WO1999038946A1

WO1999038946A1 - Perfumes encapsulated in alkali-water soluble polymers, preparation method and use in detergent compositions

Info

Publication number: WO1999038946A1
Application number: PCT/FR1999/000211
Authority: WO
Inventors: Hélène LANNIBOIS-DREAN; Mikel Morvan; Daniel Joubert
Original assignee: Rhodia Chimie
Priority date: 1998-02-02
Filing date: 1999-02-02
Publication date: 1999-08-05
Also published as: FR2774390A1; AU2170399A; EP1060235A1; FR2774390B1

Abstract

The invention concerns a perfuming system (SP) comprising a perfume encapsulated in an alkali-water soluble (AS) organic polymer (pAS), preferably consisting in an alkali-water soluble copolymer derived from the emulsion polymerisation of ethylenically unsaturated monomers polymerisable by radical polymerisation. The invention also concerns the use of the system as perfuming agent in detergent compositions for washing clothes, and the detergent compositions.

Description

1

ENCAPSULATED PERFUMES IN ALKALI-WATER-SOLUBLE POLYMERS,

THEIR PREPARATION PROCESS AND THEIR USE

IN DETERGENT COMPOSITIONS

The subject of the present invention is a perfuming system comprising a perfume encapsulated in an alkali-water-soluble organic polymer obtained by emulsion polymerization of ethylenically unsaturated monomers, its preparation process, its use as a perfuming agent in detergent compositions and detergent compositions comprising said system. Laundry detergents generally contain perfumes; it has been found that during their storage, the powdered detergents for washing machines in particular, lose from 20 to 90% of the perfume introduced, which requires the introduction at the start of very high quantities of perfume to maintain a sufficient scent at time of product use.

The Applicant has found a perfume encapsulation system making it possible to release the perfume only essentially during the washing of the laundry.

A first subject of the invention consists of a perfume system (SP) comprising a perfume in the molecular state encapsulated in particles (pAS) of an alkali-water-soluble organic polymer (AS) obtained by emulsion polymerization.

* of at least one anionic ethylenically unsaturated monomer which can be polymerized by the radical route

* and at least one nonionic ethylenically unsaturated comonomer which can be polymerized by the radical route, the amount of said anionic monomer (s) representing at least 20%, preferably from 25 to 60% by weight of the total amount of monomers. The term “perfume” means either a perfumed essence or more generally a complex composition obtained using a mixture of numerous odorous products and excipient products which ensure their homogeneity.

Said mixture generally contains at least 25% of at least one odorous compound from the group of aliphatic or aromatic ketones, aliphatic or aromatic aldehydes, condensation products of aldehydes and amines, aromatic or aliphatic lactones, aromatic ethers or esters or aliphatic, aliphatic alcohols, saturated or unsaturated hydrocarbons, linear, cyclic or aromatic, terpene, polynuclear or not ...

As an example of an odorous compound, the following may be mentioned: - hexylcinnamic aldehyde, - 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde, - 7-acetyl-1, 2,3,4, 5.6J, 8-octahydro-1 J, 6J-tetramethylnaphthalene, - benzyl salicylate,

- 7-acetyl-1, 1, 3,4,4,6-hexamethyltetralin, - p-tert-butylcyclohexyl acetate,

- methyl dihydro jasmonate,

- β-naphthol methyl ether,

- methyl-β-naphthylketone, - 2-methyl-2- (p-isopropylphenyl) -propionaldehyde,

- le1, 3,4,6J, 8-hexahydro-4,6,6J, 8,8-hexamethyl-cyciopenta-γ-2-benzo-pyrane,

- dodecahydro-3a, 6,6,9a-tetramethylnaphto [2,1 b] bifuran,

- Panisaidehyde,

- coumarin, - cedrol,

- vanillin,

- ethylvanillin,

- Pheliotropin,

- ethylene brassylate, - isobomylcyclohexanol,

- cyclopentadecanolide,

- isoamyl acetate,

- tricyclodecenyl acetate,

- tricyclodecenyl propionate, - β-phenylethyl alcohol,

- terpineol,

- the linalool,

- linalyl acetate,

- geraniol, - nerol,

- 2- (1,1-dimethylethyl) cyclohexanol acetate,

- benzyl acetate,

- terpenes (orange),

- Peugenol, - diethyl phthalate,

- essential oils, resins or resinoids (orange oil, lemon, patchouli, Peruvian beaume, resinoid olibanum, styrax, coriander, lavandin, lavender ...).

Said encapsulated perfume is in a molecular state, that is to say dissolved in said organic polymer and / or a third solvent. The amount of perfume which may be present in said perfume system (SP) can range from 20 to 70, preferably from 40 to 60 parts by weight of perfume per 100 parts by weight of alkali-water-soluble polymer (AS). The term "alkali-water-soluble" polymer (AS) means a polymer capable of dissolving or dispersing in an aqueous medium of pH greater than 7, preferably of pH at least 9.5 at a temperature of range from 20 to 90 ° C. This is not water-soluble at a pH below 7. Said alkali-water-soluble polymers (AS), are derived from at least one anionic ethylenically unsaturated monomer which can be polymerized by the radical route and from at least one ethylenically unsaturated comonomer which can be polymerized by radical way.

As examples of anionic monomers, mention may be made of:. ethylenically unsaturated α-β carboxylic acids, such as acrylic, methacrylic, maleic, itaconic acids ...

. ethylenically unsaturated α-β sulfonated monomers, such as vinylbenzene sulfonate ...

The level of anionic monomer is of course a function of the hydrophilia thereof.

Preferably, said anionic monomers are carboxylic monomers.

As examples of nonionic monomers, there may be mentioned:

. vinyiaromatic monomers: styrene, vinyltoluene .... alkyl esters of α-β ethylenically unsaturated acids: methyl acrylates and methacrylates, ethyl ...

. vinyl or allyia esters of saturated carboxylic acids: acetates, propionates ...

. vinyl or vinylidene halides: chlorides ...

. aliphatic conjugated dienes: butadiene .... ethylenically unsaturated α-β nitriies: acrylonitrile ...

. hydroxyaikyl esters of α-β ethylenically unsaturated acids: hydroxyethyl and hydroxypropyl acrylates and methacrylates ...

. amides of α-β ethylenically unsaturated acids: acrylamide, methacrylamide ...

Said alkali-water-soluble polymers (AS) can also be derived from a monomer composition additionally containing at least one polyfunctional crosslinking comonomer (MR) (containing at least two ethylenic unsaturations) and / or at least one nonionic amphiphilic comonomer (MG) ethylenically unsaturated capable of forming graft copolymers with the other comonomers. Said polyfunctional crosslinking comonomer (s) (MR) may or may represent of the order of 0.01 to 1%, preferably 0.01 to 0.5% of all monomers of the monomer composition.

By way of example of crosslinking comonomers (MR), there may be mentioned: glyoxal bis acrylamide ethylene glycol diacrylate or dimethacrylate trimethylolpropanetrimethacrylate, pentaerithritol triacrylate polyallyl ethers of ethylene glycol, glycerol, pentaerithritol, diethylene glycol allyl acrylylbenzene divinylbenzene alinylbenzene

Said or said nonionic amphiphilic comonomer (s) grafting (MG) can or can represent up to 20% of all the monomers.

By way of example of grafting amphiphilic comonomers (MG), mention may be made of those of formula

CH2 = C (R ¹ ) -C (0) -0- [CH ₂ -CH (R ² ) O] _m - [CH (R ³ ) -CH ₂ 0] _n -R ⁴ in which. R ^" is a hydrogen atom or a methyl radical

. R ² and R ³ , identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms

. R ⁴ is. an alkyl radical containing from 8 to 30 carbon atoms. a phenyl radical substituted by one to three 1-phenylethyl groups. an alkylphenyl radical containing from 8 to 10 carbon atoms

. n ranges from 6 to 100 and m from 0 to 50, provided that n is greater than or equal to m and their sum is between 6 and 100.

Mention may very particularly be made of the amphiphilic comonomers described in EP-A-705 854 and US-A-4 384 096, in particular the grafting comonomer (MG ′) of formula above, in which R ¹ is a methyl radical, R ² is a hydrogen atom, m is 25, n is zero and R ⁴ is a C22H45 alkyl radical.

As examples of alkali-water-soluble polymers (AS), mention may in particular be made of derived copolymers. of a monomer composition consisting of acrylic and / or methacrylic esters and at least 30% of acrylic and / or methacrylic acid

. of said monomer composition further containing a crosslinking comonomer glyoxal bis acrylamide or ethylene glycol dimethacrylate

. of said monomer composition additionally containing the grafting comonomer (MG ') The particles of water-soluble polymers (pAS) derived from ethylenically unsaturated monomers comprise at their surface at least 0.1% of their weight of at least one anionic emulsifying agent , non-ionic or amphoteric. As examples of emulsifying agents, mention may be made of: - anionic emulsifiers such as: fatty acid salts; alkylsulfates (sodium lauryl sulfate), alkylsulfonates, alkylarylsulfonates (sodium dodecyibenzene sulfonates, sodium di-butylnaphthalene sulfonate), alkylsulfosuccinates or succinamates (disioctylsulfosuccinamate disodium, n-octadecylsulfosuccinamodic disodium alphosphatamines); sodium dodecyldiphenylether disulfonate; sulfonates of alkylphenolpolyglycolic ethers; ester salts of alkylsulfopolycarboxylic acids; the condensation products of fatty acids with oxy- and aminoalkanesulfonic acids; sulfated derivatives of polyglycolic ethers; sulfated esters of fatty acids and polyglycols; alkanolamides of sulfated fatty acids; - non-ionic emulsifiers such as

. ethoxylated or ethoxy-propoxylated fatty alcohols. ethoxylated or ethoxy-propoxylated triglycerides. ethoxylated or ethoxy-propoxylated fatty acids. ethoxylated or ethoxy-propoxylated sorbitan esters. ethoxy-containing or ethoxy-propoxylated fatty amines

. ethoxylated or ethoxy-propoxylated di (1-phenylethyl) phenols. ethoxylated or ethoxy-propoxylated tri (1-phenylethyl) phenols. ethoxylated or ethoxy-propoxylated alkyl phenols. ethylene polyoxides. fatty acid alkanolamides

Among the amphoteric emulsifiers, mention may be made of alkyl betaines, alkyldimethyl betaines, alkylamidopropyl betaines, alkylamidopropyl dimethyibetaines, alkylt methyl sulfobetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphodiacetates, alkylamphodiacetates, alkylamphoethanes alkylsultaines or alkylamidopropyl-hydroxysultaines, condensation products of fatty acids and protein hydrolysates, amphoteric derivatives of alkylpolyamines such as Amphionic XL® sold by Rhône-Poulenc, Ampholac 7T / X® and Ampholac 7C / X ® marketed by Berol Nobel, proteins or protein hydrolysates. Preferably, said emulsifier is anionic or nonionic.

A first embodiment of the invention consists of a perfume system (S'P) in the form of an aqueous dispersion (latex) (LSP) of particles (pSP) of perfume system (SP). This dispersion (LSP) can contain of the order of 10 to 50%, preferably of the order of 20 to 50% of its weight of particles (pSP) of perfuming system (SP).

The particle diameter (pSP) of the perfuming system (SP) can be of the order of 20 to 700 nanometers, preferably of the order of 100 to 400 nanometers. The aqueous dispersion (LSP) of the perfume system can be prepared by introducing said perfume in liquid form into said alkali-water-soluble polymer (AS) which is in the form of a latex (LAS), the introduction of the perfume being able to be carried out either at during the actual synthesis of said alkali-water-soluble polymer by aqueous emulsion polymerization, or after the synthesis of said alkali-water-soluble polymer by aqueous emulsion polymerization.

Preferably, the introduction of the perfume into the latex of soluble alkali polymer (LAS) is carried out after the step of polymerization in aqueous emulsion of the monomer composition. Said alkali-water-soluble polymer (LAS) latex has a dry extract of alkali-water-soluble polymer similar, but slightly lower, than that of the latex (LSP) of the perfume system to be prepared; similarly, the particle size (pAS) of alkaline water-soluble polymer (AS) of the latex (LAS) is similar, but slightly smaller, than that of the particles (pSP) of the latex (LSP) of the perfume system to be prepared. The particles (pAS) of the latex (LAS) have on their surface at least one emulsifying agent, at a rate of the order of 0.1 to 15% of the weight of dry polymer. This emulsifier level is a function of the size of the latex particles.

The nature of said emulsifier (s) has already been mentioned above.

The perfume present in the liquid state can be introduced directly into the latex (LAS) of alkali-water-soluble polymer, if it is sufficiently "swelling" of the polymer, or assisted if necessary by a swelling "transfer" solvent of the polymer .

Among the transfer solvents, mention may be made of

. esters such as ethyl acetate, methyl propionate, the mixture of glutarate / adipate / methyl succinate (solvent "RPDE") .... ketones such as methyl ethyl ketone, cyclohexanone ...

. alcohols such as propanol, pentanol, cyclohexanol ...

. linear or cyclic aliphatic hydrocarbons such as heptane, decane, cyclohexane, decaline ...

. chlorinated aliphatic derivatives such as dichloromethane .... aromatic derivatives such as toluene, ethylbenzene ...

. chlorinated aromatic derivatives such as trichlorobenzene ...

. dialkylethers

The presence of a transfer solvent is generally not necessary for a liquid perfume.

It is possible to add, if necessary, to the latex (LAS) of alkali-water-soluble polymer, an additional quantity of emulsifying agent, in particular of non-ionic polyoxyalkylenated emulsifying agent, of the type of those already mentioned above. This quantity additional may represent of the order of 0.1 to 2%, preferably of the order of 0.1 to 0.2% of the weight of perfume used.

The perfume introduced is brought into contact with the latex (LAS), with stirring at a temperature of 20 to 50 ° C for 1 to 24 hours. A second embodiment of the invention consists of a perfuming system

(S "P) being in the form of dry solid granules (G), dispersible in water. Said dry granules (G), comprise particles (pSP) of the perfume system (SP) comprising said perfume encapsulated in the state molecular in said solid alkaline water-soluble polymer (AS), said particles (pSP) being dispersed in and encapsulated by a matrix in at least one dry solid, water-soluble or water-dispersible organic compound (MO), at least 0.1% by weight of at least one emulsifying agent relative to the weight of alkali-water-soluble polymer (AS) occurring at the matrix (MO) / particle (pSP) interface of the perfuming system (SP).

For a good implementation of this second mode, said granules (G) dispersible in water, comprise:

- from 5 to 90%, preferably from 40 to 85% of their weight of the perfume system (SP)

- from 3 to 90%, preferably from 10 to 60%, very particularly from 15 to 50% of water-soluble or water-dispersible (MO) organic matrix.

Among the water-soluble or water-dispersible (MO) organic compounds that may be mentioned

- water-soluble or water-dispersible polypeptides (PP) of natural or synthetic origin

- polyelectrolytes (PE) in acid form belonging to the family of weak polyacids - oses, osides or water-soluble or water-dispersible polyholosides (O)

- amino acids or water-soluble or water-dispersible amino acid (AA) salts

- surfactants (TA) whose binary water-surfactant phase diagram includes a fluid isotropic phase at 25 ° C up to a concentration of at least 50% by weight of surfactant, followed by a rigid liquid crystal phase of hexagonal or cubic type at higher concentrations, stable at least up to 60 ° C.

- or their mixtures.

Among the water-soluble or water-dispersible synthetic polypeptides (PP) which may constitute the crust, mention may be made of homopolymers or copolymers derived from the polycondensation of amino acids or of amino acid precursors, in particular aspartic and glutamic acid or their precursors , and hydrolysis. These polymers can be homopolymers derived from aspartic or glutamic acid as well as copolymers derived from aspartic acid and glutamic acid in any proportions, or copolymers derived from aspartic acid and / or 8

glutamic and other amino acids. Among the copolymerizable amino acids, there may be mentioned glycine, alanine, leucine, isoleucine, phenylananine, methionine, histidine, praline, lysine, serine, threonine, cysteine ...

Among the polypeptides (PP) of plant origin which can constitute the matrix, mention may be made of proteins of plant origin; these are preferably hydrolyzed, with a degree of hydrolysis less than or equal to 40%, for example from 5 to less than 40%.

Among the proteins of vegetable origin, mention may be made, by way of indication, of the proteins originating from protein seeds, in particular those of peas, faba beans, lupins, beans, and lentils; proteins from cereal grains, especially those from wheat, barley, rye, corn, rice, oats, and millet; proteins from oil seeds, especially those from soybeans, peanuts, sunflowers, rapeseed, and coconuts; proteins from the leaves, especially alfalfa, and nettles; and proteins from plant organs from buried reserves, notably that of potatoes and beets. Among the proteins of animal origin, mention may be made, for example, of muscle proteins, in particular stroma proteins, and gelatin; proteins from milk, in particular casein, lactoglobulin; and fish protein.

The protein is preferably of vegetable origin, and more particularly comes from soybeans or wheat. The polyelectrolyte (PE) can be chosen from those resulting from the polymerization of monomers which have the following general formula

(R ¹ ) (R ² ) C = C (R ³ ) COOH formula in which R ¹ , R ² , and R ³ are identical or different and represent

. a hydrogen atom,. a hydrocarbon radical containing from 1 to 4 carbon atoms, preferably methyl

. a -COOH function

. a radical -R-COOH, where R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene residue containing 1 or 2 carbon atoms, methylene in particular. By way of nonlimiting examples, mention may be made of acrylic, methacrylic, maleic, fumaric, itaconic and crotonic acids.

Also suitable are the copolymers obtained from the monomers corresponding to the preceding general formula and those obtained using these monomers and other monomers, in particular vinyl derivatives such as vinyl alcohols and copolymerizable amides such as acrylamide or methacrylamide. Mention may also be made of the copolymers obtained from alkyl vinyl ether and maleic acid. as well as those obtained from vinyl styrene and maleic acid which are described in particular in the KIRK-OTHMER encyclopedia entitled "ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY" - Volume 18 - 3rd edition - Wiley interscience publication - 1982.

The preferred polyelectrolytes have a low degree of polymerization. The molecular mass by weight of the polyelectrolytes is more particularly less than 20,000 g / mole. Preferably, it is between 1000 and 5000 g / mole.

Among the dares (O) there may be mentioned aldoses such as glucose, mannose, galactose, ribose, and ketoses such as fructose.

Osides are compounds which result from the condensation, with elimination of water, of daring molecules between them or even of daring molecules with non-carbohydrate molecules. among the osides, the holosides which are formed by the combination of exclusively carbohydrate units are preferred, and more particularly the oligoholosides (or oligosaccharides) which contain only a limited number of these units, that is to say a number which is generally lower. or equal to 10. As examples of oligoholosides, mention may be made of sucrose, lactose, cellobiose, maltose and trehalose.

The water-soluble or water-dispersible polyholosides (or polysaccharides) are highly depolymerized; they are described for example in the work of P. ARNAUD entitled "organic chemistry course", Gaultier-Villars editors, 1987. More particularly, these polyholosides have a molecular mass by weight of less than 20,000 g / mole. By way of nonlimiting example of highly depolymerized polyholosides, mention may be made of dextran, starch, xanthan gum and galactomannans such as guar or carob, these polysaccharides preferably having a melting point above 100 ° C. and a solubility in water of between 50 and 500 g / l.

Among the amino acids (AA), there may be mentioned monocarboxylated or dicarboxylated mono-amino acids, monocarboxylated diamine acids and their water-soluble derivatives.

Amino acids (AA) preferably have a side chain with acid-base properties; they are chosen in particular from Parginine, lysine, histidine, aspartic, glutamic and hydroxyglutamic acids; they can also be in the form of derivatives, preferably water-soluble; they may, for example, be sodium, potassium or ammonium salts, such as sodium glutamate, aspartate or hydroxyglutamate.

With regard to the surfactants (TA) likely to constitute the organic matrix (MO), the description of the fluid isotropic phases and rigid liquid crystal of hexagonal or cubic type is given in the work of R.G. LAUGHLIN entitled

"The AQUEOUS PHASE BEHAVIOR OF SURFACTANTS" - ACADEMIC PRESS - 1994.

Their identification by diffusion of radiation (X and neutrons) is described in 10

the work of V. LUZZATI entitled "BIOLOGICAL MEMBRANES, PHYSICAL FACT AND FUNCTION" - ACADEMIC PRESS - 1968.

More particularly, the rigid liquid crystal phase is stable up to a temperature at least equal to 55 ° C. The fluid isotropic phase can be poured, while the rigid liquid crystal phase cannot.

Among the surfactants (TA), mention may be made of ionic glycolipid surfactants, in particular derivatives of uronic acids (galacturonic, glucuronic acids, D-mannuronic, L-iduronic, L-guluronic, etc.), having a substituted hydrocarbon chain or unsaturated or unsaturated comprising from 6 to 24 carbon atoms and preferably from 8 to 16 carbon atoms, or their salts. This type of product is described in particular in patent application EP 532 370. Other examples of surfactant (TA) are amphoteric surfactants such as the amphoteric derivatives of alkyl poiyamines such as Pamphionic XL®, Mirataine H2C- HA® marketed by Rhône Poulenc as well as PAmpholac 7T / X® and PAmpholac 7C / X® marketed by Berol Nobel.

The perfume system (S "P) in the form of dry solid granules, can be obtained by removing water / drying an aqueous dispersion (D) comprising said latex (LSP) of particles (pSP) of perfume system (SP ) and said water-soluble or water-dispersible organic compound capable of forming the matrix (MO). For a good implementation of the process, the level of dry extract of the aqueous dispersion (D) comprising the mixture of latex (LSP) and of organic compound ( MO) is of the order of 20 to 70%, preferably of the order of 30 to 60% by weight. Said process can be carried out by

- addition to the latex (LSP) of at least one organic compound (MO) and optionally a dispersing agent

- then elimination of the water / drying of the aqueous dispersion obtained.

The amount of optional dispersing agent can be of the order of 0.02 to 20% by weight relative to the weight of dry alkali water-soluble polymer (AS). The presence of a dispersing agent is generally favorable, in particular when the organic compound (MO) is not a surfactant (TA) or a protein.

Among the dispersing agents which can be used, mention may be made of nonionic, anionic or amphoteric emulsifying agents.

When the organic compound (MO) is a polypeptide (PP) or an amino acid (AA), said emulsifying agent is chosen from anionic or amphoteric emulsifiers. When the organic compound (MO) is a polyelectrolyte (PE), said emulsifying agent (AE) is chosen from nonionic or amphoteric emulsifiers. When the organic compound (MO) is a ose, oside or polyholoside, said emulsifying agent is chosen from anionic emulsifiers. 1 1

Among the nonionic emulsifiers, there may be mentioned in particular polyoxyalkylenated derivatives such as ethoxylated or ethoxy-propoxylated fatty alcohols

- ethoxylated or ethoxy-propoxylated triglycerides

- ethoxylated or ethoxy-propoxylated fatty acids - ethoxylated or ethoxy-propoxylated sorbitan esters

- ethoxylated or ethoxy-propoxylated fatty amines

- ethoxylated or ethoxy-propoxylated di (phenyl-1 ethyl) phenols

- tri (1-phenylethyl) ethoxylated or ethoxy-propoxylated phenols

- ethoxylated or ethoxy-propoxylated alkyl phenols The number of oxyethylene (OE) and / or oxypropylene (OP) units of these nonionic surfactants usually varies from 2 to 100 depending on the HLB (hydrophilic / lipophilic balance) desired. More particularly, the number of OE and / or OP units is between 2 and 50. Preferably, the number of OE and / or OP units is between 10 and 50.

Ethoxylated or ethoxy-propoxylated fatty alcohols generally contain from 6 to 22 carbon atoms, the OE and OP units being excluded from these numbers. Preferably, these units are ethoxylated units.

The ethoxylated or ethoxy-propoxylated triglycerides can be triglycerides of plant or animal origin (such as lard, tallow, peanut oil, butter oil, cottonseed oil, oil flaxseed, olive oil, fish oil, palm oil, grape seed oil, soybean oil, castor oil, rapeseed oil, coconut oil, coconut oil and are preferably ethoxylated.

The ethoxylated or ethoxy-propoxylated fatty acids are fatty acid esters (such as for example oleic acid, stearic acid), and are preferably ethoxylated.

The ethoxylated or ethoxy-propoxylated sorbitan esters are cyclized fatty acid sorbitol esters comprising from 10 to 20 carbon atoms such as lauric acid, stearic acid or oleic acid, and are preferably ethoxylated.

The term ethoxylated triglyceride is intended in the present invention, both the products obtained by ethoxylation of a triglyceride with ethylene oxide as those obtained by transesterification of a triglyceride with a polyethylene glycol. Likewise, the term ethoxylated fatty acid includes both the products obtained by ethoxylation of a fatty acid with ethylene oxide and those obtained by transesterification of a fatty acid with a polyethylene glycol.

Ethoxylated or ethoxy-propoxylated fatty amines generally have from 10 to 22 carbon atoms, the OE and OP units being excluded from these numbers, and are preferably ethoxylated.

The ethoxylated or ethoxy-propoxylated alkylphenols are generally 1 or 2 alkyl groups, linear or branched, having 4 to 12 carbon atoms. By way of example, mention may in particular be made of octyl, nonyl or dodecyl groups. 12

Examples of non-ionic surfactants from the group of ethoxy or ethoxy-propoxylated alkylphenols, ethoxylated di (phenyl-1 ethyl) phenols and tri (1-ethyl phenyl) phenols, ethoxy or ethoxy-propoxylates may be mentioned in particular di (phenyl-1 ethyl) phenox ethoxylated with 5 EO units, di (phenyl-1 ethyl) phenol ethoxylated with 10 EO units, tri (phenyl-1 ethyl) phenol ethoxylated with 16 EO units, tri (phenyl -1 ethyl) ethoxylated phenol with 20 EO units, tri (1-phenyl ethyl) ethoxylated phenol with 25 EO units, tri (1-phenylethyl) ethoxylated phenol with 40 EO units, tri (1-phenyl ethyl) phenols ethoxy-propoxylated with 25 EO + OP units, nonylphenol ethoxylated with 2 EO units, nonylphenol ethoxylated with 4 EO units, nonylphenol ethoxylated with 6 EO units, nonylphenol ethoxylated with 9 EO units, nonylphenol ethoxy-propoxylated with 25 units OE + OP, ethoxy-propoxylated nonylphenols with 30 OE + OP units, ethoxy-propoxylated nonylphenols with 40 OE + OP units, ethoxy-propoxylated nonylphenols with 55 OE + OP units, ethoxy-propoxylated nonylphenols with 80 OE + OP units. Among the anionic emulsifiers, mention may be made of the water-soluble salts of alkylsulphates, of alkylethersulphates, alkylisethionates and alkyltaurates or their salts, aikylcarboxylates, aikylsulfosuccinates or alkylsuccinamates, alkylsarcosinates, alkyl derivatives of hydricysates, acylaspartates, phosphates, alkyl esters and / or alkyl ether and / or alkylaryl ether. The cation is generally an alkali or alkaline earth metal, such as sodium, potassium, lithium, magnesium, or an ammonium group NR ₄ ⁺ with R, identical or different, representing an alkyl radical substituted or not by a oxygen or nitrogen atom.

Among the amphoteric emulsifiers, mention may be made of alkyl betaines, alkyldimethyl betaines, alkylamidopropyl betaines, alkyl amidopropyl dimet betaines, alkyltrimethyl sulfobetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphodiacetates, alkylampho-amphionates, alkylampho-propylates alkylsultaines or alkylamidopropyl-hydroxysultaines, condensation products of fatty acids and protein hydriysates, amphoteric derivatives of alkylpolyamines such as Amphionic XL® sold by Rhône-Poulenc, Ampholac 7T / X® and Ampholac 7C / X® marketed by Berol Nobel, proteins or protein hydrolysates.

The operation of removing the water / drying the aqueous dispersion can be carried out by any means known to those skilled in the art, in particular by lyophilization (ie freezing, then sublimation) or preferably by drying by atomization. Spray drying can be carried out in any known device, such as an atomization tower combining spraying carried out by a nozzle or a turbine with a stream of hot air. The conditions of implementation depend on the type of matrix of 13

organic compound (MO) and atomizer used; these conditions are generally such that the temperature of the entire product during drying does not exceed 150 ° C, preferably does not exceed 110 ° C.

The granules (G) obtained are dispersible in water, at room temperature, by simple stirring, to give a pseudo-latex of the perfuming system (SP).

Said granules (G) can optionally also contain an anti-caking agent or a filler, such as in particular calcium carbonate, kaolin, silica, a bentonite, etc., which can be added totally or partially, either to the aqueous dispersion before removal of the water, either during the atomization step or else to the final granule composition.

Another subject of the invention consists in the use in detergent compositions for washing clothes (industrial or household washing), of said perfuming system (SP), in particular in the form of an aqueous dispersion (LSP) or in the form of granules (S "P), as a scenting agent for textile fibers and detergent compositions themselves.

According to the invention, said perfuming system can be used in an amount of approximately 0.01 to 0.5%, preferably 0.05 to 0.2% by weight, expressed in quantity of perfume relative to the detergent composition.

A final object of the invention consists of detergent compositions for washing clothes (industrial or household washing), comprising said perfuming system (SP), in particular in the form of an aqueous dispersion (LSP) or in the form of granules (S "P).

According to the invention, said detergent compositions may contain approximately 0.01 to 0.5%, preferably 0.05 to 0.2% of their weight of the perfume system, expressed as perfume.

The detergent compositions according to the invention comprise at least one surfactant, in an amount generally of the order of 5 to 60% by weight, preferably from 8 to 50% by weight.

Among these, there may be mentioned the anionic or nonionic surfactants usually used in the field of detergency for washing clothes. The detergent compositions which are the subject of the invention may also comprise usual additives, such as mineral or organic detergency builders, in an amount such that the total amount of detergency builder is from 5 to 80% by weight of said composition, preferably from 8 to 40% by weight, anti-fouling agents, anti-redeposition agents, bleaching agents, fluorescent agents, foam suppressants, agents softeners, enzymes and other additives. 14

The following examples are given by way of illustration.

Example 1

Characteristics of the encapsulation latex ^* starting monomer composition (% by weight). butyl acrylate 10%

. ethyl acrylate 56.4%

. methacrylic acid 33.6%

^* emulsifiers 0.955% compared to all of the monomers (0.015% of ethoxylated nonylphenol containing 25 EO units on average per mole, in the form of ammonium salt + 0.94% of sodium tetrapropylbenzene sulfonate)

* dry extract = 38.9%

^* particle diameter = around 200 nanometers

Ethylated nonylphenol containing 30 EO units on average per mole is introduced into the above latex as a dispersing agent, in an amount corresponding to 0.2% of the weight of the perfume composition to be encapsulated.

Is introduced dropwise, with mechanical stirring, the perfume composition in an amount corresponding to 44% by weight relative to the weight of polymer above dry.

The medium is left stirring at 30 ° C for 4 hours. An encapsulated perfuming system is thus obtained, in the form of a latex.

Example 2

The operation described in Example 1 is repeated, using

^* as starting latex, that derived from the following monomer composition and from the following characteristics

. butyl acrylate 7.25%

. ethyl acrylate 56, 15%

. methacrylic acid 33.6%

. glyoxal bis acrylamide 300 ppm. emulsifier 1.5% relative to all of the monomers

(ethoxylated nonylphenol containing 9 EO units on average per mole, in the form of ammonium salt)

. dry extract = 38,%

. particle diameter = approximately 200 nanometers * as dispersing agent, ethoxylated oleocetyl alcohol containing 25 EO units on average per mole

* an amount of perfume composition corresponding to 50% by weight relative to the weight of polymer above dry. 15

An encapsulated perfuming system is thus obtained, in the form of a latex.

Example 3 In a mixer, the following dispersion is prepared:

Composition% by weight encapsulated perfuming system, in the form of a latex, of Example 1 or 2 89%

(expressed in aqueous dispersion)

Amphionic XL ^* (marketed by RHODIA 2.1% polyacrylic acid (Mw = 2000) 8.9%

* solution in water of alkylaminocarboxylate, with 40% of dry extract, including 10% of sodium chloride

1 kg of this dispersion is atomized under standard conditions of a NIRO® type atomization column (115 ° C at the inlet and 60 ° C at the outlet). A pourable powder is obtained.

Claims

16

1) Perfume system (SP) comprising a perfume encapsulated in the molecular state in particles (pAS) of an alkali-water-soluble organic polymer (AS) obtained by emulsion polymerization

^* of at least one anionic ethylenically unsaturated monomer which can be polymerized by the radical route

^* and at least one nonionic ethylenically unsaturated comonomer which can be polymerized by the radical route, the amount of said anionic monomer (s) representing at least 20%, preferably from 25 to 60% by weight of the total amount of monomers.

2) System according to claim 1), characterized in that the perfume (P) is a perfumed essence or comprises odorous compounds from the group of aliphatic or aromatic ketones, aliphatic or aromatic aldehydes, condensation products of aldehydes and amines , aromatic or aliphatic lactones, aromatic or aliphatic ethers or esters, aliphatic alcohols, linear, cyclic or aromatic, terpene, polynuclear or non-saturated or unsaturated hydrocarbons.

3) System according to claim 1) or 2), characterized in that the quantity of perfume (P) present in said perfuming system (SP), can range from 20 to 70, preferably from 40 to 60 parts by weight of perfume per 100 parts by weight of alkali water-soluble polymer (AS).

4) System according to any one of claims 1) to 3), characterized in that the alkali-water-soluble polymer (AS) is an organic polymer capable of dissolving or dispersing in an aqueous medium of pH greater than 7, preferably a pH of at least 9.5 at a temperature of the order of 20 to 90 ° C.

5) System according to any one of claims 1) to 4), characterized in that the anionic monomer is chosen from α-β ethylenically unsaturated carboxylic acids, such as acrylic, methacrylic, maleic, itaconic acids and α sulfonated monomers -β ethylenically unsaturated, such as vinylbenzene sulfonate.

6) System according to any one of claims 1) to 4), characterized in that the nonionic monomer is chosen from 17

. vinyl aromatic monomers. alkyl esters of α-β ethylenically unsaturated acids. vinyl or allyl esters of saturated carboxylic acids. vinyl or vinylidene halides. conjugated aliphatic dienes

. ethylenically unsaturated α-β nitriles

. hydroxyalkyl esters of α-β ethylenically unsaturated acids

. amides of α-β ethylenically unsaturated acids

7) System according to any one of claims 1) to 6), characterized in that the alkali-water-soluble copolymers (AS) are derived from a monomer composition additionally containing at least one polyfunctional crosslinking comonomer (MR) and / or minus an ethylenically unsaturated non-ionic amphiphilic comonomer (MG) capable of forming graft copolymers with the other comonomers.

8) System according to claim 7), characterized in that the cross-linking comonomer (s) polyfunctional (s) (MR) represents (s) of the order of 0.01 to 1%, preferably from 0.01 to 0.5% of all the monomers of the monomer composition.

9) System according to claim 7), characterized in that the (s) non-ionic amphiphilic comonomer (s) grafting (s) (MG) represents (s) up to 20% of the all of the monomers.

10) System according to claim 9), characterized in that the grafting nonionic amphiphilic comonomer (MG) has the formula

CH ₂ = C (R ¹ ) -C (0) -0- [CH ₂ -CH (R ² ) 0] _m - [CH (R ³ ) -CH ₂ 0] _n -R ⁴ in which

. R1 is a hydrogen atom or a methyl radical

. R ² and R 3, identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms. R ⁴ is. an alkyl radical containing from 8 to 30 carbon atoms. a phenyl radical substituted by one to three 1-phenylethyl groups. an alkylphenyl radical containing from 8 to 10 carbon atoms. n ranges from 6 to 100 and m from 0 to 50, provided that n is greater than or equal to m and their sum is between 6 and 100. 18

11) System according to any one of claims 1) to 10), characterized in that the alkali-water-soluble copolymer (AS) is chosen from those derived

. of a monomer composition consisting of acrylic and / or methacrylic esters and at least 30% of acrylic and / or methacrylic acid. of said monomer composition further containing a crosslinking comonomer glyoxal bis acrylamide or ethylene glycol dimethacrylate. of said monomer composition further containing the grafting comonomer of formula

CH ₂ = C (R ¹ ) -C (0) -0- [CH ₂ -CH (R ² ) 0] _m - [CH (R ³ ) -CH ₂ 0] _n -R ⁴ in which R ¹ is a methyl radical, R ² is a hydrogen atom, m is 25, n is zero and R ⁴ is a C ₂₂ H45 alkyl radical.

12) System according to any one of claims 1) to 11), characterized in that the particles (pAS) of alkali-water-soluble copolymers derived from ethylenically unsaturated monomers comprise at their surface at least 0.1%, preferably 0 , 1 to 15% of their weight of at least one anionic, nonionic or amphoteric emulsifying agent.

13) System according to any one of claims 1) to 12), characterized in that it is in the form of particles (pSP) in aqueous dispersion (latex) (LSP).

14) System according to claim 13), characterized in that the dispersion (LSP) contains of the order of 10 to 50%, preferably of the order of 20 to 50% of its weight of particles (pSP) in diameter on the order of 20 to 700 nanometers, preferably on the order of 100 to 400 nanometers.

15) System according to claim 13) or 14), characterized in that the dispersion (LSP) is capable of being obtained by introducing said perfume in the liquid state into the particles (pAS) of alkali-water-soluble polymer (AS) by bringing said perfume into contact, optionally using a transfer solvent, with said alkali-water-soluble polymer (AS) which is in the form of a latex (LAS) of particles (pAS) having on their surface at least an emulsifying agent, at a rate of at least 0.1%, preferably of the order of 0.1 to 15% of the weight of dry polymer.

16) System according to claim 15), characterized in that the introduction of the perfume is carried out jointly with that of an additional quantity of emulsifying agent representing of the order of 0.1 to 2%, preferably order of 0.1 to 0.2% of the weight of perfume used. 19

17) System according to claim 15) or 16), characterized in that the introduction of the perfume by contacting with the latex (LAS) is carried out with stirring at a temperature of 20 to 50 ° C for 1 to 24 hours .

18) System according to any one of claims 1) to 12), characterized in that it is in the form of dry solid granules (G), dispersible in water.

19) System according to claim 18), characterized in that said granules (G) comprise particles (pSP) of the system (SP) comprising said perfume encapsulated in the molecular state in said solid alkali-water-soluble polymer (AS), said particles (pSP) being dispersed in and encapsulated by a matrix in at least one dry, solid, water-soluble or water-dispersible organic compound (MO), at least 0.1% by weight of at least one emulsifying agent relative to the weight of alkali polymer -soluble (AS) occurring at the matrix (MO) / particle (pSP) interface of the perfume system (SP).

20) System according to claim 18) or 19), in the form of dry solid granules (G) characterized in that said granules (G) comprise:

21) System according to any one of claims 18) to 20), characterized in that the water-soluble or water-dispersible organic compound (MO) is chosen from:

- polyelectrolytes (PE) in acid form, belonging to the family of weak polyacids

- water-soluble or water-dispersible oses, osides or polyholosides (O)

- amino acids or water-soluble or water-dispersible amino acid (AA) salts

- or their mixtures. 20

22) System according to claim 21), characterized in that the polypeptides (PP) are chosen from

- synthetic homopolymers or copolymers derived from the polycondensation of amino acids or amino acid precursors, preferably aspartic and / or glutamic acid or their precursors, and hydrolysis

- proteins of plant origin, in particular soy or wheat, preferably hydrolyzed with a degree of hydrolysis less than or equal to 40%

- proteins of animal origin, especially those from milk.

23) System according to claim 22), characterized in that the polyelectrolytes

(PE) are chosen from weak polyacids with a molecular weight by weight of less than 20,000 g / mole, preferably between 1,000 and 5,000 g / mole.

24) System according to any one of claims 19) to 23), characterized in that when the organic compound (MO) is a polypeptide (PP) or an amino acid (AA), the emulsifying agent at the matrix interface (MO) / particles (pSP) is chosen from anionic or amphoteric emulsifiers, when the organic compound (MO) is a polyelectrolyte (PE), said emulsifying agent is chosen from nonionic or amphoteric emulsifiers, when the organic compound ( MO) is a dare, oside or polyholoside (O), said emulsifying agent is chosen from anionic emulsifiers.

25) System according to any one of claims 19) to 24), characterized in that the granules (G) are capable of being obtained by

- Addition to the latex (LSP) defined in any one of claims 13) to 17), of at least one organic compound (MO) and optionally of a dispersing agent

- then elimination of the water / drying of the aqueous dispersion obtained.

26) System according to claim 25), characterized in that the quantity of dispersing agent is of the order of 0.02 to 20% by weight relative to the weight of dry alkaline water-soluble polymer (AS).

27) System according to claim 25) or 26), characterized in that the drying of the dispersion is carried out by lyophilization or by atomization.

28) System according to any one of claims 25) to 27), characterized in that anti-caking agents are introduced during the drying step. 21

29) Use in detergent compositions for washing laundry of the system which is the subject of any one of claims 1) to 28), as a perfuming agent for textile fibers and detergent compositions themselves.

30) Detergent compositions for washing clothes comprising the system which is the subject of any one of claims 1) to 28).

31) Use according to claim 29) or detergent compositions according to claim 30), characterized in that the perfuming system is used at a rate of approximately 0.01 to 0.5%, preferably from 0.05 to 0 , 2% by weight, expressed in quantity of perfume relative to the detergent composition.