbon atoms;

- silicones, especially amino silicones;

- hydrocarbons or hydrocarbon fractions;

- insoluble monomer in water, in particular used for polymerizations isocyanate with polyols or for latex polymerizations, - the precursors of insoluble resins or macromonomers in water, such as alkyd or isocyanate compounds. As oils / fats / waxes of animal origin include, among others, sperm whale oil, whale oil, seal oil, shark oil, cod liver oil, pork fat, sheep fat (tallow), perhydrosqualene, beeswax, alone or mixed. As examples of oils / fats / waxes of plant origin, may be mentioned, among others, rapeseed oil, sunflower oil, peanut oil, olive oil , walnut oil, corn oil, soybean oil, avocado oil, linseed oil, hemp oil, grape seed oil, oil copra, palm oil, cottonseed oil, babassu oil, jojoba oil, sesame oil, castor oil, macadamia oil, oil sweet almond, carnauba wax, shea butter, cocoa butter, peanut butter, alone or mixed. Concerning mineral oils / waxes include among other naphthenic oils, paraffin (petroleum jelly), iso-paraffin, paraffin waxes, alone or mixed. The products obtained from the alcoholysis of the abovementioned oils can also be used. Among the essential oils include no intention of limitation, oils and / or essences of mint, spearmint, peppermint, menthol, vanilla, cinnamon, bay, anise, d eucalyptus, thyme, sage, cedar leaf, nutmeg, citrus (lemon, lime, grapefruit, orange), fruit (apple, pear, peach, cherry, plum, strawberry, raspberry, apricot , pineapple, grapes, etc.), alone or in mixtures. Regarding the fatty acids, the latter, saturated or unsaturated, comprise 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and may comprise one or more ethylenic unsaturations, conjugated or unconjugated. It should be noted that said acids may comprise one or more hydroxyl groups. Examples of saturated fatty acids include palmitic, stearic and behenic acid. Examples of unsaturated fatty acids include myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic, ricinoleic, and mixtures thereof. In regard to the fatty acid esters include the esters of the acids listed above, for which the portion derived from the alcohol contains 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, etc. As examples of alcohols of these esters include ethanol and those corresponding to the abovementioned acids. Among the suitable polyols of these esters include preferably glycerol. The non-aqueous phase may comprise a silicone or a mixture of several of them. We often speak of silicone oils. The amino silicones are particularly useful in the fields of detergents. Below gives more details about the silicones. It may be in particular an oil, a wax or a resin into a linear polyorganosiloxane, cyclic, branched or crosslinked. Said polyorganosiloxane has preferably a dynamic viscosity measured at 25 ° C and shear rate of 0.01 Hz for a stress of 1500 Pa (performed on a Carrimed ® type CSL2-500) comprised between 10 4 to 10 9 cP. It may include:

• a nonionic organopolysiloxane • a polyorganosiloxane having at least one cationic or potentially cationic function

• a polyorganosiloxane having at least one anionic or potentially anionic functional • an amphoteric polyorganosiloxane having at least one cationic function or potentially cationic and at least one anionic or potentially anionic functional Preferably, it is a polyorganosiloxane not -ionique or amine. Examples of organopolysiloxanes which may be mentioned: linear organopolysiloxanes, cyclic or crosslinked formed of nonionic organosiloxane units of the general formula (R) a (X) bS O) [4- (a + b)] / 2 0) in which formula

• the symbols R are identical or different and represent an alkyl hydrocarbon radical, linear or branched, having from 1 to 4 carbon atoms, aryl, especially phenyl;

• the symbols X are identical or different and represent a hydroxyl group, an alkoxy radical linear or branched, having 1 to 12 carbon atoms, a function OCOR ', wherein R' represents an alkyl group containing from 1 to 12 carbon atoms, preferably 1 carbon atom;

• a is 0, 1, 2 or 3

• b is 0, 1, 2 or 3

• a + b is 0, 1, 2 or 3

Preferentially, said polyorganosiloxane is at least substantially linear, and most preferably linear. For example, there may be mentioned in particular the α-ω bis oils (hydroxy) polydimethylsiloxane, α-ω bis oils (trimethyl) polydimethylsiloxane, cyclic polydimethylsiloxanes, polymethylphenylsiloxanes. polyorganosiloxanes linear, cyclic or crosslinked comprising, per mole, at least one ionic organosiloxane unit or nonionic surfactant of the general formula (R) a (X) b (B) cSi (O) [4 - (a + b + c) ] / 2 in which formula 00

• the symbols R are identical or different and represent an alkyl monovalent hydrocarbon radical, linear or branched, having from 1 to 4 carbon atoms, aryl, especially phenyl; • the symbols X are identical or different and represent a hydroxyl group, an alkoxy radical linear or branched, having 1 to 12 carbon atoms, a function OCOR ', wherein R' represents an alkyl group containing from 1 to 12 carbon atoms, preferably 1 carbon atom;

• the symbols B are identical or different and represent an aliphatic and / or aromatic and / or cyclic hydrocarbylene group containing up to 30 carbon atoms, optionally interrupted by one or more oxygen and / or nitrogen and / or sulfur, optionally bearing one or more ether, ester, thiol, hydroxyl, amino optionally quaternized, carboxylate, the symbol B is preferably bonded to silicon via an Si-C-;

• a is 0, 1 or 2 • b is 0, 1 or 2

• c represents 1 or 2

• a + b + c is 1, 2 or 3

Examples of substituents corresponding to the symbol (B) in formula (II) above, there may be mentioned - the polyether groups of the formula - (CH 2) n - (OC 2 H 4) m - (OC 3 H 6) m -OR ', wherein n is 2 or 3, m and p each range from 0 to 30 and R' represents an alkyl residue containing from 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms , primary amino groups, secondary, tertiary or quaternized, such as those of formula - R 1 -N (R 2) (R 3) where

the symbol 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,

the symbols R 2 and R 3, same or different are H. an alkyl or hydroxyalkyl group containing from 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms,. an alkyl amino group, preferably primary, the alkyl group contains from 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, optionally substituted and / or interrupted with at least one nitrogen atom and / or oxygen, said amino group optionally being quaternized, for example by a hydrohalic acid or an alkyl or aryl halide. Mention may in particular those of the formulas - (CH 2) 3 NH 2 - (CH 2) 3 NH 3 + X '

- (CH 2) 3 N (CH 3) 2 (CH 2) 3 N + (CH 3) 2 (C 18 H 37) X '.

- (CH 2) 3 NHCH 2 CH 2 NH 2 - (CH 2) 3 N (CH 2 CH 2 OH) 2

- (CH 2) 3 N (CH 2 CH 2 NH 2) 2

Preferentially, the amino functional polyorganosiloxanes carriers, exhibit in their chain, per 100 total carbon silicon, 0.1 to 50, preferably from 0.3 to 10, especially from 0.5 to 5 carbon aminofonctionalisés silicon. sterically hindered piperidyl groups the formula III

where R 4 * is a divalent hydrocarbon radical chosen from: * linear or branched alkylene radicals having 2 to 18 carbon atoms; * Alkylene-carbonyl radicals whose linear or branched alkylene part contains 2 to 20 carbon atoms; * Alkylene-cyclohexylene radicals whose linear or branched alkylene part contains 2 to 12 carbon atoms and the cyclohexylene portion contains 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 wherein R 7 radicals identical or different, 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 7 radicals have the meanings indicated above; radicals of formula -R 8 -O-R 9 - O-CO-R 8 in which R 8 and R 9 radicals are identical or different, represent alkylene radicals having 2 to 12 carbon atoms and the radical R 9 is optionally substituted with a hydroxyl radical; U represents -O- or -NR 10 -, R 10 being a radical chosen from a hydrogen atom, a linear or branched alkyl having 1 to 6 carbon atoms and a divalent radical of formula:

wherein 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 1 to 12 carbon atoms, one of the valency bonds (that of R 11) being connected to the atom of -NR 10 -, the other (that of R 4) being connected to a silicon atom; 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 O ".

or piperidyl groups sterically hindered formula IV

* R '4 is chosen from a trivalent radical of formula: - (CH,) m CH \ co where m represents a number from 2 to 20, and a trivalent radical of formula:

where p is 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 having 1 to 6 carbon atoms; * R 5 and R 6 have the same meanings as . those given above for formula III Preferably said polyorganosiloxane sterically hindered amino function is a linear polyorganosiloxane, cyclic or three-dimensional of formula (V):

wherein: (1) the symbols Z, which are identical or different, represent R 1 below and / or the symbol B below; (2) the symbols R 1, R 2 and R 3, 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, preferably a hydroxy radical, an ethoxy radical, a methoxy radical or a methyl radical; (3) the symbols B, which are identical functional groups and / or different, represent a group to function (s) piperidinyl (s) sterically hindered (s) selected from those mentioned above; and (4) - the number of organosiloxy without group B ranges from 10 to 450, preferably from 50 to 250; - the number of organosiloxy with a group B ranges from 1 to 5, preferably 1 to 3; - 0 <w <10 and 8 <x <448. Either Preferably, said polyorganosiloxane is linear. For example polyorganosiloxanes commercial products that can be implemented as hydrophobic phase (A), we can mention the RHODORSIL® 21645 oils, RHODORSIL® Extrasoft marketed by Rhodia.

The non-aqueous phase may comprise water-insoluble monomers, used in particular for polymerization processes in emulsion, eg for the manufacture of latex. Finally, it is specified that it is not excluded that the non-aqueous phase comprises a quantity of water, or water soluble monomers, which does not exceed the water solubility limit or in monomer in said phase. Examples of monomers that may constitute the non-aqueous phase, or be comprised in said phase include, alone or as mixtures:

- esters of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation;

- esters of saturated carboxylic acids having 8 to 30 carbon atoms, optionally bearing a hydroxyl group;

- unsaturated nitriles β-ethylenically, vinyl ethers, vinyl esters, vinylaromatic monomers, halides of vinyl or vinylidene; - hydrocarbon monomers, linear or branched, aromatic or not, comprising at least one ethylenic unsaturation;

- the macromonomers deriving from such monomers. These include in particular:

- esters of (meth) acrylic acid with an alcohol having 1 to 12 carbon atoms such as methyl (meth) acrylate, (meth) acrylate,

Propyl (meth) acrylate, (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl acrylate, 2-ethylhexyl, isodecyl acrylate ;

- vinyl acetate, vinyl Versatate®, vinyl propionate, vinyl chloride, vinylidene chloride, methyl vinyl ether, ethyl vinyl ether; - vinyl nitriles include more particularly those having from 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile;

- styrene, α-methylstyrene, vinyltoluene, butadiene, chloroprene. It is noted that the non-aqueous internal phase may comprise a phase, aqueous or non-dispersed form of an emulsion therein. The emulsion is then a multiple emulsion.

The dendritic polymer emulsion according to the invention comprises, as emulsifying agent, a dendritic polymer. The term "dendritic polymer" refers to macromolecular compounds comprising several branches. It can be regular dendrimers or hyperbranched polymers. The dendritic polymer comprises hydrophobic groups and hydrophilic groups. The hydrophobic groups may be included in repeating units in the polymer. This may be for example at least divalent alkylene groups with at least three consecutive carbon atoms, or groups comprising at least divalent a phenyl moiety, e.g., phenylene. It is advantageously a group of formula - (CH 2) n - where n is greater than or equal to 3, for example 4, 5, 6, or 11, and / or a group of formula -C 6 H -. The hydrophilic groups may be included in repeating units in the polymer and / or be included at the ends of polymer chains. When the emulsion is a direct emulsion, the aqueous phase being the external phase, at least a portion of the hydrophilic or potentially hydrophilic groups are preferably groups present at the ends of polymer chains. The hydrophilic groups included in repeating units are often regarded as functions of polymerization. This is for example groups, or functions, of formula -COO- (polyesters), -O- (polyethers), -CONH- (polyamide), -OCOO- (polycarbonate), -NH-COO- (polyurethane) , -N <(polyamine), -NH-CO-NH- (urea), -CO- NH-CO- (imide). It is noted that it is not excluded that the ends of polymer chains include hydrophobic groups such as alkyl groups. The presence of such groups can help to modulate the emulsifying properties of the dendritic polymer. The hydrophobic groups may be included in repeating units in the polymer and / or be included at the ends of polymer chains. When the emulsion is an invert emulsion, the aqueous phase is the internal phase, at least a portion of the hydrophobic groups are preferably groups present at the ends of polymer chains. It is noted that it is not excluded that the ends of polymer chains comprise hydrophilic groups or potentially hydrophilic. The presence of such groups can help to modulate the emulsifying properties of the dendritic polymer. When the emulsion is a multiple emulsion comprising an inner aqueous phase, an intermediate phase and an outer aqueous phase, the internal phase and the intermediate phase comprising an internal reverse emulsion, the intermediate phase and the external phase constituting an outer direct emulsion, and when the external direct emulsion and the inner inverse emulsion comprise the dendritic polymer, it preferably comprises hydrophobic groups and hydrophilic groups (or potentially hydrophilic) at the end of the polymer chains.

The dendritic polymer may preferably comprise hydrophilic or potentially hydrophilic groups (based e.g., pH) at the ends of polymer chains. Moreover the nature and properties of these groups can be more easily controlled, modified or varied, either during the polymerization or after, by post-functionalization. The dendritic polymer may preferably comprise hydrophobic groups at the ends of polymer chains. Moreover the nature and properties of these groups can be more easily controlled, modified or varied, either during the polymerization or after, by post-functionalization.

Examples of hydrophilic groups include: - the acid groups such as sulfonic groups, phosphonic, carboxylic acids, and their basic forms sulfonate, phosphate, phosphonate, carboxylate, - amino groups, primary, secondary, tertiary, their acid forms ammonium, and quaternary ammonium groups. It is mentioned that the hydrophilicity of a group may depend on the pH. In this application, hydrophilic group denotes groups which are hydrophilic at any pH, as well as groups whose hydrophilicity depends on the pH (potentially hydrophilic groups). Examples of hydrophobic groups include: - alkyl groups, saturated or unsaturated, aryl, aralkyl, or alkylaryl, for example phenyl or naphthyl, silicones or silanes groups, - fluorinated groups.

Examples of dendritic polymers include: - polypropylene imine dendrimers, such as Straburst® range on the market by the company DS - dendrimers polyamidoester (or polyester amide), such as placing on the range HYBRANE® market by the company DSM, - polyamidoamine dendrimers (PAMAM) - polyether dendrimers - hyperbranched polymers diaminobutane-aminopropyl DAB (PA) n - hyperbranched polyesters, such as range BOLTORN® marketing by Perstorp . Hyperbranched polyesters and polyamides include hyperbranched dendritic polymers particularly suitable for the implementation of the invention.

According to an interesting embodiment, the dendritic polymer is a polymer obtainable by a process comprising the steps of:

Step a) polycondensation of at least one polyfunctional monomer of formula (I), comprising at least three reactive functions polycondensation AR- (B) f (I) in which formula - f is an integer greater than or equal to 2, preferably ranges from 2 to 10, particularly is 2 - the symbol a represents a reactive functional group or a group carrying a reactive function selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors - the symbol B represents a reactive functional group or a group carrying a reactive function selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato or their precursors, antagonist a - the symbol R represents a linear aliphatic polyvalent hydrocarbonné or branched, cycloaliphatic or aromatic group containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms of oxygen , Nitrogen, sulfur or phosphorus, said remainder optionally having functions or non-functional groups capable of reacting with the functional groups A and B, Step b) optionally, hydrophilic functionalizing at least part of the polymer obtained in step polycondensation. The symbol B represents a reactive functional antagonist of the reactive functional group A; this means that the function B is capable of reacting with the function A by condensation. Thus, the antagonistic functions

- an amino function include the carboxy functions (amide formation), isocyanato (a urea formation), oxiranyl (formation of a secondary or tertiary amine β-hydroxylated)

- a carboxy function, include amino functions (amide formation), hydroxy (ester formation), isocyanato (amide formation).

- a fonctione hydroxy, include carboxy functions (ester formation), oxiranyl (formation of an ether), isocyanato (amide formation)

- an oxiranyl function, include hydroxy functions (formation of an ether), carboxy (formation of an ester), amino (formation of a secondary or tertiary amine β-hydroxylated)

- a function isocyanato, include amino, hydroxy, carboxy - a halogen function, include the hydroxy functions. Among the amino precursors include in particular amine salts such as hydrochloride.

Among the carboxy precursors which may be mentioned in particular the esters, preferably C1-C4, particularly C1-C2, acid halides, anhydrides, amides.

Among the precursors of hydroxyl function, there may be mentioned epoxy. According to an alternative embodiment said polycondensation operation is carried out additionally in the presence:

• at least one difunctional monomer in linear form of formula (II) or the corresponding cyclic form, comprising two reactive functions polycondensation / polymerization A'-R'-B '(II) wherein: - the symbol A ', identical to or different from a, represents a reactive function selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist B and B' - the symbol B ', identical to or different from B represents a reactive functional group selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist a and a '- the symbol R', identical to or different from R, represents a versatile hydrocarbonné linear or branched aliphatic, cycloaliphatic or aromatic group containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms oxygen, nitrogen, sulfur or phos phorus, said remainder optionally having functions or not susceptible functional groups to react with the A, A ', B and B', the reactive function A ', being capable of reacting with the functional B and / or function B' by condensation;The reactive function B ', being capable of reacting with the function A and / or function A' by condensation;

• and / or at least a "heart" monomer of formula (III), comprising at least one function capable of reacting by condensation with the monomer of formula (I) and / or the monomer of formula (II) R 1 - (B ") n (III) in which formula - n is an integer greater than or equal to 1, preferably from 1 to 100, most preferably from 1 to 20 - the symbol B" is a reactive function which is identical or different B or B ', selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist a and a' - the symbol R 1 is a linear aliphatic polyvalent hydrocarbonné or branched, cycloaliphatic or aromatic containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms oxygen, nitrogen, sulfur or phosphorus, or an organosiloxane or polyorganosiloxane rest, said radical R 1 optionally bearing functions or are functional groups not capable of reacting with the A, A ', B, B' and B ", the reactive function B" being capable of reacting with the function A and / or function A 'by condensation;

• and / or at least monofunctional monomer "chain-limiting" of formula (IV) A "-R 2 (IV) in which formula - the symbol A" is a reactive function, the same as or different from A or A ' selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist B, B 'and B "- the symbol R 2 is a linear aliphatic polyvalent hydrocarbonné or branched, cycloaliphatic or aromatic containing 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms oxygen, nitrogen, sulfur or phosphorus, or a radical organosiloxane or polyorganosiloxane, said radical R 2 optionally bearing functions or functional groups not capable of reacting with the A, A ', A ", B, B' and B", the reactive function A ", being capable of reacting with the functional B and / or function B 'and / or function B "by condensation; at least one of the reactive functions of at least one of the monomers of formula (II), (III) or (IV) capable of reacting with an antagonist function of the polyfunctional monomer of formula (I). Preferentially, the functions A, A ', A "and B, B', B" are chosen from reactive functional groups or groups bearing reactive functional groups chosen from amino, carboxy, hydroxy, oxiranyl or their precursors . Even more preferably said functional groups are chosen from reactive functional groups or carriers of reactive functional amino and carboxy, or precursors thereof. For good implementation of the invention:

- the molar ratio of the monomer of formula (I) to the monomer of formula (II) is advantageously greater than 0.05, preferably ranging from 0.125 to 2;

- the molar ratio of the monomer of formula (III) to the monomer of formula (I) is advantageously less than or equal to 1, preferably less than or equal to 1/2, and even more preferably ranges from 0 to 1/3; said ratio particularly is from 0 to 1/5;

- the molar ratio of the monomer of formula (IV) to the monomer of formula (I) is advantageously less than or equal to 10, preferably less than or equal to 5; said ratio particularly is from 0 to 2, when f is equal to 2. The elementary entity considered to define the different molar ratios is the molecule. It goes without saying that the term "condensation reaction" also includes the concept of addition reaction when one or more antagonistic functions of at least one of the monomers used is included in a ring (lactams, lactones, epoxide for example). Examples of monomer (I) include: - 5-amino-isophthalic acid,

- 6-amino-undecanedioic acid,

- 3-dihydrogen aminopimelic,

- aspartic acid - glutamic acid,

- 3,5-diaminobenzoic acid,

- 3,4-diaminobenzoic acid,

- lysine,

- the α acid, α-bis (hydroxymethyl) -propionic acid - the acid α, α-bis (hydroxymethyl) -butyric acid

- the α acid, α-tris (hydroxymethyl) -acetic acid

- the α acid, α-bis (hydroxymethyl) -valérique

- the α acid, α-bis (hydroxy) -propionic acid

- 3,5-dihydroxybenzoic acid - or mixtures thereof Examples of difunctional monomer of formula (II) include:

- the ε-caprolactam

- aminocaproic acid,

- para or meta-aminobenzoic acid, - 11-amino-undecanoic acid,

- lauryllactam

- amino-12-dodecanoic acid

- hydroxyacetic acid (glycolic acid)

- hydroxyvaleric acid - hydroxypropionic acid

- hydroxypivalate

- glycolide

- the δ-valerolactone

- the β-propiolactone - the ε-caprolactone

- lactide

- lactic acid

- or mixtures thereof More preferably, the bifunctional monomers of formula (II) are monomers used for the manufacture of linear thermoplastic polyamides.

Thus, there may be mentioned ω-aminoalkanoic compounds comprising a hydrocarbon chain having from 4 to 12 carbon atoms, or the lactams derived from these amino acids such as ε-caprolactam. The preferred bifunctional monomer for the implementation of the invention is ε-caprolactam. According to an advantageous embodiment of the invention, at least some of the difunctional monomers (II) are in prepolymer form. As examples of monomer (III) include:

- aromatic or aliphatic monoamines, such as dodecylamine, octadecylamine, benzylamine ...

- aromatic or aliphatic monobasic acids containing 1 to 32 carbon atoms, such as benzoic acid, acetic acid, propionic acid, saturated fatty acids or not (dodecanoic acid, oleic, palmitic, stearic ...)

- the monofunctional alcohols or epoxides, such as ethylene oxide, epichlorohydrin ...

- the isocyanates such as phenylisocyanate ... - diprimary diamines, linear or branched saturated aliphatic preferably having 6 to 36 carbon atoms such as, for example, hexamethylenediamine, trimethylhexamethylenediamine diamine, tétraméthylèndiamine, n xylene diamine

- saturated aliphatic dicarboxylic acids having from 6 to 36 carbon atoms such as, for example, adipic acid, azelaic acid, sebacic acid, or maleic anhydride

- difunctional alcohols or epoxides, such as ethylene glycol, diethylene glycol, pentanediol, glycidyl ethers of monohydric alcohols containing 1 to 24 carbon atoms

- diisocyanates, such as toluene diisocyanates, hexamethylene diisocyanate, phenyl diisocyanate, isophorone diisocyanate

- triamines, or tribasic aliphatic or aromatic polyacid, triols or polyols commela N, N, N-tris (2-aminoethyl) amine, melamine ..., citric acid, acid 1, 3,5- benzene tricarboxylic ..., 2,2,6,6-tetra- (β-carboxyethyl) cyclohexanone, trimethylolpropane, glycerol, pentaerythritol, di-glycidyl ethers of alcohols, tri- or poly-functional

- polymeric compounds such as polyoxyalkylene mono- or poly- amines marketed under the tradename Jeffamine ®,

- amino polyorganosiloxanes, such as amino polydimethylsiloxane.

The monomers (III), preferred "core" are: hexamethylene diamine, adipic acid, JEFFAMINE ® T403 sold by the company Huntsman acid, 1, 3,5-benzenetricarboxylic acid, 2,2, 6,6-tetra- (β-carboxyethyl) cyclohexanone. As examples, the monomers (IV) include:

- aromatic or aliphatic monoamines, such as dodecylamine, octadecylamine, benzylamine. Most of these compounds are generally regarded as hydrophobic. - aromatic or aliphatic monobasic acids containing 1 to 32 carbon atoms, such as benzoic acid, acetic acid, propionic acid, saturated fatty acids or not (dodecanoic acid, oleic, palmitic, stearic ...) . Most of these compounds are generally regarded as hydrophobic.

- the monofunctional alcohols or epoxides, such as ethylene oxide, epichlorohydrin. Most of these compounds are generally regarded as hydrophobic.

- isocyanates such as phenyl isocyanate. Most of these compounds are generally regarded as hydrophobic.

- polymeric compounds such as monoamino polyoxyalkylene by example sold under the trademark JEFFAMINE M ®, such as Jeffamine ® M 1000 and

JEFFAMINE M 2070 ®. Most of these compounds are generally regarded as hydrophilic.

- monoaminées of silicone chains, such as polydimethylsiloxane monoamine. Most of these compounds are generally regarded as hydrophobic. - N, N-dimethylaminoethyl Propyl Ine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

- N, N-diethylamino Propyl Amine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

- N, N-DiButhyl Amino Propyl Amine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

- N- (3-aminopropyl) morpholine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

- N-Methyl-N '- 3-aminopropyl) Piperazine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate). - N- (3-aminopropyl) piperidine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

- mixtures of these compounds. Among the functional groups may be present in the monomers (I)

(IV) and not capable of reacting with the A, A ', A ", B, B' and B" that may especially be mentioned functions that provide or enhance the hydrophilicity of the dendritic polymers implement the invention. For example there may be mentioned quaternary ammonium, nitrile, sulfonate, phosphonate, phosphate, hydroxyl, ethylene oxide, ether, amine ternary (basic or quaternizable). there may be mentioned: - the sulfonic acid 4-amino-benzene and its ammonium or alkali metal salts, especially sodium [monomer of formula (II)]

- 5-sulfo salicylic acid [monomer of formula (II)]

- acid D- or L-2-amino-5 phosphoro valeric [monomer of formula (II)]

- sulfobenzoic acid and its ammonium or alkali metal [monomer of formula (III) or (IV)]

- chloride époxypropyltriméthylarnmonium [monomer of formula (III) or (IV)]

- polyethylene glycol polytioxyle,

- amino methyl phosphonic acid [monomer of formula (IV)]. The hydrophilic functions can in particular be carried by the monomer (IV), for example by one of the following monomers:

- polymeric compounds such as monoamino polyoxyalkylene by example sold under the trademark JEFFAMINE M ®, such as Jeffamine ® M 1000 and JEFFAMINE M 2070 ®. Most of these compounds are generally regarded as hydrophilic. - N, N-dimethylaminoethyl Propyl Amine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

- N, N-diethylamino Propyl Amine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

- N, N-DiButhyl Amino Propyl Amine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

- N- (3-aminopropyl) morpholine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

- N-Methyl N '- (3-Amino) Propyl Piperazine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate). - N- (3-aminopropyl) piperidine (hydrophilic or potentially hydrophilic, because basic or quaternizable for example with dimethyl sulfate).

Finally, the dendritic polymer may have the end of the polymer chains a mixture of hydrophilic groups and hydrophobic groups, for example provided by the monomers (IV) and / or acid-base control. It is thus possible to modulate the emulsifying properties, and optionally make the action of the dendritic polymer sensitive to external conditions may trigger stabilization or destabilization of the emulsion. This mode is preferable in the context of achieving multiple emulsions. A -COOH group association for example are cited or COO 'and alkyl groups.

Dendritic polymers described above, can be treated as tree structures with a focal point formed by the function A and a periphery packed terminations B. It is pointed out that the fact that the periphery is packed terminations B n not exclude that terminations B are present at the chain ends located closer to the heart of the dendritic polymer. Furthermore, when present, the difunctional monomers (II) are spacer elements in the three dimensional structure. They allow control of the branching density. When present, the monomers (III) form nuclei. The monofunctional monomers (IV) "chain-limiting", are located on the periphery of the dendrimers. It is pointed out that the fact that the periphery is filled with monofunctional monomers (IV) does not exclude that monofunctional monomers (IV) are present at the chain ends located closer to the heart of the dendritic polymer. The presence of monomers (III) and (IV) makes it possible in particular to control the molecular weight. Preferentially, the dendritic polymers used according to the invention are hyperbranched polyamides; they are obtained from at least one monomer of formula (I) having as reactive polycondensation functions, amino, and carboxy antogonistes functions, or of a monomer composition further containing at least one monomer of formula (II ) and / or (III) and / or (IV) having the at least same type (s) (s) function (s) reactive (s) polycondensation, all or part of the monomer of formula (II) which can be replaced by a lactam. The polycondensation operation / polymerization may be carried out in a known melt or solvent phase manner, the monomer of formula (II), when present, can favorably act as a solvent. The operation can be favorably effected in the presence of at least one polycondensation catalyst and optionally at least one antioxidant compound. Such catalysts and antioxidant compounds are known to the skilled person. As examples of catalysts there may be mentioned phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acids, such as 2- (2'-pyridyl) ethylphosphonic acid, phosphites such as ts (2,4-di-tert-butylphenyl) phosphite. Examples of antioxidant include bi-hindered phenolic antioxidants base, such as N, N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), the 5-tert-butyl-4-hydroxy-2-methylphenyl sulfide. Hyperbranched polyamides having hydrophilic functionality nonréactives with the A, A ', A ", B, B' and B", may be obtained by implementation of a monomer of formula (III) and / or (IV) having one or more polyoxyethylene groups (e.g. monomer Familie amino polyoxyalkylene Jeffamines) and / or a monomer of formula (IV) having quaternary ammonium, nitrile, sulfonate, phosphonate, phosphate. Another embodiment consists, after preparation of a hyperbranched polymer by polycondensation of nonfunctionalized monomers, modifying the terminal functions of said hyperbranched polyamide by reaction with a compound having hydrophilic functional groups. It may for example be a compound having a tertiary amino group, quaternary ammonium, nitrile, sulfonate, phosphonate, phosphate or polyoxyethylene groups. The terminal functional groups can also be modified by simple reaction of acid-base type ionizing fully or partially included groups at chain ends. For example carboxylic acid end groups (e.g., groups B, B 'and / or B "), can be rendered anionic by adding a base. The amine end groups (e.g., groups B, B 'and / or B ") can be made cationic by adding an acid. Note that the functionalization may be total or partial. It is preferably greater than 25% by number, based on the total carried free functional groups (B, B ', B "). It is noted that it is not excluded to carry out a hydrophobic partial functionalization after preparation of the dendritic polymer. it is thus possible to modulate the emulsifying properties, and optionally make the action of the dendritic polymer sensitive to external conditions may trigger stabilization or destabilization of the emulsion.

The molar mass by weight of said dendritic polymers, hyperbranched polyamides in particular, may range between 500 and 1 000 000 g / mol, preferably from 1000 to 500 000 g / mol, even more preferably from 3000 to 20,000 g / mol. The molar mass weight can be measured by size exclusion chromatography. The measurement is performed in an eluting phase composed of 70% by volume of water Millipore 18 megaohms and 30% by volume of methanol, containing 0.1 M NaNO 3; it was adjusted to pH 10 (1/1000 NH 4 OH 25%). The molecular weight was determined in known manner by means of the light scattering values.

Quantities - Formulation The weight ratio between the amounts of internal phase and external phase is preferably from 0.1 / 99.9 to 95/5, more preferably between 1/99 and 10/90. The weight ratio between the quantities of dendritic polymer and the internal phase is preferably between 0.05 / 100 and 20/100, more preferably between 0.5 and 20/100, even between 5/100 and 20/100 . Furthermore, the proportion by weight of dendritic polymer in all of the emulsion is preferably between 0.05% and 10%, even more preferably between 0.1% and 5%, for example of the order of 1 %. The droplet size of the emulsions may depend on the amount of emulsifying agent (dendritic polymer optionally with other agents such as surfactants) used and / or the amount of energy implementation for preparing the 'emulsion. A low proportion of emulsifying agent, the droplet size may be mostly limited (lower limit, large droplets) by the amount of emulsifying agent. The higher the proportion of emulsifier, the larger droplets are small. We often talk then of poor diet. A higher proportion of emulsifying agent, the size may be mostly limited (lower limit) by the amount of energy. The greater the amount of energy, the greater the droplets. We often talk about diet. In the case where the emulsion does not comprise another emulsifier that the dendritic polymer, the boundary between the diet and the diet may be of the order of a few%, for example 1/100 2 / 100 (weight ratio between the quantities of dendritic polymer and internal phase), for a direct emulsion. It is mentioned, without this constituting a limitation to the invention, it has been noticed that the critical concentration (by weight of dendritic polymer) between the diet and the diet does not seem to depend on the molecular weight of the polymer dendritic. Without being bound to any theory, it is believed that the dendritic polymer is present at the interface between the aqueous phase and the hydrophobic phase in the form of aggregated objects around the droplets. Thus one can for example ensure that the droplet size is modulated by varying the nature of the internal phase, the proportions of the various constituents, including the emulsifier, and the process parameters (speed and duration mixture to impart energy).

Other ingredients The emulsions of the invention are compositions which in addition to the above mentioned ingredients may include other ingredients. The nature and amount of these other ingredients may depend on the destination or use of the emulsion. These additional ingredients are known to the skilled person. For example the emulsion may comprise additional emulsifying agents, known, in combination with the dendritic polymer, including surfactants, in particular non-ionic or cationic surfactants, water-soluble amphiphilic polymers, comb polymers or block polymers. In the context of multiple emulsions, it is specified that each of the aqueous phases may include agents for controlling the osmotic pressure. It may for example be a salt selected from halides of alkali or alkaline earth metals, (such as sodium chloride, calcium chloride), or a sugar (such as gluocse) or a polysaccharide (such as dextran), or a mixture. Generally, the emulsions may comprise nonionic, anionic, cationic or amphoteric (zwitterionic surfactants being within amphoteric). The emulsions may also include pH control agents, active ingredients, perfumes ....

Method The emulsions according to the invention may be prepared by conventional emulsification processes. Such processes conventionally involve mixing more or less energetically different ingredients: immiscible phases, the emulsifying agent, and optionally other ingredients. To this mixture, some of the ingredients may holdings were mixed, dissolved or dispersed beforehand. Thus it may be advantageous to use an aqueous phase in which the dendritic polymer has been introduced beforehand, prior to mixing said aqueous phase with the water-immiscible phase. The mixture can be designed as a more or less vigorous stirring. In the case where the internal phase is of low viscosity (viscosity less than 1 Pa · s) can advantageously operate under vigorous stirring, for example using a device of Ultra-Turrax ®, microfluidizer or other homogenizer high pressure. In the case where the internal phase is viscous (viscosity greater than 1 Pa.s, preferably above 5 Pa · s) can advantageously operate with a blade frame. The temperature at which the emulsion is prepared may depend on the phases implemented. Thus, one can choose to adjust the temperature to modulate the viscosity of the different phases implemented. Note that it may be convenient to add to the internal phase a heat-induced compound. The stirring time can be determined easily by the skilled person. It generally depends on the device used. In diet, it can partially determine the droplet size. It was also noted that the emulsions may be made using a self-emulsification process. Under certain conditions, a mixture comprising the compound which will constitute the internal phase and the one or more emulsifying agents, may form emulsions by simply adding water, with very gentle stirring. We talk to this mixture of self-emulsifying compositions. Such compositions find use in particular in the field of agriculture, in formulating phytosanitary insoluble liquid compounds in water directly on the farm ( "tank mix") and in the field of coatings and paints (including isocyanates bases).

Applications The emulsions according to the invention can be used in many application areas. Particularly cites the areas of formulation komatiks products (care of skin, hair, makeup), detergents (laundry, dishes or hard surfaces), paints or coatings. In the field of detergents or cosmetics, the dendritic polymer of the invention may be used as emulsion vector or triggering agent for deposition onto a surface of an emulsion compound, for example a silicone. Thus, a stable emulsion is prepared of a compound to be deposited (e.g., silicone), and triggers the deposition by modifying the outer phase, for example by dilution or by pH change, so as to modify the hydrophilicity of groups including in the dendritic polymer (modification to make them more hydrophobic). The emulsion can then be destabilized, and the emulsified compound is deposited on a surface, for example a textile surface (detergency), or on the skin or hair (cosmetic, conditioning effect). The emulsified compound may also be brought to the surface by mere affinity of the dendritic polymer to the surface by adsorption, for example. Whatever the mechanism, destabilization of the emulsion, or affinity for a surface can be considered the dendritic polymer as an emulsion vector. It is particularly useful in shampoos or in the textile care compositions. These mechanisms can also be used to deposit or treatment of metals, glass, or clays. In the field of cosmetics, the emulsions have the advantage of being substantially free of surfactant and no foaming in the absence of a surfactant. The dendritic polymer can be combined with a surfactant. In this case the dendritic polymer has an effect on the emulsification, without increasing the foaming associated with the presence of surfactant. In addition, in the absence of a surfactant, the polymer dendritrique does not foam, and in the presence of a low-foaming surfactant, it improves the emulsification or emulsion stability properties without increasing foaming. Avoid totally foaming or does not increase it avoids implementing binding emulsification processes. On the other hand some products are not intended to foam. This is usually creams, lotions or gels to be applied to the skin or lips. As regards the field of paints and coatings, emulsions according to the invention may, for example emulsions of alkyd or isocyanate-type (emulsion in water of an alkyd or an isocyanate). The emulsion may be an emulsion of monomers for the latex preparation. The emulsion according to the invention can be used in paints, preferably aqueous, or itself constitute a preferably aqueous paint, and be implemented to convey such a hydrophobing agent on a building material surface type, plaster , cement, wood ..., with release of the hydrophobizing agent by deposition and drying of the paint on the surface. It can also be implemented for the processing of metals. Similarly, it can be used in cosmetic compositions or itself be an aqueous cosmetic composition (moisturizing creams, sun creams, makeup products, hair styling gels ...); the hydrophobic phase can be or contain any hydrophobic active material care (such as conditioning agents, conditioning agents ...), anti-UV agents, pigments, dyes ... It may also be implemented to provide to surfaces of a woven or non-woven cellulosic origin and / or synthetic, for personal hygiene or cleaning the house, to be brought into contact with the skin, as care wipes, cleaning or removing make-up ( "wipes") tissue paper ( "tissue"), feminine protection ( "towels"), diapers ( "diapers") etc ..., of the intrinsic benefits to the non aqueous phase and hydrophobic / or active substances contained in the hydrophobic phase, and during the preparation of said surfaces or by post-treatment of said surfaces. Can be thus conferred softening, odor, perfume, bactericide etc ... It can also be used during manufacturing or post-processing cartons or cardboard packaging, to provide hydrophobic properties, anti-odor, bactericides, perfuming ... the emulsion according to the invention (E) is particularly useful for conveying and depositing a hydrophobic active material (constituting the hydrophobic or ranging phase in the hydrophobic phase) on a surface or a substrate (S) to hydroxyapatite (tooth), a surface or a keratinous substrate (skin, hair, leather) or a surface or a textile substrate. When said substrate (S) is hydroxyapatite (teeth), the hydrophobic phase may contain hydrophobic agents having cooling properties, agents to fight against plaque, antiseptic agents ... The emulsion (E) may be included or forming itself a composition for dental or oral hygiene, composition intended to be rinsed or diluted. It may include toothpaste, mouthwash ... The substrate (S) may especially be a keratinous surface, such as skin and hair. The hydrophobic phase can be or contain any hydrophobic active material care (such as conditioning agents, conditioning agents ...), anti-UV agents, pigments, dyes ...; the emulsion (E) may be included in or forming itself a cosmetic composition intended to be rinsed or diluted; it can be in particular a shampoo, a conditioner, a shower gel ... The substrate (S) may be of leather; the hydrophobic phase can be or contain any hydrophobic active material capable of providing hydrophobicity to substrate, softness, flexibility, vis-à-vis protection against external agents etc .... Interestingly, said substrate (S) is a textile material. The textile substrate may be in the form of textile fibers or articles made from natural fibers (cotton, flax or other cellulosic natural materials, wool ...), artificial (viscose, rayon ...) or synthetic ( polyamide, polyester ...) or mixtures thereof. Preferentially, said substrate is a textile surface in a cellulosic material, especially cotton. The hydrophobic phase is preferably a material for textile care ( "textile care agent"). The benefits of a lubricating hydrophobic phase to a textile substrate include the contribution of sweetness properties (softness), anti-crease (anti-wrinkling), ironing facilitated (easy-ironing), of resistance to abrasion (vis-à-vis protection including aging when wearing clothing or repeated washing operations), elasticity, color protection, fragrance retention ... other active ingredients providing other benefits in the field of care of textile fiber articles can be mentioned in particular fragrances; preferably, these are dissolved in the hydrophobic phase. The substrate or the surface (S) may be present in an aqueous liquor (B). The aqueous liquor (B) is present wherein the textile substrate to acquire benefits, can be very varied. It may be, without limitation, a dipping bath, washing, rinsing, padding ... The emulsion 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 of textile fiber articles, in order to convey a hydrophobic care agent ( "textile care agent") and / or any active ingredient another useful hydrophobic, and 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 operation ( s) to the main washing operation in the case of a detergent composition for washing, or during the subsequent drying operation in the case of a rinse composition. The emulsion in the form of a multiple emulsion containing a hydrophobic phase of care, as a detergent composition or a detergent composition for washing laundry in a washing machine, implementing the wash cycle, without adding liquid rinse fabric softener to the rinse cycle, allowed to bring in washed linen properties of softness, flexibility, anti-crease (anti-wrinkling), ironing facility (easy-ironing), resistance to abrasion, to elasticity, color protection, retention of perfumes ... the emulsion (E) in the form of a multiple emulsion containing a hydrophobic phase of care, as rinse composition or in a composition for rinsing the machine, allows to bring the laundry after drying properties of softness, flexibility, anti-crease (anti-wrinkling), ironing facilitated (easy-ironing), abrasion resistance, elasticity, protective color, fragrance retention s

The deposition of the hydrophobic phase containing or constituted of an active material (A) on the substrate may be a deposition by adsorption, co-crystallisation, entrapment and / or adhesion. The amount of emulsion in the form of a multiple emulsion may be present in a composition for washing articles made of textile fibers, according to the third object of the invention, corresponds to an amount of hydrophobic phase representing from 0.0001% to 25 %, preferably from 0.0001% to 5% of the total weight of the composition, with the relative amounts of emulsion, expressed as a multiple emulsion, and an aqueous medium (B) equivalent to a dilution of from 2 to 100 times the volume of said emulsion. The amount of the form of a multiple emulsion emulsion may be present in a rinsing composition of the articles made of textile fibers, according to the third object of the invention, corresponds to an amount of hydrophobic phase representing from 0.0001% to 25 %, preferably from 0.0001% to 5% of the total weight of the composition, with the relative amounts of emulsion, expressed as a multiple emulsion, and an aqueous medium (B) equivalent to a dilution of from 2 to 100 times the volume of said emulsion. A washing composition in compacted powder or not, or liquid, articles made of textile fibers may contain at least one surfactant preferably selected from anionic surfactants and nonionic surfactants or mixtures thereof. Among the anionic surfactants, there may be mentioned alkyl (C 8 -Cι 5) benzene sulphonates (in a proportion of 0-30%, preferably 1-25%, more preferably 2-15% by weight). In addition there may be mentioned primary or secondary alkyl sulphates, particularly (C 8 -C 15) primary sulphates; alkyl ether sulphates; olefin sulfonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; ester sulfonates of fatty acids; sodium salts are generally preferred. Among the nonionic surfactants, there may be mentioned those ethoxylates of primary or secondary alcohols, especially those ethoxylates of aliphatic alcohols in C 8 -C 20 alkyl having from 1 to 20 moles of ethylene oxide per mole of alcohol, especially ethoxylates of primary or secondary aliphatic alcohols C 10 -C 15 alkyl having from 1 to 10 moles of ethylene oxide per mole of alcohol; can also be mentioned non-ethoxylated non-ionic surfactants such as alkylpolyglucosides, glycerol monoethers, and polyhydroxyamides (glucamides). Preferably the rate of nonionic surfactant agents is 0-30%, preferably 1-25%, more preferably 2-15% by weight. The choice and amount of the surfactant depends on the intended use of the detergent composition. The surfactant systems to choose for washing textiles by hand or machine are well known to formulators.

Amounts of surfactants as high as 60% by weight may be present in compositions for washing by hand. Quantities of 5-40% by weight are generally suitable for textile washing machine. Typically these compositions comprise at least 2% by weight, preferably 2-60%, more preferably 15-40% and particularly 25-35% by weight.

It is also possible to include cationic surfactants mono-alkyl. There may be mentioned quaternary ammonium salts of the formula R 1 R 2 R 3 R 4 N + X 'where the R groups are long hydrocarbon chains or short alkyl, hydroxyalkyl or alkyl ethoxylated, X being an against-ion (R 1 is alkyl C 8 -C 22, preferably C 8 -C 10 or C 12 -Cι, R 2 is methyl, R 3 and R 4 the same or different is a methyl or hydroxymethyl group); and cationic esters, such as choline esters.

Detergent compositions for most washing machine, generally contain a different anionic surfactant soap or a nonionic surfactant, or mixtures thereof, and optionally a soap. Detergent compositions for fabric washing typically contain at least one detergent adjuvant ( "builder"); the total amount of detergency builder is typically from 5-80%, preferably 10-60% by weight. There may be mentioned inorganic builders such as sodium carbonate, crystalline or amorphous aluminosilicates (10-70%, preferably 25-50% dry), layer silicates, inorganic phosphates (Na orthophosphate, pyrophosphate and tripolyphosphate). Further details of particularly suitable aluminosilicates and zeolites are given in WO 03/020819. Mention may also be of organic builders such as polyacrylates polymers, acrylic / maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, mono-, di- and tri-succinates glycerol, dipicolinates, hydroxyethyliminodiacetates, malonates succinates or alkyl or alkenyl; fatty acid salts sulfonates .... Preferably, organic builders are citrates (5-30%, preferably 10-25% by weight), acrylic polymers, more especially acrylic / maleic copolymers ( 0.5-10%, preferably 1-10% by weight). When powder compacted or not, the compositions can favorably contain a bleaching system, especially peroxy compounds such as inorganic persalts (perborates, percarbonates, perphosphates, persilicates and persulphates, 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 in an amount of 0.1-35%, preferably 0.5-25% by weight. It can be associated with a bleach activator to improve the low temperature bleaching; it is favorably present in an amount of 0.1-8%, preferably 0.5-5% by weight. The preferred activators are peroxycarboxylic acids, including peracetic acid and pernonanoiques. Mention may very particularly be mentioned N, N, N ', N', - tetracetyl ethylenediamine (TAED) and sodium nonanoyloxybenzene sulfonate (SNOBS) .. The compositions also typically include one or more enzymes, in particular proteases, amylases, cellulases , oxidases, peroxidases and lipases (0.1- 3% by weight), fragrances, anti-redeposition agents, anti-fouling, anti-color transfer, nonionic softening agents ... the detergent compositions for washing textiles may also be in the form of nonaqueous liquid tablets in an envelope of a material dispersing in the washing medium such as polyvinyl alcohol for example. They comprise at least one water-miscible alcohol, such as isopropyl alcohol, in an amount of from 5 to 20% by weight. .

They may contain at least one surfactant preferably selected from anionic surfactants and nonionic surfactants or mixtures thereof, in an amount of from 20 to 75% by weight. They may further comprise detergency adjuvants ( "builders") organic, such as sodium citrates, phopsphonates ..., in an amount of from 5 to 20% by weight; .They may also comprise fragrances, dyes ... The compositions for rinsing articles made of textile fibers may contain cationic softeners or nonionic. They can represent from 0.5 to 35%, preferably 1-30%, more preferably 3-25% by weight of the rinse composition. Cationic softeners are quaternary ammonium compounds substantially non-water-soluble, 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 . Most preferably the softening compounds have two alkyl or alkenyl chains containing at least 16 carbon atoms, and particularly at least 50% of alkyl or alkenyl groups have 18 carbon atoms or more. Most preferably the alkyl chains linear or alkenyl are predominant. In the softening rinse formulas trade, is very commonly used quaternary ammonium compounds having two long aliphatic chains, such as distearyl dimethyl ammonium chloride, ditallow alkyl dimethyl ammonium of.

The rinse compositions may further comprise nonionic softeners, such as lanolin; lecithins and other phospholipids are also suitable. The rinse compositions may also contain nonionic stabilizers such as linear alcohols C 8 -C 22 alkoxylated with 10 to 20 moles of alkylene oxide, alcohols Cι 0 -C 20 and mixtures thereof. The amount of nonionic stabilizing agent is 0.1-10%, preferably 0.5-5%, especially 1-4% by weight of the composition. The molar ratio of quaternary ammonium compound and / or other cationic softening agent to the stabilizing agent is favorably 40 / 1-1 / 1, preferably 18 / 1-3 / 1.

The composition may further comprise fatty acids, especially alkyl or alkenyl acids (C 8 -C 2) monocarboxylic or their polymers; preferably they are saturated and non-saponified, such as oleic acid, lauric acid or tallow. 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 at 0.5-20%, preferably 1-10 wt%. The molar ratio of quaternary ammonium compound and / or other cationic softening agent to fatty acid is favorably 10 / 1-1 / 10.

Other details or advantages of the invention will become apparent from the examples below, without limitation.

Example 1 Synthesis of a hyperbranched copolyamide-terminated carboxylic acid by melt copolycondensation of 1,3,5-benzene tricarboxylic acid (noted BTC, heart type molecule R 1 -B "3, with B '= COOH ) of the 5-aminoisophthalic acid (noted AIPA, branching molecule AR- B 2, with A = NH2 and B = COOH), and ε-caprolactam (denoted CL, spacer A '-R'-B', with A '= NH2 and B' = COOH). The respective overall composition is 1/6/6 in BTC / AIPA / CL. The reaction is carried out in a 500 ml glass reactor commonly used in the laboratory for the melt synthesis of polyesters or polyamides. The monomers are completely loaded at the start of the test. The reactor was immersed in a Wood's alloy metal bath at 100 ° C and kept under mechanical stirring at 80 t / min. successively introducing into the reactor 72.7 g of ε- caprolactam (0.64 mol), 116.4 g of 5-aminoisophthalic acid (0.64 mol), 22.5 g of 1, 3, 5-benzenetricarboxylic acid (0.11 mol) and 0.53 g of a 50% aqueous solution (w / w) of hypophosphorous acid. The reactor is placed under a low stream of dry nitrogen. Stirring is then set to 50 t / min and the reaction mass was gradually heated from 100 ° C to 250 ° C, in about 250 min. The temperature is then maintained at 250 ° C in the tray.

After 60 minutes under these conditions, the reactor is placed under gradual vacuum of 60 min. The minimum vacuum is then maintained for an additional 60 min. Approximately 10.6 g of distillate are recovered. At cycle end, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 182.5 g of polymer are collected. The hyperbranched copolyamide obtained is a white solid.

Example 2 Synthesis of a hyperbranched copolyamide-terminated carboxylic acid by melt copolycondensation of 1,3,5-benzene tricarboxylic acid (noted BTC, heart molecule type R 1 -B "3, with B '= COOH ) of the 5-aminoisophthalic acid (noted AIPA, branching molecule type AR- B 2, with A = NH2 and B = COOH), and ε-caprolactam (denoted CL, spacer A '-R'-B', with A '= NH2 and B' = COOH). The respective overall composition is 1/25/25 in BTC / AIPA / CL.

The same reactor as described in Example 1 is employed. The monomers are completely loaded at the start of the test. The reactor was immersed in a Wood's alloy metal bath at 100 ° C and kept under mechanical stirring at 80 t / min. successively introducing into the reactor 79.5 g of ε-caprolactam (0.70 mol), 127.2 g of 5-aminoisophthalic acid (0.70 mol), 5.9 g of 1, 3, 5-benzenetricarboxylic acid (0.03 mol) and 0.49 g of a 50% aqueous solution (w / w) of hypophosphorous acid. The reactor is placed under a low stream of dry nitrogen. Stirring is then set to 50 t / min and the reaction mass was gradually heated from 100 ° C to 250 ° C, in about 250 min. The temperature is then maintained at 250 ° C in the tray.

After 60 minutes under these conditions, the reactor is placed under gradual vacuum of 60 min. The minimum vacuum is then maintained for an additional 60 min. About 11, 3 g of distillate are recovered. At cycle end, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 162.2 g of polymer are collected. The hyperbranched copolyamide obtained is a white solid.

Example 3: Neutralization with sodium hydroxide of a hyperbranched copolyamide carboxylic acid terminated 1/25/25 overall composition respectively BTC / AIPA / CL, synthesized in Example 2. 50.0 g of hyperbranched copolyamide obtained in Example 2 are finely ground and dispersed in 300ml of water. The mixture is put under mechanical stirring with an anchor and gradually added aqueous 35% sodium hydroxide mass. The pH is regularly checked with pH paper and kept at around 10. 22,12g of soda are needed to achieve a stable pH. The solution is then filtered and lyophilized. 48.8 g of fine white powder was collected. Elemental analysis of sodium gives an average content of 9% by weight, a carboxylate group content of 3480 meq sodium / kg.

Example 4 Synthesis of a hyperbranched copolyamide-terminated polyalkylene oxide by copolycondensation melt tricarboxylic 1,3,5-benzenetricarboxylic acid (BTC noted, heart molecule type -B R "3, with B '= COOH), amino-5 isophthalic acid (noted AIPA, AR B 2 branching molecule, with A = NH2 and B = COOH), of ε-caprolactam (denoted CL, spacer A '- R'-B', with A '= NH2 and B' = COOH) and Jeffamine ® M1000 (denoted M1000 type blocker A "-R 2, with A '= NH 2). The respective overall composition is 1/25/25/28 in BTC / AIPA / CL / M1000. The same reactor as described in Example 1 is employed. The monomers are completely loaded at the start of the test. The reactor was immersed in a Wood's alloy metal bath at 100 ° C and kept under mechanical stirring at 80 t / min. successively introducing into the reactor 23.9 g of ε-caprolactam (0.21 mol) of Jeffamine M1000 236,2g ® (0.24 mol), 38.2 g of 5-aminoisophthalic acid (0.21 mol), 1, 8 g of 1, 3,5-benzenetricarboxylic acid (0.008 mol) and 0.22 g of a 50% aqueous solution (w / w) of hypophosphorous acid. The reactor is placed under a low stream of dry nitrogen. Stirring is then set to 50 t / min and the reaction mass was gradually heated from 100 ° C to 250 ° C, in about 250 min. The temperature is then maintained at 250 ° C in the tray.

After 60 minutes under these conditions, the reactor is placed under gradual vacuum of 60 min. The minimum vacuum is then maintained for an additional 60 min. About 7.0 g of distillate are recovered. At cycle end, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 281, 5 g of polymer are collected. The hyperbranched copolyamide obtained is a translucent viscous liquid.

Example 5 Synthesis of a hyperbranched copolyamide-terminated polyalkylene oxide and carboxylic acid by melt copolycondensation of 1,3,5-benzene tricarboxylic acid (noted BTC, heart molecule type R 1 -B "3, with B '= COOH), amino-5 isophthalic acid (noted AIPA, branching molecule ARB 2, with A = NH2 and B = COOH), of ε-caprolactam (CL noted, spacer type A'-R'-B ', with A' = NH2 and B '= COOH) and Jeffamine ® M1000 (denoted M1000 type blocker A "-R 2, with A' = NH 2) - the respective overall composition is 1/25/25/21 in BTC / AIPA / CL / M1000.

The same reactor as described in Example 1 is employed. The monomers are completely loaded at the start of the test. The reactor was immersed in a Wood's alloy metal bath at 100 ° C and kept under mechanical stirring at 80 t / min. successively introducing into the reactor 29.3 g of ε-caprolactam (0.26 mol),

221, 7 g of Jeffamine M1000 ® (0.22 mol), 46.9 g of 5-aminoisophthalic acid (0.26 mol), 2.2 g of 1, 3,5-benzenetricarboxylic acid (0.010 mol) and 0.24 g of a 50% aqueous solution (w / w) of hypophosphorous acid. The reactor is placed under a low stream of dry nitrogen. Stirring is then set to 50 t / min and the reaction mass was gradually heated from 100 ° C to 250 ° C, in about 250 min. The temperature is then maintained at 250 ° C in the tray.

After 60 minutes under these conditions, the reactor is placed under gradual vacuum of 60 min. The minimum vacuum is then maintained for an additional 60 min. About 11, 9 g of distillate are recovered. At cycle end, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 285.8 g of polymer are collected. The hyperbranched copolyamide obtained is a translucent viscous liquid, which cures in a wax at room temperature.

EXAMPLES 6 TO 9 Preparation of direct water emulsions in oil, containing 20% ​​by weight of oily phase and 80% aqueous phase.

Is used as an emulsifying agent of the hyperbranched copolyamide (HBPA) prepared according to the previous examples. The amount of HBPA used for the preparation of the emulsion is previously dissolved in water to form the aqueous phase. Thereof is adjusted to a desired pH by adding a solution of HCl or NaOH

1N.

The oil phase is added to the aqueous phase with stirring using a stirrer type of rotor / stator (Ultra-turrax) rotating at 9500 t min. After addition, stirring was continued for 2 min.

The emulsion thus obtained is then subjected to 3 passes at a pressure of 250 bar or 500 bar in a high pressure homogenizer (MICROFLUIDIZER M110

S). the emulsion particle size was measured and obtained with a laser diffraction granulometer (HORIBA LA-910 particle size analyzer) and follows in time the evolution of the particle size and changes in macroscopic stability of the emulsion in order to observe the instability phenomena that may occur (coalescence, Oswald ripening, creaming or sedimentation of the droplets due to the difference of the densities of oil and water).

Example 6: Influence of HBPA concentration in the aqueous phase on the size of the emulsion.

emulsion is prepared comprising 0.25 to 5% by weight of HBPA relative to the oil. Is used HBPA according to Example 1 and an HBPA according to Example 2. The pH of the aqueous phase is adjusted to 6.0-6.5. The oil phase is hexadecane. The homogenization pressure is 500 bar.

Measuring the median radius (R) of the emulsion depending on the HBPA / oil concentration. It shows that the definition of poor areas (P) and rich (R) polymer and the size of the emulsion for a given polymer concentration are relatively independent of the molecular weight of the dendritic polymer. The results are presented in Table I below.

Table I

Example 7: Emulsions prepared with HBPA according to Example 2, and various oils

The emulsion contains 1% by weight of HBPA according to Example 2 with respect to the oil (or 0.2% o in the emulsion). The pH of the aqueous phase is adjusted to 6.0-6.5. 3 oils are studied: hexadecane, a polydimethylsiloxane silicone oil (Rhodorsil V100 Rhodia), a rapeseed methyl ester (Phytorob 926-65 Novance) The emulsions are subjected to 3 passes at 200 bar in the Microfluidizer. in terms of stability results are presented in Table I below. Table I

* Increase in droplet size due to Oswald ripening generated by the relatively high solubility of the ester of rapeseed in water.

EXAMPLE 8 Emulsions prepared with HBPA according to Examples 1 or 4. Influence of the nature of the chain ends.

The emulsions contain between 0.5 and 5% by weight of HBPA relative to the oil (0.1 to 1.0% in the emulsion) The oil phase is hexadecane. The emulsions are subjected to 3 passes at 200 bar in the Microfluidizer M110S (3 passages at 500 bar with HBPA amine terminated). The results are presented in Table II below.

Table II

Creaming observed after 8 days is due to the large density difference between hexadecane and water which results in the gradual increase toward the upper part of the larger droplets emulsion.

Example 9 Emulsions prepared with HBPA according to Example 1. Influence of pH of the aqueous phase.

The emulsion contained 5% by weight of HBPA relative to the oil (1% in the emulsion). 3 emulsions are prepared with an aqueous phase at three different pH: 10.4 - 7.0 - 5.5. At pH 5.5 the polymer is used in oil solubility limit is a rapeseed methyl ester (Novance Phytorob 926-65). The emulsions are subjected to 3 passes at 200 bar in the Microfluidizer. The results are presented in Table III below.

At pH 5.5 the polymer is in the limit of solubility in water and it is in this pH range than its affinity for oil / water interface is the largest which explains the very good stability of emulsions and the absence coalescence. The solubility and the affinity of the polymer to water increases with the pH and results in a less good stability of interfaces and the development of a coalescing increasingly important. The increase of the median diameter observed even at pH 5.5 is due to Oswald ripening generated by the solubility of rapeseed ester in water.

Example 10 Synthesis of a hyperbranched copolyamide with carboxylic acid end groups and octadecylene by copolycondensation melt of benzene-1,3,5-tricarboxylic (noted BTC, heart type molecule R 1 -B "3, with B" = COOH), amino-5 isophthalic acid (noted AIPA, branching molecule ARB type 2, with A = NH2 and B = COOH), of I 'ε-caprolactam (denoted CL, spacer A' -R'-B ', with A' = NH2 and B '= COOH) and octadecylamine (denoted C18, type blocker A "-R 2, with A' = NH 2). The respective overall composition is 1/25/25/2 in BTC / AIPA / CUC18. The same reactor as described in Example 1 is employed. A Wood's alloy metal bath is used for heating the reaction mixture. Is introduced into the reactor 74.3 g of ε-caprolactam (0.656 mol) and 66.4 g of deionized water at room temperature. After dissolution, 118.9 g of 5-amino isophthalic acid (0.656 mol), 5.5 g of benzenesulfonic acid 1, 3,5-tricarboxylic (0.026 mol) and 0.476 g of a 50% aqueous solution ( w / w) of hypophosphorous acid are added. The reaction mixture was then stirred mechanically to 50t min. A weak stream of dry nitrogen is formed and heating at 100 ° C is engaged. The reaction mass is then heated rapidly to 100 ° C to 165 ° C in about 15 min. An isothermal plate is carried out at this temperature for 150 min. After a plateau time when the distillation bottom product with water is achieved, 14.1 g of octadecyl amine (0.052 mol) are added to the reaction mixture. After 150 min total, the temperature was raised to 250 ° C over about 15-20 minutes and is then maintained until the top end of the synthesis.

After 2 hours plateau, the reactor is gradually put under vacuum over a period of 60 min then kept under partial vacuum in order to limit foaming (36 mBar) for an additional hour. At cycle end, the stirring is stopped and the reactor allowed to cool to room temperature under a stream of nitrogen. 192.5 g of polymer are collected. The hyperbranched copolyamide obtained is a white solid and is finely ground to its subsequent use.

Example 11: Emulsion inverse 50/50 water in oil An aqueous solution comprising 10% by weight of hyperbranched copolyamide of Example 10 and 0.6% NaCl is prepared and brought to pH = 6.3 with NaOH. 10 g of this aqueous solution are gradually added to 10 g of the silicone oil Rhodorsil Extrasoft, marketed by Rhodia. The mixture was sheared using a frame paddle at 400 rpm for 1-5 minutes. Optical microscopy shows that the droplet size of said emulsion is less than equal to 1 .mu.m.

Example 12: multiple emulsion water in oil in water 45/45/10

external aqueous phase: An aqueous solution comprising 10% by weight of Synperonic PE / F127, commercially available from Uniqema and 0.6% NaCl is prepared.

Emulsification by inverting 90/10 phases:

2 g of the external aqueous phase are added to 18 g of the inverse emulsion of Example 11 (internal emulsion) and the whole is sheared using a frame paddle at 100 rpm for 2.5 minutes. Example 13: Emulsion 35/65 water-in-oil inverse

internal aqueous phase: An aqueous solution comprising 10% by weight of hyperbranched copolyamide of Example 10 and 0.6% NaCl is prepared and brought to pH = 6.3 with NaOH (or HCl).

7 g of this aqueous solution are gradually added to 13 g of silicone oil

Rhodorsil Extrasoft, marketed by Rhodia. The mixture was sheared using a frame paddle at 400 rpm for 1-5 minutes.

Optical microscopy shows that the droplet size of said emulsion is less than equal to 1 .mu.m.

Example 14: multiple emulsion water in oil in water 28/52/20

external aqueous phase: An aqueous solution comprising 10% by weight of Synperonic PE / F127 available from Uniqema and 0.6% NaCl is prepared. Emulsification by inverting 80/20 phases:

4 g of the external aqueous phase are added to 16 g of the inverse emulsion of Example 13 and the whole is sheared using a frame paddle at 100 rpm for 2.5 minutes.

Example 15 A multiple emulsion comprising a single polymeric emulsifier for the inner emulsion and the inverse emulsion

The procedure described in Examples 11 and 12, except that replaces the Synperonic PE / F127 by the hyperbranched copolyamide of Example 10. a stable multiple emulsion is obtained.

Example 16: Introduction of a multiple emulsion in detergent medium

Is placed 1 g of detergent Ariel Regular marketed by Procter & Gamble, Tide marketed by Procter & Gamble in 100 TH hardness of water = 30 ° F, and the multiple emulsion silicone 0.1 g oil equivalent example 12. was stirred with a magnetic stirrer at 25-30 ° C. Samples are taken after 2, 20 and 120 minutes and under a microscope it was observed that the emulsion structure is preserved.

Claims

1. An emulsion comprising an internal phase, an external phase, and an emulsifier polymer, one phase being an aqueous phase, characterized in that the emulsifying polymer is a dendritic polymer.
2. Emulsion according to the preceding claim, characterized in that the dendritic polymer is dispersible or soluble in water, the pH of the emulsion.
3. Emulsion according to any of the preceding claims, characterized in that the dendritic polymer is a hyperbranched polymer comprising hydrophobic groups and hydrophilic groups or potentially hydrophilic.
4. Emulsion according to any of the preceding claims, characterized in that the emulsion is a direct emulsion, the aqueous phase being the external phase, and in that at least part of the hydrophilic or potentially hydrophilic groups are present in groups ends of polymer chains.
5. Emulsion according to one of claims 1 to 3, characterized in that the emulsion is a reverse emulsion, the aqueous phase being the phase is the internal phase, and in that at least a portion of the hydrophobic groups are present at the ends of polymer chains.
6. Emulsion according to any of the preceding claims, characterized in that the emulsion is a multiple emulsion comprising an inner aqueous phase, an intermediate phase and an outer aqueous phase, the internal phase and the intermediate phase comprising an internal inverse emulsion , the intermediate phase and the external phase constituting an outer direct emulsion, and in that at least one emulsion selected from the opposite inner emulsion and the external direct emulsion comprises the dendritic polymer.
7. Emulsion according to the preceding claim, characterized in that the external direct emulsion and the inner inverse emulsion comprise the dendritic polymer.
8. Emulsion according to any of the preceding claims characterized in that the dendritic polymer is a hyperbranched polyamide or a hyperbranched polyester.
9. Emulsion according to any of claims 1 to 6, characterized in that the dendritic polymer is a hyperbranched polymer obtainable by a process comprising the steps of: a) polycondensation in order to obtain a polymer of monomers comprising at least one polyfunctional monomer having at least three reactive functions, of formula (I): AR (B), (I) in which formula - f is an integer greater than or equal to 2, preferably is from 2 to 10, most preferably is 2 - the symbol a represents a reactive functional group or a group carrying a reactive function selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors - the symbol B represents a reactive functional group or a group carrying a reactive function selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato or their precursors, antagonist a - the symbol R is a linear aliphatic polyvalent hydrocarbonné or branched, cycloaliphatic or aromatic group containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms oxygen, nitrogen, sulfur or phosphorus, said remainder optionally having functions or non-functional groups capable of reacting with the functional groups A and B, step b) optionally, hydrophilic functionalizing at least part of the polymer obtained in the polycondensation step.
10. Emulsion according to the preceding claim characterized in that the monomers of step a) include:
• at least one difunctional monomer in linear form of formula (II) in the corresponding cyclic form, comprising two reactive functions polycondensation / polymerization A'-R'-B '(II) wherein: - the symbol A', identical to or different from a, represents a reactive function selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist B and B '- the symbol B', identical to or different from B, represents a reactive functional group selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist a and a '- the symbol R', identical to or different from R, is a linear aliphatic polyvalent hydrocarbonné or branched , cycloaliphatic or aromatic group containing from 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms oxygen, nitrogen, sulfur or phosphorus, edit radical optionally bearing functions or non-functional groups capable of reacting with the A, A ', B and B', the reactive function A ', being capable of reacting with the functional B and / or function B' by condensation ; The reactive function B ', being capable of reacting with the function A and / or function A' by condensation;
• and / or at least one "heart" monomer of formula (III), comprising at least one function capable of reacting by condensation with the monomer of formula (I) and / or the monomer of formula (II) R 1 - (B ") n (III) in which formula - n is an integer greater than or equal to 1, preferably from 1 to 100, most preferably from 1 to 20 - the symbol B" is a reactive function, same or different from B or B ', selected from amino, carboxy functions, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist a and a' - the symbol R 1 is a linear aliphatic polyvalent hydrocarbonné or branched cycloaliphatic-containing or aromatic 1 to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms oxygen, nitrogen, sulfur or phosphorus, or a radical organosiloxane or polyorganosiloxane, said radical R 1 optionally bearing functions or some functional groups not capable of reacting with the A, A ', B, B' and B ", the reactive function B" being capable of reacting with the function A and / or function A 'by condensation;
• and / or at least one monofunctional monomer "chain-limiting" of formula (IV) A "-R 2 (IV) in which formula - the symbol A" is a reactive function, the same as or different from A or A ', selected from amino, carboxy, hydroxy, oxiranyl, halo, isocyanato, or their precursors, antagonist B, B 'and B "- the symbol R 2 is a linear aliphatic polyvalent hydrocarbonné or branched cycloaliphatic 1 containing or aromatic to 50, preferably from 3 to 20 carbon atoms, optionally interrupted by one or more heteroatoms oxygen, nitrogen, sulfur or phosphorus, or an organosiloxane or polyorganosiloxane rest, said radical R 2 optionally bearing functions or not susceptible functional groups to react with the A, A ', A ", B, B' and B", the reactive function A ", being capable of reacting with the functional B and / or function B 'and / or function B "by condensation; • at least one of the reactive functions of at least one of the monomers of formula (II), (III) or (IV) capable of reacting with an antagonist function of the polyfunctional monomer of formula (I).
1 1. An emulsion according to one of Claims 9 or 10, characterized in that the A, A ', A "and B, B', B" are chosen from reactive functional groups or groups bearing reactive functional groups chosen from the amino, carboxyl, hydroxyl, oxiranyl, or their precursors.
12. Emulsion according to one of claims 9 to 11, characterized in that at least one monomer chain limiter is used, said monomer being hydrophilic or potentially hydrophilic.
13. Emulsion according to any of the preceding claims, characterized in that it is a formulation of a cosmetic product, detergent, paint or coating.
14. Emulsion according to the preceding claim, characterized in that the formulation of cosmetic product is a product for the care of the skin or hair.
15. Use of a dendritic polymer as defined in any preceding claim, as an emulsifying agent.
16. Use according to the preceding claim, in a formulation of a cosmetic product, a detergent product, a paint or a coating.
17. Use according to the preceding claim, characterized in that the formulation of cosmetic product is a product for the care of the skin or hair.
EP20040787480 2003-09-29 2004-09-29 Emulsions comprising a dendritic polymer and use of a dendritic polymer as an emulsification agent Withdrawn EP1667636A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US50678803 true 2003-09-29 2003-09-29
PCT/FR2004/002461 WO2005032497A3 (en) 2003-09-29 2004-09-29 Emulsions comprising a dendritic polymer and use of a dendritic polymer as an emulsification agent

Publications (1)

Publication Number Publication Date
EP1667636A2 true true EP1667636A2 (en) 2006-06-14

Family

ID=34421556

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20040787480 Withdrawn EP1667636A2 (en) 2003-09-29 2004-09-29 Emulsions comprising a dendritic polymer and use of a dendritic polymer as an emulsification agent

Country Status (3)

Country Link
US (1) US20070202071A1 (en)
EP (1) EP1667636A2 (en)
WO (1) WO2005032497A3 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101005825B (en) * 2004-08-17 2011-02-09 荷兰联合利华有限公司 Hair care composition comprising a dendritic macromolecule
US8097343B2 (en) * 2004-08-31 2012-01-17 Triton Systems, Inc. Functionalized dendritic polymers for the capture and neutralization of biological and chemical agents
WO2006087227A3 (en) * 2005-02-21 2006-11-09 Basf Ag Active substance composition comprising at least one nitrogen atom-containing, hyperbranched polymer
WO2007098888A1 (en) * 2006-03-03 2007-09-07 Dsm Ip Assets B.V. Hair care compositions
ES2558227T3 (en) * 2008-06-19 2016-02-02 Dsm Ip Assets B.V. Preparations shampoos
US20110293552A1 (en) * 2008-12-22 2011-12-01 Leo Derici Hair care composition comprising a dendritic macromolecule
WO2010117460A1 (en) * 2009-04-08 2010-10-14 Michigan Molecular Institute Surface modification of reverse osmosis membranes by hydrophilic dendritic polymers
CN102712702A (en) 2010-01-20 2012-10-03 巴斯夫欧洲公司 Method for producing an aqueous polymer dispersion
US8722796B2 (en) * 2010-01-20 2014-05-13 Basf Se Process for preparing an aqueous polymer dispersion
US9622951B2 (en) 2012-10-29 2017-04-18 The Procter & Gamble Company Personal care compositions

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4558120A (en) * 1983-01-07 1985-12-10 The Dow Chemical Company Dense star polymer
US4587329A (en) * 1984-08-17 1986-05-06 The Dow Chemical Company Dense star polymers having two dimensional molecular diameter
US5276110A (en) * 1992-08-12 1994-01-04 National Research Council Of Canada Highly regular multi-arm star polymers
US20010011109A1 (en) * 1997-09-05 2001-08-02 Donald A. Tomalia Nanocomposites of dendritic polymers
FR2772770B1 (en) * 1997-12-19 2000-01-28 Oreal New compounds selected from hyperbranched polymers and dendrimers having a particular group, process for the preparation, use and compositions comprising
US6369118B1 (en) * 1998-09-09 2002-04-09 University Of Pittsburgh Biocompatible emulsifier
FR2783418B1 (en) * 1998-09-17 2000-11-10 Oreal Antiwrinkle composition comprising a combination of polymers tensors of synthetic origin and / or natural and dendritic polyesters
FR2783417B1 (en) * 1998-09-17 2002-06-28 Oreal Cosmetic or dermatological topical compositions comprising dendritic polyester
FR2791989A1 (en) * 1999-04-06 2000-10-13 Oreal In particular cosmetic composition comprising polymers having a star structure, said polymers and their use
FR2793252B1 (en) * 1999-05-05 2001-07-20 Rhodianyl Hyperbranched copolyamide, based composition of this hyperbranched copolyamide and obtaining method thereof
US6420479B1 (en) * 2000-12-29 2002-07-16 National Starch And Chemical Investment Holding Corporation Star polymer colloidal stabilizers
US20030070926A1 (en) * 2001-09-18 2003-04-17 Ola Forsstrom-Olsson Landmarks and use thereof
FR2840622B1 (en) * 2002-06-11 2004-07-23 Rhodia Chimie Sa Composition for treating textile fiber articles comprising a dendritic polymer
US7001580B2 (en) * 2002-12-31 2006-02-21 3M Innovative Properties Company Emulsions including surface-modified organic molecules

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005032497A2 *

Also Published As

Publication number Publication date Type
WO2005032497A3 (en) 2005-07-21 application
US20070202071A1 (en) 2007-08-30 application
WO2005032497A2 (en) 2005-04-14 application

Similar Documents

Publication Publication Date Title
US20040234475A1 (en) Oil-in-oil emulsions comprising a silicone, dispersions and use of said emulsions
US20040048996A1 (en) Polymmonium-polysiloxane compounds, methods for the production and use thereof
US6124490A (en) Zwitterionic siloxane polymers and ionically cross-linked polymers formed therefrom
US20040138400A1 (en) Polysiloxane polymers, method for their production and the use thereof
US20080209645A1 (en) Surface Treatment Compositions Comprising Saccharide-Siloxane Copolymers
US20110020260A1 (en) Long-wear and water resistant mascara composition enhancing volume and shine
US6652867B1 (en) Compositions containing organic oil-in-water emulsions, salts, alcohols and solvents
WO1997032917A1 (en) Silicone aminopolyalkyleneoxide block copolymers
CN1040051A (en) Multifunction detergent and its preparation
US4978462A (en) Compositions and process for the treatment of textiles comprising a resinous branched polyorganosiloxane and a polydiorganosiloxane in an aqueous dispersion
O'Lenick Silicone emulsions and surfactants
WO1996033800A1 (en) Compositions containing diol and/or diol alkoxylate
WO2008110590A1 (en) Liquid laundry detergent compositions
US20140030206A1 (en) Silicone Polymers
US6258367B1 (en) Cosmetic composition comprising at least one nonionic amphiphilic associative polyurethane and at least one quaternary silicone
US6395790B1 (en) Siloxane emulsions
US20150030643A1 (en) Amino Silicone Nanoemulsion
US6864349B2 (en) Aqueous suspensions containing polymerized fatty acid-based polyamides
US20050053569A1 (en) Use of cationic block copolymers to assist the deposition of simple or multiple emulsions
WO2011064255A1 (en) Hydrophilic/lipophilic modified polysiloxanes as emulsifiers
WO2006005767A1 (en) Phyllosilicate-containing polysiloxane compositions
JP2000053769A (en) Polyorganosiloxane emulsion and cosmetic containing the same
US20080146484A1 (en) Ion-triggerable, water-disintegratable wet wipe having a salt-stable emulsified wetting composition therein
EP0468703A1 (en) Shampoo system
DE19750245A1 (en) Use of anionic geminal surfactant(s) in cosmetic applications

Legal Events

Date Code Title Description
17P Request for examination filed

Effective date: 20060323

AK Designated contracting states:

Kind code of ref document: A2

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 (to any country) deleted
RIN1 Inventor (correction)

Inventor name: MORVAN, MIKEL

Inventor name: ANTHONY, OLIVIER

Inventor name: TOURAUD, FRANCK,HAMEAU DE NORMANDIE

Inventor name: KARAGIANNI, KATARINA

Inventor name: SENECHAL, ALAIN

Inventor name: ROSSIN, RENE,LES HAUTS DU GOLF

Inventor name: SASSI, JEAN-FRANCOIS

RIN1 Inventor (correction)

Inventor name: TOURAUD, FRANCK,HAMEAU DE NORMANDIE

Inventor name: ANTHONY, OLIVIER

Inventor name: MORVAN, MIKEL

Inventor name: ROSSIN, RENE

Inventor name: SENECHAL, ALAIN

Inventor name: SASSI, JEAN-FRANCOIS

Inventor name: KARAGIANNI, KATARINA

RIN1 Inventor (correction)

Inventor name: TOURAUD, FRANCK,HAMEAU DE NORMANDIE

Inventor name: SASSI, JEAN-FRANCOIS

Inventor name: ROSSIN, RENE

Inventor name: MORVAN, MIKEL

Inventor name: ANTHONY, OLIVIER

Inventor name: SENECHAL, ALAIN

Inventor name: KARAGIANNI, KATARINA

17Q First examination report

Effective date: 20111028

18D Deemed to be withdrawn

Effective date: 20121218