EP1053293B1 - System granulates comprising a hydrophobic organic active substance encapsulated in an alkali-water soluble solid organic polymer - Google Patents

Abstract

The invention concerns solid granulates of a system comprising at least a hydrophobic organic active substance (for example an active detergent substance) encapsulated in solid particles of an alkali-water soluble organic polymer derived by emulsion polymerisation, said particles being dispersed in and encapsulated by a matrix in a water soluble or water dispersible dry organic compound. The invention also concerns the use of said granulates in detergent compositions, in particular for cleaning hard surfaces or for washing clothes and the detergent compositions.

Description

The present invention relates to dry solid granules of a system comprising particles of at least one hydrophobic organic active material (for example example of detergency active ingredient) encapsulated in solid particles of a alkali-water-soluble organic polymer obtained by emulsion polymerization, said particles being dispersed in and encapsulated by a matrix into a compound dry organic water-soluble or water-dispersible; it also relates to a process for preparation of said granules, as well as the use of said granules as an additive, in particular as a detergency additive, in compositions intended for a medium alkaline aqueous or capable of forming with water an alkaline aqueous medium, in particular in detergent compositions; the invention also relates to the compositions detergents comprising said additive.

"Active detergency material" means any active material capable of to be present in a detergent composition.

Active ingredients, such as biocides, bleach activators, optical brighteners, anti-UV agents, antioxidants, catalysts bleaching ..., may be present and cause problems, either because of their condition physical (liquid to be adsorbed on a support, in the case of powdered detergents) or stability or aggressiveness towards other additives of the formulation in which they are content.

The Applicant has found an encapsulation system for active ingredients hydrophobic organic, in particular hydrophobic active detergents, allowing the active ingredient to be released only essentially in an alkaline medium, by example while washing the laundry.

A first object of the invention consists of dry solid granules (G), dispersible in water, of a system (S) comprising particles (pS), said particles (pS) comprising at least one hydrophobic organic active material (MA) encapsulated in solid particles (pAS) of an alkali-water-soluble organic polymer (AS) obtained by emulsion polymerization of at least one monomer anionic ethylenically unsaturated, radically polymerizable and at least one free radical polymerizable ethylenically unsaturated comonomer, the amount of said anionic monomer (s) representing at least 10%. of preferably at least 20%. especially from 25 to 60% by weight of the amount total of monomers. said particles (pS) being dispersed in and encapsulated by a matrix in au minus a dry, water-soluble or water-dispersible (MO) solid organic compound, at least 0.1% by weight of at least one emulsifying agent relative to the weight of copolymer alkali-water-soluble (AS) occurring at the matrix (MO) / particle (pS) interface of system (S).

All active materials, whether solid, liquid (as such or in solution in a solvent) are suitable for the invention, insofar as they are not miscible or are only very slightly miscible in water.

By slightly miscible is meant active materials whose solubility in water at pH 7 does not exceed 20% by weight, preferably not 10% by weight.

Subsequently, the term active material is understood to be a pure active material as it is. or in a solvent, either a mixture of active ingredients as such or in a solvent.

As examples of active ingredients (MA), mention may be made of active ingredients hydrophobic detergents, such as, for example, bleaching catalysts, biocidal agents, bleach activators, anti-UV agents, brighteners optical, antioxidant agents.

As examples of biocidal agents, mention may be made of bactericides (triclosan, etc.), fungicides.

As examples of bleach activators, we can mention those generating in the detergent medium a carboxylic peroxyacid, such as tetraacetylethylenediamine, tetraacetyl methylenediamine ....

As examples of optical brighteners, mention may be made of stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanines, thiophene

As examples of anti-UV agent or antioxidant agent, mention may be made of vanillin and its derivatives.

As examples of bleaching catalysts, mention may be made of derivatives of manganese or other metals, such as those described in US-A-5,246,621, US-A-5,244 594, US-A-5 194 416, US-A- 5 114 606, EP-A-549 271, EP-A-549 272, EP-A-544 440, EP-A-544 490, US-A-4 430 243, US-A-5 114 611, US-A-4 728 455, US-A-5 284 944, US-A-5 246,612 ...

The amount of active material (AM) that may be present in said particles (pS) of the system (S), can range from 20 to 70. preferably from 40 to 60 parts by weight of active ingredient (MA) per 100 parts by weight of alkali-water-soluble polymer (AS).

The term “alkali-water-soluble” (AS) polymer is understood to mean a polymer capable of dissolve or disperse in an aqueous medium with a pH above 7, preferably with a pH of at least 9.5 at a temperature of the order of 20 to 90 ° C. This one is not water soluble at a pH below 7.

Said alkali-water-soluble polymers (AS) are derived from at least one monomer anionic ethylenically unsaturated, radically polymerizable and at least one nonionic ethylenically unsaturated comonomer that can be polymerized by the radical route.

• les acides carboxyliques α-β éthyléniquement insaturés, comme les acides acrylique, méthacrylique, maleique, itaconique ...
• les monomères sulfonés α-β éthyléniquement insaturés, comme le vinylbenzène sulfonate ...

As examples of anionic monomers, there may be mentioned:

• ethylenically unsaturated α-β carboxylic acids, such as acrylic, methacrylic, maleic, itaconic acids, etc.
• ethylenically unsaturated α-β sulfonated monomers, such as vinylbenzene sulfonate ...

The level of anionic monomer is of course a function of its hydrophilicity.

Preferably, said anionic monomers are monomers carboxylic.

• les monomères vinylaromatiques : styrène, vinyltoluène ...
• les alkylesters d'acides α-β éthyléniquement insaturés : acrylates et méthacrylates de méthyle, éthyle ...
• les esters de vinyle ou d'allyle d'acides carboxyliques saturés : acétates, propionates ...
• les halogénures de vinyle ou de vinylidéne : chlorures ...
• les diènes aliphatiques conjugués : butadiène ...
• les nitriles α-β éthyléniquement insaturés : acrylonitrile ...
• les hydroxyalkylesters d'acides α-β éthyléniquement insaturés : acrylates et
• méthacrylates d'hydroxyéthyle, d'hydroxypropyle ...
• les amides d'acides α-β éthyléniquement insaturés : acrylamide, méthacrylamide ...

As examples of nonionic monomers, there may be mentioned:

• vinyl aromatic monomers: styrene, vinyl toluene ...
• the alkyl esters of ethylenically unsaturated α-β acids: methyl and ethyl acrylates and methacrylates, etc.
• vinyl or allyl esters of saturated carboxylic acids: acetates, propionates ...
• vinyl or vinylidene halides: chlorides ...
• aliphatic conjugated dienes: butadiene ...
• ethylenically unsaturated α-β nitriles: acrylonitrile ...
• hydroxyalkyl esters of α-β ethylenically unsaturated acids: acrylates and
• hydroxyethyl methacrylates, hydroxypropyl methacrylates ...
• amides of α-β ethylenically unsaturated acids: acrylamide, methacrylamide ...

Said alkali-water-soluble polymers (AS) can also be derived from a composition monomer further containing at least one polyfunctional crosslinking comonomer (MR) (containing at least two ethylenic unsaturations) and / or at least one comonomer ethylenically unsaturated nonionic amphiphilic (MG) capable of forming graft copolymers with the other comonomers.

• le glyoxal bis acrylamide
• l'éthylène glycol diacrylate ou diméthacrylate
• le triméthylolpropanetriméthacrylate, le pentaérithritol triacrylate
• les polyallyl éthers d'éthylène glycol, de glycérol, de pentaérithritol, de diéthylèneglycol
• l'acrylate d'allyle
• le divinylbenzène, le trivivylbenzène et les alkyldivinylbenzènes
• le divinyl éther

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, pentaerythritol triacrylate
• polyallyl ethers of ethylene glycol, glycerol, pentaerythritol, diethylene glycol
• allyl acrylate
• divinylbenzene, trivivylbenzene and alkyldivinylbenzenes
• divinyl ether

• R¹ est un atome d'hydrogène ou un radical méthyle
• R² et R³, identiques ou différents, représentent un atome d'hydrogène ou un radical alkyle contenant de 1 à 4 atomes de carbone
• R⁴ est
  • un radical alkyle contenant de 8 à 30 atomes de carbone
  • un radical phényle substitué par un à trois groupements 1-phényléthyle
  • un radical alkylphényle contenant de 8 à 10 atomes de carbone
• n va de 6 à 100 et m de 0 à 50, sous réserve que n soit supérieur ou égal à m et leur somme comprise entre 6 et 100.

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

• R ¹ 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 C ₂₂ H ₄₅ alkyl radical.

• d'une composition monomère constituée d'esters acryliques et/ou méthacryliques et d'au moins 30% d'acide acrylique et/ou méthacrylique
• de ladite composition monomère contenant en outre un comonomère réticulant glyoxal bis acrylamide ou éthylène glycol diméthacrylate
• de ladite composition monomère contenant en outre le comonomére greffant (MG').

As examples of alkali-water-soluble copolymers (AS), mention may be made in particular of derivative 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 further containing the grafting comonomer (MG ').

• de 5 à 90%, de préférence de 40 à 85 % de leur poids de particules (pS) de système (S)
• de 3 à 90%, de préférence de 10 à 60%, tout particulièrement de 15 à 50% de matrice organique hydrosoluble ou hydrodispersable (MO).

For a good implementation of the invention, said granules (G) dispersible in water, comprise:

• from 5 to 90%, preferably from 40 to 85% of their weight of system particles (pS)
• from 3 to 90%, preferably from 10 to 60%, very particularly from 15 to 50% of water-soluble or water-dispersible (MO) organic matrix.

• les polypeptides (PP) d'origine naturelle ou synthétique hydrosolubles ou hydrodispersables
• les polyélectrolytes (PE) sous forme acide, appartenant à la famille des polyacides faibles, ayant en particulier une masse moléculaire inférieure à 20 000 g/mole, de préférence comprise entre 1 000 et 5 000 g/mole
• les oses, osides ou polyholosides hydrosolubles ou hydrodispersables (O)
• les acides aminés ou sels hydrosolubles ou hydrodispersables d'acides aminés (AA)
• les agents tensioactifs (TA) dont le diagramme de phases binaire eau-tensio-actif, comporte une phase isotrope fluide à 25°C jusqu'à une concentration d'au moins 50 % en poids de tensio-actif, suivie d'une phase cristal liquide rigide de type hexagonale ou cubique à des concentrations supérieures, stable au moins jusqu'à 60°C.
• ou leurs mélanges.

Among the water-soluble or water-dispersible organic compounds which can constitute the matrix (MO), mention may be made

• water-soluble or water-dispersible polypeptides (PP) of natural or synthetic origin
• polyelectrolytes (PE) in acid form, belonging to the family of weak polyacids, having in particular a molecular mass of less than 20,000 g / mole, preferably between 1,000 and 5,000 g / mole
• water-soluble or water-dispersible oses, osides or 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 phase Rigid hexagonal or cubic liquid crystal 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 shell, mention may be made of homopolymers or copolymers derived from the polycondensation of amino acids or amino acid precursors, in particular aspartic and glutamic acid or their precursors, and hydrolysis. These polymers can be either homopolymers derived from aspartic acid or glutamic as copolymers derived from aspartic acid and glutamic acid in any proportions, or copolymers derived from aspartic acid and / or glutamic and other amino acids. Among the copolymerizable amino acids, it is possible to quote glycine, alanine, leucine, isoleucine, phenyl alanine, methionine, histidine, proline, lysine, serine, threonine, cysteine ...

Among the polypeptides (PP) of plant origin which can constitute the matrix, may include 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, for information, of proteins from protein seeds, especially those from peas, faba beans, lupins, beans, and lentils; proteins from cereal grains in particular those of wheat, barley, rye, corn, rice, oats, and millet; the proteins from oil seeds including soybeans, peanuts, sunflower, rapeseed, and coconut; protein from the leaves including alfalfa, and nettles; and proteins from plant organs of buried reserves, notably that of potatoes and beets.

Among proteins of animal origin, there may be mentioned, for example, proteins muscles, particularly stroma proteins and gelatin; proteins from milk, especially casein, lactoglobulin: and fish proteins.

The protein is preferably of plant origin, and more particularly comes from soy or wheat.

• un atome d'hydrogène,
• un radical hydrocarboné contenant de 1 à 4 atomes de carbone, méthyle de préférence
• une fonction -COOH
• un radical -R-COOH, où R représente un reste hydrocarboné contenant de 1 à 4 atomes de carbone, de préférence un reste alkylène contenant 1 ou 2 atomes de carbone, méthylène tout particulièrement.

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 and methacrylic acids, maleic, fumaric, itaconic, crotonic.

Also suitable are the copolymers obtained from the monomers corresponding to the above 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. We can also mention the copolymers obtained from alkyl vinyl ether and maleic acid as well as those obtained from vinyl styrene and maleic acid which are in particular described 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 weight 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 that result from condensation, with elimination of water, molecules of oses between them or even molecules of oses with non-carbohydrate molecules. among the osides, the holosides which are formed by the combination of exclusively carbohydrate motifs and more particularly oligoholosides (or oligosaccharides) which contain only a limited number of these units, that is to say a number generally less than or equal to 10. As examples of oligoholosides, one can mention sucrose, lactose, cellobiose, maltose and trehalose.

The water-soluble or water-dispersible polyholosides (or polysaccharides) are strongly depolymerized; they are described for example in the work of P. ARNAUD titled "organic chemistry course". Gaultier-Villars editors. 1987 More specifically. these polyholosides have a molecular weight by weight of less than 20,000 g / mole.

By way of nonlimiting example of highly depolymerized polyholosides, it is possible to cite dextran, starch, xanthan gum and galactomannans such as guar or carob, these polysaccharides preferably having a melting point greater than 100 ° C and a solubility in water between 50 and 500g / l.

Among the amino acids (AA), mention may be made of monocarboxylated or dicarboxylated monoamine 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 arginine, 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 RG LAUGHLIN entitled "The AQUEOUS PHASE BEHAVIOR OF SURFACTANTS "- ACADEMIC PRESS - 1994. Their identification by diffusion of radiation (X and neutrons) is described in 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 ...), 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 amphoteric derivatives of alkyl polyamines such as amphionic XL®, Mirataine H2C-HA® marketed by Rhône Poulenc as well as Ampholac 7T / X ® and Ampholac 7C / X® sold by Berol Nobel.

The granules (G) comprise at least 0.1% by weight relative to the weight of alkali-water-soluble polymer (AS) of at least one emulsifying agent, having the matrix (MO) / particles (pS) interface of system (S).

By way of examples of emulsifying agents, mention may be made of nonionic emulsifying agents. anionic or amphoteric.

• les alcools gras éthoxylés ou éthoxy-propoxylés
• les triglycérides éthoxylés ou éthoxy-propoxylés
• les acides gras éthoxylés ou éthoxy-propoxylés
• les esters de sorbitan éthoxylés ou éthoxy-propoxylés
• les amines grasses éthoxylées ou éthoxy-propoxylées
• les di(phényl-1 éthyl) phénols éthoxylés ou éthoxy-propoxylés
• les tri(phényl-1 éthyl) phénols éthoxylés ou éthoxy-propoxylés
• les alkyls phénols éthoxylés ou éthoxy-propoxylés

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

The number of oxyethylene (OE) and / or oxypropylene (OP) units of these surfactants non-ionic 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.

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

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

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

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

In the present invention, the term ethoxylated triglyceride is intended both products obtained by ethoxidation of a triglyceride by ethylene oxide than those obtained by transesterification of a triglyceride with a polyethylene glycol.

Likewise, the term ethoxylated fatty acid includes both the products obtained ethoxylation of a fatty acid by ethylene oxide than 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 from preferably ethoxylates.

Ethoxylated or ethoxy-propoxylated alkylphenols are generally 1 or 2 groups alkyl, linear or branched, having 4 to 12 carbon atoms. As an example we can cite in particular the octyl, nonyl or dodecyl groups.

As examples of nonionic surfactants from the group of ethoxy alkylphenols or ethoxy-propoxylated, ethoxylated di (phenyl-1 ethyl) phenols and tri (1-ethyl phenyl) ethoxy or ethoxy-propoxylated phenols, mention may be made in particular of di (phenyl-1 ethyl) ethoxylated phenol with 5 OE units, di (1-phenylethyl) ethoxylated phenol with 10 OE units, tri (1-phenylethyl) ethoxylated phenol with 16 OE units, tri (1-phenyl) ethyl) ethoxylated phenol with 20 EO units, tri (1-phenyl ethyt) ethoxylated phenol with 25 EO units, tri (1-phenylethyl) ethoxylated phenol with 40 EO units, tri (1-phenyl) ethyl) ethoxy-propoxylated phenols with 25 units OE + OP, nonylphenol ethoxylated with 2 OE units, ethoxylated nonylphenol with 4 OE units, ethoxylated nonylphenol with 6 OE units, ethoxylated nonylphenol with 9 OE units, ethoxy-propoxylated nonylphenols with 25 OE + OP units, 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 units OE + OP.

Among the anionic emulsifiers, mention may be made of the water-soluble salts of alkylsulphates, of alkylethersulphates, alkylisethionates and alkyltaurates or their salts, alkylcarboxylates, alkylsulfosuccinates or alkyisuccinamates, alkylsarcosinates, alkyl derivatives of protein hydrolysates, 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, alkyldimethylbetaines, alkylamidopropylbétaines, alkylamidopropyldiméthylbétaines, alkyltrimethyl-sulfobetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphodiacetates, alkylampho-propionates. alkylamphodipropionates, alkyisultaines or alkylamidopropyl-hydroxysultaines. the condensation products of fatty acids and protein hydrolysates. drifts amphoteric alkylpolyamines such as Amphionic XL® marketed by Rhône-Poulenc, Ampholac 7T / X® and Ampholac 7C / X® marketed by Berol Nobel, the proteins or protein hydrolysates.

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 is chosen from nonionic or amphoteric emulsifiers. When the compound organic (MO) is a dare, oside or polyholoside (O), said emulsifying agent is chosen among anionic emulsifiers.

Said dry solid granules (G), can be obtained by removing water / drying an aqueous dispersion (D) comprising said system particles (pS) (S) and said water-soluble or water-dispersible organic compound capable of forming the matrix (MO).

For a good implementation of the process, the dry extract rate of the dispersion aqueous (D) comprising the mixture of particles (pS) and organic compound (MO) is of the order of 20 to 70%, preferably of the order of 30 to 62% by weight.

• addition à une dispersion aqueuse (latex) (LS) de particules (pS), d'au moins un composé organique (MO) et éventuellement d'un agent dispersant
• puis élimination de l'eau/séchage de la dispersion aqueuse obtenue.

Said process can be carried out by

• addition to an aqueous dispersion (latex) (LS) of particles (pS), at least one organic compound (MO) and optionally a dispersing agent
• then elimination of the water / drying of the aqueous dispersion obtained.

Said dispersion (latex) (LS) of particles (pS) of system (S) may contain of the order of 10 to 50%, preferably of the order of 20 to 50% of its weight of said particles (pS) of system (S).
The diameter of the particles (pS) of system (S) can be of the order of 20 to 700 nanometers, preferably of the order of 100 to 400 nanometers.

The aqueous dispersion (LS) of system (S) can be prepared by introducing said active material (MA) in said alkali-water-soluble polymer (AS) occurring in the form of a latex (LAS), the introduction of the active material (MA) being able to be carried out either during the actual synthesis of said alkali-water-soluble polymer by polymerization in aqueous emulsion, either after the synthesis of said alkali-water-soluble polymer by polymerization in aqueous emulsion.

Preferably, the introduction of the active material (MA) into the latex of soluble alkali polymer (LAS) is carried out after the emulsion polymerization step aqueous composition of the monomer.

• émulsifiants anioniques comme : les sels d'acides gras ; les alkyisulfates (lauryl sulfate de sodium), alkylsulfonates, alkylarylsulfonates (dodécylbenzène sulfonates de sodium. di-butylnaphtalène sulfonate de sodium) ; alkylsulfosuccinates ou succinamates (dioctylsulfosuccinamate disodique. n-octadécylsulfosuccinamate disodique), alkylphosphates alcalins ; le dodècyldiphénylether disulfonate de sodium ; des sulfonates d'éthers alkylphénolpolyglycoliques ; les sels d'esters d'acides alkylsulfopolycarboxyliques ; les produits de condensation des acides gras avec les acides oxy- et amino-alcanesulfoniques ; les dérivés sulfatés des éthers polyglycoliques ; les esters sulfatés d'acides gras et de polyglycols ; les alcanolamides d'acides gras sulfatés;
• émulsifiants non ioniques comme
  • les alcools gras éthoxylés ou éthoxy-propoxylés
  • les triglycérides éthoxylés ou éthoxy-propoxylés
  • les acides gras éthoxylés ou éthoxy-propoxylés
  • les esters de sorbitan éthoxylés ou éthoxy-propoxylés
  • les amines grasses éthoxylées ou éthoxy-propoxylées
  • les di(phényl-1 éthyl) phénols éthoxylés ou éthoxy-propoxylés
  • les tri(phényl-1 éthyl) phénols éthoxylés ou éthoxy-propoxylés
  • les alkyls phénols éthoxylés ou éthoxy-propoxylés
  • les polyoxydes d'éthylène
  • les alcanolamides d'acides gras

Parmi les émulsifiants amphotères, on peut citer les alkyl-bétaïnes, les alkyldiméthylbétaïnes, les alkylamidopropylbétaines, les alkylamidopropyldiméthylbétaïnes, les alkyltriméthyl-sulfobétaïnes, les dérivés d'imidazoline tels que les alkylamphoacétates, alkylamphodiacétates, alkylampho-propionates, alkylamphodipropionates, les alkylsultaïnes ou les alkylamidopropyl-hydroxysultaïnes, les produits de condensation d'acides gras et d'hydrolysats de protéines, les dérivés amphotères des alkylpolyamines comme l'Amphionic XL® commercialisé par Rhône-Poulenc, Ampholac 7T/X® et Ampholac 7C/X® commercialisés par Berol Nobel, les protéines ou hydrolysats de protéines.
D'une manière préférentielle, ledit émulsifiant est anionique ou non-ionique.The latex particles (pAS) (LAS) have on their surface at least one emulsifying agent, at a rate of at least 0.1%, more generally 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.
As examples of emulsifying agents, mention may be made of:

• anionic emulsifiers such as: fatty acid salts; alkyisulfates (sodium lauryl sulfate), alkylsulfonates, alkylarylsulfonates (sodium dodecylbenzene sulfonates. sodium di-butylnaphthalene sulfonate); alkylsulfosuccinates or succinamates (disodium dioctylsulfosuccinamate. n-octadecylsulfosuccinamate disodium), alkaline alkylphosphates; sodium dodeccyldiphenylether disulfonate; sulfonates of alkylphenolpolyglycolic ethers; ester salts of alkylsulfopolycarboxylic acids; the condensation products of fatty acids with oxy- and amino-alkanesulfonic acids; sulfated derivatives of polyglycolic ethers; sulfated esters of fatty acids and polyglycols; alkanolamides of sulfated fatty acids;
• non-ionic emulsifiers like
  • 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 (1-phenylethyl) phenols
  • ethoxylated or ethoxy-propoxylated tri (1-phenylethyl) phenols
  • ethoxylated or ethoxy-propoxylated alkyl phenols
  • polyethylene oxides
  • fatty acid alkanolamides

Among the amphoteric emulsifiers, mention may be made of alkyl betaines, alkyldimethyl betaines, alkylamidopropyl betaines, alkylamidopropyldimethyl betaines, alkyltrimethyl sulfobetaines, imidazoline derivatives such as alkylamphoacetates, alkylamphodiacetates alkyl propionates, alkyl propionates alkyl propionates, alkyl propionates, alkyl propionates, alkyl propionates, alkyl propionates, alkyl propites) -hydroxysultaines, condensation products of fatty acids and protein hydrolysates, amphoteric derivatives of alkylpolyamines such as Amphionic XL® marketed 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.

• les esters comme l'acétate d'éthyle, le propionate de méthyle, le mélange de glutarate /adipate / succinate de méthyle (solvant "RPDE") ...
• les cétones comme la méthyléthylcétone, la cyclohexanone ...
• les alcools comme le propanol, le pentanol, le cyclohexanol ...
• les hydrocarbures aliphatiques et cycliques comme l'heptane, le décane, le cyclohexane, la décaline ...
• des dérivés aliphatiques chlorés comme le dichlorométhane ...
• des dérivés aromatiques comme le toluène, l'éthylbenzène ...
• des dérivés aromatiques chlorés comme le trichlorobenzène ...
• les dialkylethers

The active ingredient (MA) 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 "transfer" solvent swelling 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 ...
• aliphatic and cyclic 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

It is possible to add, if necessary, to the latex (LAS) of alkali-water-soluble polymer, a additional amount of emulsifier, especially nonionic emulsifier polyoxyalkylenated, 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 the active ingredient (MA) used.

The active material (MA) introduced is brought into contact with the latex (LAS), under stirring at a temperature of 20 to 50 ° C for 1 to 24 hours.

Said "transfer" solvent can optionally be removed by evaporation under empty if the active material (MA) is a solid.

The organic compound (MO) is then added to the latex (LS) of system (S), thus that possibly a dispersing agent.

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 non-ionic, anionic or amphoteric emulsifying agents; examples of such emulsifying agents have already been mentioned above.

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 is chosen from nonionic or amphoteric emulsifiers. When the compound organic (MO) is a dare, oside or polyholoside (O), said emulsifying agent is chosen among anionic emulsifiers.

The operation of removing water / drying the aqueous dispersion of particles (pS) and of organic compound (MO) can be carried out by any means known to the skilled person, in particular by lyophilization (that is say freezing, then sublimation) or preferably by spray drying.
Spray drying can be carried out in any known device, such as an atomization tower associating a spraying carried out by a nozzle or a turbine with a stream of hot air. The conditions of implementation depend on the type of active material, the type of matrix of 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 agitation. to give a pseudo system latex (S).

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

The system (S) forming the subject of the invention can be used as an additive in compositions intended for an alkaline aqueous medium or capable of forming with water an alkaline aqueous medium, in particular as a detergency additive in detergent compositions, preferably in powder form, in particular for cleaning hard surfaces or for washing clothes (industrial or household washing).

In particular, another object of the invention consists in the use in detergent compositions, in particular for cleaning hard surfaces or for washing clothes (industrial or household washing), system granules (S), as an additive of detergency.
In general, said system granules (G) (S) can be used in amounts corresponding to the doses of the encapsulated active ingredient usually used in detergent compositions.

A final object of the invention consists of detergent compositions for the cleaning of hard surfaces or for washing clothes (industrial or household washing), comprising said system granules (G) (S).

The detergent compositions according to the invention comprise at least one agent surfactant, preferably chosen from anionic or nonionic surfactants, in an amount generally of the order of 1 to 70% by weight, preferably from 5 to 60% by weight, more particularly from 8 to 50% by weight.

The detergent compositions which are the subject of the invention can also include common additives, such as builders inorganic or organic, in amounts such as the total amount of detergency builder or of the order of 5 to 80% by weight of said composition, preferably from 8 to 40% by weights, anti-soiling agents, anti-deposition agents, bleaching, fluorescent agents, foam suppressants, softeners, enzymes and other additives such as alcohols, agents buffers, fillers, pigments ...

The following examples are given by way of illustration.

Example 1 Characteristics of encapsulation latex

• starting monomer composition (% by weight)
  • butyl acrylate 10%
  • ethyl acrylate 56.4%
  • methacrylic acid 33.6%
• emulsifiers 0.955% relative to all of the monomers (0.015% of ethoxylated nonylphenol containing 25 EO units on average per mole, under the ammonium salt form + 0.94% sodium tetrapropylbenzene sulfonate)
• dry extract = 38.9%
• particle diameter = about 200 nanometers

A 400 g / l solution of triclosan in RPDE solvent is prepared.
A mixture is prepared by introducing into 20g of the above latex, 0.8ml of RPDE and 2ml of RHODASURF T (non-ionic surfactant of RHONE-POULENC) at 5g / l, mixture which is brought to 50 ° C.
5 ml of the triclosan solution are added dropwise to this mixture, with mechanical stirring.
The medium is left under stirring at 50 ° C for 1 hour, then 1 hour at room temperature.
An encapsulated biocidal system is thus obtained, in the form of a latex.

Example 2

The following dispersion is prepared in a mixer: Composition % in weight encapsulated biocidal system, in the form of a latex, of Example 1 (expressed in aqueous dispersion) 89% Amphionic XL (marketed by RHODIA) 2.1% polyacrylic acid (Mw = 2000) 8.9%

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

Example 3

The following dispersion is prepared in a mixer: Composition % in weight encapsulated biocidal system, in the form of a latex, of Example 1 (expressed in aqueous dispersion) 85.4% FP940 1.4% FP900 13.2%

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

Example 4

The following dispersion is prepared in a mixer: Composition % in weight encapsulated biocidal system, in the form of a latex, of Example 1 in aqueous dispersion) 89% (expressed FP940 * 1.4% FP900 ** 6.6% Sucrose 6.6%

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

Claims (31)

1. Water-dispersible dry solid granules (G) of a system (S) comprising particles (pS),
   said particles (pS) comprising at least one hydrophobic organic active material (AM) encapsulated in solid particles (pAS) of an alkali-water-soluble organic polymer (AS) obtained by emulsion polymerization of at least one ethylenically unsaturated anionic monomer which can undergo radical-mediated polymerization and of at least one ethylenically unsaturated nonionic comonomer which can undergo radical-mediated polymerization, the amount of said anionic monomer(s) representing at least 10%, preferably at least 20%, most particularly from 25% to 60%, by weight of the total amount of monomers,
   said particles (pS) being dispersed in and encapsulated by a matrix made of at least one water-soluble or water-dispersible dry solid organic compound (MO), at least 0.1% by weight of at least one emulsifier relative to the weight of alkali-water-soluble copolymer (AS) being present at the interface: matrix (MO)/particles (pS) of system (S).
2. Granules according to Claim 1, characterized in that the active material (AM) is chosen from detergent active materials.
3. Granules according to Claim 1 or 2, characterized in that the active material (AM) is chosen from bleaching catalysts, biocides, bleaching activators, anti-UV agents, optical brighteners and antioxidants.
4. Granules according to any one of Claims 1 to 3, characterized in that the amount of active material (AM) ranges from 20 to 70 and preferably from 40 to 60 parts by weight of active material per 100 parts by weight of alkali-water-soluble polymer (AS).
5. Granules according to any one of Claims 1 to 4, characterized in that the alkali-water-soluble polymer (AS) is capable of dissolving or dispersing in an aqueous medium with a pH of greater than 7, preferably with a pH of at least 9.5 at a temperature from about 20°C to 90°C.
6. Granules according to any one of Claims 1 to 5, characterized in that the anionic monomer is chosen from α,β-ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid or itaconic acid, and α,β-ethylenically unsaturated sulphone-containing monomers, such as vinylbenzene sulphonate.
7. Granules according to any one of Claims 1 to 6, characterized in that the nonionic monomer is chosen from:

   vinylaromatic monomers

   alkyl esters of α,β-ethylenically unsaturated acids

   vinyl or allyl esters of saturated carboxylic acids

   vinyl or vinylidene halides

   conjugated aliphatic dienes

   α,β-ethylenically unsaturated nitriles

   hydroxyalkyl esters of α,β-ethylenically unsaturated acids

   α,β-ethylenically unsaturated acid amides
8. Granules according to any one of Claims 1 to 7, characterized in that the alkali-water-soluble polymers (AS) are derived from a monomer composition also containing at least one polyfunctional crosslinking comonomer (MR) and/or at least one ethylenically unsaturated nonionic amphiphilic comonomer (MG) capable of forming grafted copolymers with the other comonomers.
9. Granules according to Claim 8, characterized in that the polyfunctional crosslinking comonomer(s) (MR) represent(s) from about 0.01% to 1%, preferably from 0.01% to 0.5%, of all of the monomers in the monomer composition.
10. Granules according to Claim 8, characterized in that the grafting nonionic amphiphilic comonomer(s) (MG) represent(s) up to 20% of all of the monomers.
11. Granules according to Claim 8 or 10, characterized in that the grafting nonionic amphiphilic comonomer (MG) has the formula CH₂=C(R¹)-C(O)-O-[CH₂-CH(R²)O]_m-[CH(R³)-CH₂O]_n-R⁴ in which

    R¹ is a hydrogen atom or a methyl radical

    R² and R³, which may be identical or different, represent a hydrogen atom or an alkyl radical containing from 1 to 4 carbon atoms

    R⁴ is

    an alkyl radical containing from 8 to 30 carbon atoms

    a phenyl radical substituted with 1 to 3 1-phenylethyl groups

    an alkylphenyl radical containing from 8 to 10 carbon atoms

    n ranges from 6 to 100 and m ranges from 0 to 50, with the proviso that n is greater than or equal to m and their sum is between 6 and 100.
12. Granules according to any one of Claims 1 to 11, characterized in that the alkali-water-soluble polymer (AS) is chosen from those derived

    from a monomer composition consisting of acrylic and/or methacrylic esters and of at least 30% acrylic and/or methacrylic acid

    from said monomer composition also containing a glyoxalbisacrylamide or ethylene glycol dimethacrylate crosslinking comonomer

    from said monomer composition also containing the grafting comonomer of formula CH₂=C(R¹)-C(O)-O-[CH₂-CH(R²)O]_m-[CH(R³)-CH₂O]_n-R⁴ in which
    R¹ is a methyl radical, R² is a hydrogen atom, m is equal to 25, n is equal to zero and R⁴ is a C₂₂H₄₅ alkyl radical.
13. Granules according to any one of Claims 1 to 12, characterized in that the water-soluble or water-dispersible organic compound (MO) is chosen from:

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

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

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

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

    surfactants (TA) whose water-surfactant binary phase diagram comprises an isotropic phase which is fluid 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, which is stable at least up to 60°C,

    or mixtures thereof.
14. Granules according to Claim 13, 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 acid and/or glutamic acid or precursors thereof, and hydrolysis

    proteins of plant origin, in particular from soya or from wheat, which are preferably hydrolysed with a degree of hydrolysis of less than or equal to 40%

    proteins of animal origin, in particular those originating from milk.
15. Granules according to Claim 13, characterized in that the polyelectrolytes (PE) are chosen from weak polyacids with a weight-average molecular mass of less than 20,000 g/mol, preferably between 1000 and 5000 g/mol.
16. Granules according to any one of Claims 1 to 15, characterized in that when the organic compound (MO) is a polypeptide (PP) or an amino acid (AA), the emulsifier at the matrix (MO)/particles (pS) interface is chosen from anionic and amphoteric emulsifiers, when the organic compound (MO) is a polyelectrolyte (PE), said emulsifier is chosen from nonionic and amphoteric emulsifiers, when the organic compound (MO) is an ose, oside or polyholoside (O), said emulsifier is chosen from anionic emulsifiers.
17. Granules according to any one of Claims 1 to 16, characterized in that they comprise:

    from 5% to 90%, preferably from 40% to 85%, of their weight of particles (pS) of system (S)

    from 3% to 90%, preferably from 10% to 60% and most particularly from 15% to 50%, of their weight of water-soluble or water-dispersible organic matrix (MO).
18. Process for preparing the granules forming the subject of any one of Claims 1 to 17, by elimination of water/drying of an aqueous dispersion (D) comprising said particles (pS) of system (S) and said water-soluble or water-dispersible organic compound capable of forming the matrix (MO).
19. Process according to Claim 18, characterized in that the dispersion (D) is obtained by adding at least one organic compound (MO) and optionally one dispersant to an aqueous dispersion (LS) of particles (pS).
20. Process according to Claim 18 or 19, characterized in that the dispersion (D) comprises from 5% to 90%, preferably from 40% to 85%, by dry weight of particles (pS) of system (S) and from 3% to 90%, preferably from 10% to 60% and most particularly from 15% to 50%, by dry weight of water-soluble or water-dispersible organic matrix (MO).
21. Process according to any one of Claims 18 to 20, characterized in that said dispersion (D) has a solids content of from 20% to 70% and preferably from 30% to 62% by weight.
22. Process according to any one of Claims 19 to 21, characterized in that the dispersion (LS) contains from about 10% to 50%, preferably from about 20% to 50%, of its weight of particles (pS) with a diameter of about 20 nanometres to 700 nanometres, preferably of about 100 nanometres to 400 nanometres.
23. Process according to any one of Claims 19 to 22, characterized in that the dispersion (LS) can be obtained by introducing said active material (AM) into particles (pAS) of alkali-water-soluble polymer (AS) by placing said active material in 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) containing at their surface at least one emulsifier, in a content of at least 0.1%, preferably from about 0.1% to 15%, of the weight of dry polymer.
24. Process according to Claim 23, characterized in that the introduction of said active material is carried out together with that of an additional amount of emulsifier representing from about 0.1% to 2% and preferably from about 0.1% to 0.2% of the weight of active material used.
25. Process according to Claim 23 or 24, characterized in that the introduction of said active material by placing in contact with the latex (LAS) is carried out with stirring at a temperature from 20°C to 50°C for 1 to 24 hours.
26. Process according to Claim 18, characterized in that the amount of optional dispersant in the dispersion (D) is from about 0.02% to 20% by weight relative to the weight of dry alkali-water-soluble polymer (AS).
27. Process according to any one of Claims 18 to 26, characterized in that the drying of the dispersion (D) is carried out by lyophilization or by spraying.
28. Process according to any one of Claims 18 to 27, characterized in that anticaking agents are introduced during the drying step.
29. Use of the granules forming the subject of any one of Claims 1 to 17 or which can be obtained according to the process forming the subject of any one of Claims 18 to 28, in detergent compositions, in particular for cleaning hard surfaces or for washing laundry.
30. Detergent compositions, in particular for cleaning hard surfaces or for washing laundry, comprising the granules forming the subject of any one of Claims 1 to 17 or which can be obtained according to the process forming the subject of any one of Claims 18 to 28.
31. Use according to Claim 29 or detergent compositions according to Claim 30, characterized in that the system is used in an amount corresponding to the usual working doses, in the detergent compositions, of the active material it encapsulates.