Particles with a polymeric shell and receive

 

(57) Abstract:

Describes the composition is in the form of particles containing particles with hydrophilic core within a shell containing a membrane, comprising the product of the Association (a) the product of interfacial condensation formed by the reaction between the mainly soluble in oil first reagent interfacial condensation, selected from isocyanate, epoxy and dicarboxylic acids (or higher digisat) or its derivative, which is or halogenerator, or anhydride having at least two first condensing group, and mainly water-soluble second reagent interfacial condensation, selected from a diamine (or tertiary diamines) or polyol, soluble in water, having at least two second condensation groups, and (b) oil-soluble or swelling in oil amphipatic polymer stabilizer, which will focus on the interface between oil and water and which has a repeating hydrophobic group and a repeating hydrophilic groups that are associated with the second condensation groups. Also described is a method of obtaining particles with hydrophilic core inside the shell. Technical resulte relates to condensation polymers and their receipt, in particular membranes, especially the walls of the capsules formed from such polymers. In particular, the present invention relates to the production of particles having a core of substance core encapsulated in a polymer shell, including the receipt of such particles in the form of a basically stable dispersion in the liquid.

For the formation of capsules in the form of a nucleus with a membrane known various methods. One method includes the coacervation of the polymer around the core. Methods of education coacervation coating from a solution of the polymer around the water engine, suitable for the manufacturer of the microcapsules, which can be introduced into the concentrate liquid detergent described, for example, in EP 356239 and WO 92/20771. According to this method, it is difficult to obtain a product in which the enzyme is satisfactorily retained in the particles while in the concentrate, but reliably removed from the particles by dissolution of the concentrate in the wash water.

Another known method of producing a shell of the capsules in the form of a nucleus with a membrane is an interphase polymerization, in which one or more monomers polymerized at the interface between the dispersed phase and a homogeneous phase with the formation of a shell around the dispersed phase. One of aabihirisukyby at the interface between the oil phase and water phase as a result of interaction of water-soluble reagent IFC (in aqueous phase) and oil-soluble reagent IFC (oil phase).

IFC polymerization was used to encapsulate hydrophobic or oil engine by the formation of a dispersion of oil-in-water, and calling IFC polymerization around each dispersed oil droplets. Techniques have been developed for this reaction, which was allowed acceptable satisfactory encapsulation. However, these methods are useless when the core material is an aqueous or hydrophilic and need, on the contrary, to cause the CRC polymerization in dispersion of water-in-oil, i.e., in a dispersion in which water or a hydrophilic substance core is dispersed in a homogeneous oil phase.

Although some patent examples, for example in JAPANESE-AND-63-137996, I believe that the way water-in-oil is quite manageable, we found that in practice it is difficult to obtain satisfactory results, using environmentally friendly materials. For example, there is a risk that a significant amount of product can be solid or not encapsulated, and may have application in this way halogensubstituted hydrocarbon. Maybe it will give good performance for IFC polymerization, but now it is considered environmentally undesirable. This method can be in osobennosti product, inside which made virtually all of the substance of the nucleus and particles substantially stably dispersed in the liquid.

You would think that the use of the emulsifier of water-in-oil can accelerate the formation of fine dispersion, i.e. the emulsion. However, we found that if we use conventional emulsifier of water-in-oil, such as Span 85 (trade mark), it is difficult to obtain a satisfactory dispersion of the encapsulated particles in the oil, particularly when the volume of the dispersed phase is moderately large. The increase or the efficiency of the emulsification of water-in-oil conventional type does not improve the result. On the contrary, it seems, leads to the reduction of the satisfactory formation of the shell and increase the risk of heterogeneity in the shell.

In EP-A-0671206 described IFC how to obtain shell microcapsules with a size of less than 1 m, which is characterized by the use of blockcopolymer as a protective colloid. A mixture of one IFC reagents with substance core is dispersed in water-immiscible liquid and added dropwise there another IFC reagent. In each of the examples of the material of the core is a non-aqueous core, based on the glycol, and the stabilizer Yl acrylate together with the grafted polymer of methyl methacrylate, tamilmasala and adduct of ethylene oxide with hydroxyethyl methacrylate. A similar system with a stabilizer to some extent similar to the emulsifier of water-in-oil because of its pronounced physically separated hydrophilic units (i.e., the hydrophilic block and the hydrophobic chains (i.e., the hydrophobic block). These systems produce unsatisfactory results when used according to the method described in EP 671206.

Accordingly, there remains a need in the IFC products and methods that can be implemented in the usual way using conventional and environmentally acceptable materials with obtaining satisfactory walls of the structure and product with satisfactory and certain in advance the size of the particles.

In accordance with the present invention, applicant provides a composition in the form of particles containing particles with hydrophilic core within a shell containing a membrane, comprising the product of the Association (a) the IFC product of condensation formed during the interaction of the first IFC reactant having at least two first condensing group, and the second IFC reactant having at least two second condensation groups, and (b) ampip is Oh and having recurring hydrophobic group and a repeating reactive hydrophilic groups, associated with the second condensation groups.

This Association may include the condensation reaction between the reactive hydrophilic groups and the second condensation groups. For example, when preferably reactive hydrophilic group include a carboxyl group, and the second condensation groups are amino groups, this Association may include the formation of amide condensation connection between the stabilizer and the IFC product of condensation. I believe that this happens in particular when the stabilizer is a copolymer ethyleneamines anhydride carboxylic acids, such as maleic anhydride.

However, this Association may be any other type of Association, leading to attraction between the stabilizer and the second reagent (and thus also the product of IFC-condensing). Association often involves ion Association, for example, by the formation of ionic salts between carboxyl groups and forming with them salt. For example, a polymeric stabilizer may have a carboxyl group and a salt-forming amine IFC reactant then forms them with salt. Also, is the competition between the carboxyl groups and other acidic sites in the reaction mixture.

Apparently, the best results are achieved when the polymer stabilizer is a copolymer ethyleneamines polycarboxylic acids (including dicarboxylic acid and anhydrides) such as maleic acid or maleic anhydride, and the second reagent is polyamines (including diamines, triamine and tetraamine), preferably having from two to six carbon atoms between the amino groups. It is likely that such a location adjacent carboxyl groups and a diamine or higher groups are particularly conducive to the formation of a strong Association between the amine and the stabilizer is possible due to the formation of internal cyclic salt between adjacent carboxyl groups and diaminopropane.

The present invention also provides various methods of obtaining particles with hydrophilic core within a shell formed of a substantially oil-soluble first IFC reactant having at least two groups of the first condensation, substantially water-soluble second the IFC reactant having at least two groups of the second condensation. All of these methods include the formation of emulsions water-in-oil water composition I is soluble or swellable in oil polymer stabilizer, mixing this dispersion with the first IFC reagent and carrying out the reaction between the first and second IFC reagents, which formed the shell.

In one of the preferred ways of polymeric stabilizer is amphipatic polymeric stabilizer with repetitive hydrophobic groups and repetitive reactive hydrophilic groups, and reactive hydrophilic group is associated (for example, by condensation or salt) groups of the second condensing the second IFC reactant to mix with the first IFC reagent.

In another preferred method, the polymer stabilizer is a group of the carboxylic acid in the side frame and the second IFC reactant is an amine and a dispersion of a water-in-oil homogenized prior to mixing with the first IFC reagent. This homogenization is useful not only because it formed the final desired particle size, but also because it allows for the emergence of some form of Association between the carboxyl and amino groups. For example, the homogenization is conducted under stirring, at least for one minute, usually from three to ten minutes or longer. Temperature can b the present invention the polymeric stabilizer is a statistical copolymer, formed by copolymerization of a mixture Ethylenediamine hydrophilic monomers and Ethylenediamine hydrophobic monomers.

In the following preferred method of the present invention, mixing the dispersion with the first IFC reagent is carried out by mixing the dispersion and the first IFC reactant under conditions in which the weight ratio of the variance and the second reagent remains largely constant during the mixing process.

In particular, this process is preferably carried out mass-production method, mixing the portion containing the dispersion, with the portion containing the first reagent, since using this it is easy to control the ratio of the variance and the first reagent in order to maintain its basically constant, or in any other desired proportion.

In the following preferred method of the present invention the final dispersion of particles in water-immiscible liquid is treated by adding to the dispersion, miscible with water and organic liquid (preferably surfactant) and fending off the water-immiscible liquid, thus obtaining a dispersion of particles in miscible with water and organic liquids. When jeunehomme for to make it substantially anhydrous.

The methods of the present invention and particularly those that use a polymer stabilizer, which is in any way associated with the second reagent to the reaction between the first and second reagents, allows to obtain more uniform particles in a satisfactory concentrations and, in particular, they allow to obtain a substantially stable dispersion of small encapsulated particles (at least 90 wt.% less than 30 meters). They are able to favorably influence the receipt of IFC shell. For example, the number of one of the two, or both of the reactants required to produce the shell of certain properties, can be reduced by organizing polymeric stabilizer and its quantity. In addition, particles obtained by using the stabilizer, it is easier stably dispersing in a liquid (for example, in the concentrate liquid detergent) than in the case when the polymer stabilizer is not used.

The methods of the present invention may include subsequent stage distillation, most or all of the water from the aqueous composition of the core as long as the particles will not contain largely by distillation, because some organic liquid usually is distilled over with the water.

The following aspect of the invention can be obtained other products containing the membrane. So, between the water phase and oil phase can be formed by the boundary, for example a flat surface section to obtain a flat film, or a cylindrical surface section for receiving the tube, and the membrane formed on the boundary may be a product product Association IFC condensation and amphipatic polymeric stabilizer. Although the present invention can be used to obtain this way of films, for convenience, the following description is in the context of obtaining particles.

The present invention can be used to obtain a relatively large particles, such as at least 90 wt.% more than 50 m and usually more than 100 m, and usually 90 wt.% less than 1000 m and often less than 500 meters These beads can be distinguished from the dispersion in the form of dry pellets.

Preferably the present invention is used to produce smaller particles, where, typically, 90 wt.% particles is in the dry state less than 30 meters Invention not only allows you to get to such colocate these particles largely in individual state and largely stable dispergirovannykh in not miscible with water liquid.

Referring to the particle size in the dry state, we mean particle size, measured after dispersion surpassed to provide substantially anhydrous core, the total content of water in which, for example, (based on the total weight of the particles) is less than 20% and usually less than 10 wt.%. However, if in any particular way there is no possibility to dry the dispersion, then the size in the dry state, in combination with the assessment of the extent to which shrank these particles, if they have dried up.

Saying that particles are largely individual and stably dispersed in water-immiscible fluid, we mean that the total number of particles (including agglomerated particles) greater than 30 m, is less than 10 wt.%, and that preferably does not particles, but if it still has a place, then settled particles can be easily atomized again by gently mixing. Preferably the particle size in the dry state is at least 80% (preferably 90%) by weight, less than 15 m or 20 m and, hence, again, the number of agglomerates larger than 15 m or 20 m should be small. Preferably the size in the dry state is at least to 50% less 1 m, but preferably, at least 50%, and more preferably at least 70% by weight would have a size in the range of 1-5 m

Another way to determine size is the medium size particles (based on the average by weight), preferably less than 20 m and more preferably less than 10 m, often in the range of from 1 to 5 m

First, the particles must be received in the form of a dispersion of water-in-oil-in-water-immiscible liquid. This fluid preferably does not contain halogen-substituted hydrocarbons (such as chloroform) and preferably is a hydrocarbon.

The final dispersion, optionally after distillation to turn the engine largely anhydrous, can be supplied to the user such as, for example, for inclusion in the concentrate of the detergent. However, often prefer to replace is not miscible with water, the liquid in which the resulting dispersion, another organic liquid, which may be another not miscible with water liquid, but which is typically a surfactant, or miscible with water, the liquid, and may contain some water. However, it is often more convenient to notice would then be dispersed in a substantially anhydrous liquid.

Appropriate method of implementation of such fluid replacement is a method such as described in WO 94/25560. This method includes receiving initial IFC dispersion is not miscible with water liquid, optional dehydration of dispersed particles by azeotropic distillation of the dispersion, and adding to this dispersion liquid, selected from is not miscible with water liquids and preferably surfactants and mixing with the water of liquids, which is less volatile than the first is not miscible with water, the liquid and the Stripping of the first dispersion is not miscible with water fluid up until the first number is not miscible with water, the liquid remaining in the dispersion is less than 20 wt.% with respect to the liquid phase of the dispersion.

Despite the fact that the variance is often dehydration (before, during or after addition of surfactants or other liquid), the removal of water is not significant, because often the water can satisfactorily be in equilibrium with homogeneous phase. This discovery is useful for the present invention, but it is also applicable to the processes described in WO 94/25560.

Add the liquid may be miscible with water and Italino it is a surface-active substance, generally, non-ionic surface-active agent, resulting in the fact that the final product is a dispersion of particles in surface-active substance. The number of particles in the surface-active substance or other dispersion is usually more than 5 or 10% of the dry weight and is usually greater than 20% or more. The variance can be either liquid or fusible, i.e., non-aqueous liquid can in the cold to be the wax can be melted to obtain a liquid state. For a complete description of suitable substances and process conditions reference should be made to WO 94/25560.

Thus, the present invention provides a new composition comprising a dispersion in an aqueous liquid (e.g. water surface-active substance) of particles with an aqueous core within a polymeric shell. It can be obtained by any suitable IFC or other forming the shell method, preferably using IFC using a polymer stabilizer, as described here.

The methods of the invention can be obtained a dispersion of particles of substantially non-aqueous liquid or aqueous fluid, with the size in the dry state at least 90 wt.% less than 30 m, in which these particles in mn core, surrounded by a shell formed from a condensation polymer, and the dispersion is stabilized oil-soluble or swellable in oil animationstep polymeric stabilizer. When the liquid is at room temperature is melting the wax and not a true liquid dispersion at room temperature fusible solid substance. The core may include a polymer matrix and typically involves an active ingredient, such as an enzyme.

Obtained in the invention composition can be used in any suitable way. For example, when the active ingredient is a detergent enzyme or other detergent substance dispersion in oil, surface-active substance or other liquid can be atomized in a concentrated liquid detergent, as described in the application submitted at the same time the link PRL03621WO declaring among other things, the priority of the WB 9526706.8 of December 29, 1995.

Conducting initial obtaining particles with a water core, water composition, which will form the substance of the nucleus, is dispersed in not miscible with water non-aqueous liquid. This variance include substantially water-soluble IFC reactant that is not at all ivaldi pH agent), which should be included in the shell or the core particles can be entered before, during or after encapsulation. If desired, substantially water-soluble reagent is mixed with the composition of the aqueous core before it is dispersed in water-immiscible liquid, but if desired, the reagent, and optionally other suitable components (e.g., establishing a pH agent, such as sodium hydroxide) can be mixed with the previously obtained water dispersion of the composition in water-immiscible non-aqueous liquid. In some cases, in aqueous compositions kernel IFC reactant may be water. In some cases, the formation of the shell may be made by two or more consecutive reactions.

Usually prefer a water-soluble reagent was significantly soluble in the oil phase, so that a small part of it dissolved in the oil phase or at least migrated to the interface between oil and water phases. This speeds up the desired Association between the stabilizer and substantially water-soluble reagent.

Polymer stabilizer should be entered in the oil phase before will happen IFC polymerization, but in practice usually predpochitala, although if you want some or all of the stabilizer can be added together with the aqueous composition engine or after it. Typically, the stabilizer is available in the form of a solution of the swollen or dissolved stabilizer in the oil, which is part of the overall water-immiscible liquid.

If oil-soluble IFC reactant largely directionspanel under conditions prevailing during the formation of the initial dispersion, this reagent can also be incorporated into water-immiscible liquid before or at the time of obtaining the aqueous dispersion composition of the nucleus in a water-immiscible liquid. Usually prefer to obtain a water dispersion of water the composition engine water-soluble IFC reactant in a water-immiscible liquid containing amphipatic polymer stabilizer, and then mixed with this dispersion of oil-soluble IFC reactant. Typically, oil-soluble IFC reactant do not add until, until sufficient time (usually at least 2 minutes, for example from 3 to 20 minutes) for the purpose of Association between the stabilizer and other IFC reagent. As a rule, to speed up the Association using homogenization or another way is stijene desired particle size. So, if you require a relatively large particles, can be quite simple mixing, but if you require particles of small size, may require one or more passes through a Silverson homogenizer.

This is followed by a reaction between water-soluble and oil-soluble IFC reagents. Oil-soluble reagent little or insoluble in water. Depending on the combination of reagents that may be relatively spontaneously at a temperature mixing or usual accelerate the reaction by heating the entire dispersion, for example, to a temperature in the range of 30-90oC. it May be desirable to heat or cool the dispersion to a suitable reaction temperature prior to the addition of oil-soluble reagent and/or to heat or cool the reagent (often dissolved in a solvent before adding to the dispersion. Oil-soluble reagent can be added in pure form, but to facilitate mixing of oil-soluble reagent with a pre-formed dispersion of the reagent is preferably added in the form of a solution in a suitable, for example, an organic solvent. This solvent becomes part is not miscible with water, the liquid phase of the dispersion.

To a significant degree be completed fairly quickly, for example, within five minutes after addition of oil-soluble IFC reactant, it is often desirable to continue stirring at a selected temperature reactions from at least ten minutes to an hour or more, usually at least about half an hour, to provide the maximum possible reaction time. After this mixing can be stopped and either use the composition as such or usual to expose her dehydration and preferably replacing the solvent with the General methods described above.

To mention water-soluble IFC reactant, we mean the reagent is soluble in the aqueous compositions of the kernel (or in the water when it is reagent). Referring oil-soluble IFC reactant and oil-soluble amphipathicity polymer stabilizer, we are referring agent or stabilizer, is not miscible soluble in water liquid. Accordingly, water-soluble IFC reactant dispersed in the aqueous phase and oil-soluble IFC reactant and the polymer stabilizer dispersed in water-immiscible liquid with a significant coefficient distribution, usually at least 5 and usually more than 10. For the polymer stabilizer is not trebuetsya in water), instead, it may be in the form of colloidal or other dispersion and, thus, can be described as malonebailey, and not oil-soluble.

Not miscible with water, the fluid may consist of one non-aqueous liquid, or may be a mixture of two or more non-aqueous fluids. It should not be miscible with water, in order to minimize migration of the composition of the aqueous core and a water-soluble IFC reactant in the oil phase. It can be any environmentally acceptable is not miscible with water liquid having a suitable volatility and other properties for the formation of the dispersion and for their eventual removal by distillation (if required). Preferably it is a hydrocarbon, preferably low-boiling and, therefore, volatile aliphatic hydrocarbon series. Typically, this unsaturated hydrocarbon.

The polymeric stabilizer is preferably animationstep, by which we mean that it contains repetitive hydrophilic and hydrophobic monomer units.

The polymer may be a condensation polymer, in this case, it usually is a product of oil-soluble condensation polymer with worky polymer may be polyethylene glycol or other polyhydroxybenzenes, for example, described in the WB-And-2002400, and thus the polymer may be a condensation product of polyethylene glycol with hydroxystearate acid. Preferred condensation polymer already contains a number of amino groups is formed when a water-soluble polymer is polyamines, as, for example, described in EP-A-333501. Thus, the condensation polymer may be a condensation product hydroxystearate acid and polyethylenimine. The copolymers for use in IFC processes described in EP-A-671206, but they are not as useful as ionic polymers, in particular ionic statistical polymers.

Therefore, usually preferred that the polymer was a statistical copolymer of at least one ionic and therefore hydrophilic, Ethylenediamine monomer, with at least one water-insoluble non-ionic and therefore hydrophobic ethyleneamines polymer. Calling polymer statistics, we simply mean that it is obtained by copolymerization of a mixture of monomers.

Amphipatic polymer stabilizer is preferably ion. It can be amphoteric or cationic, but preferably is anionic and takinga water-insoluble non-ionic monomer. The molar amount of the ionic monomer is usually in the range from 1 to 50% (often from 10 to 30%), based on the total molar amount of ion and water-insoluble monomers.

The use of components of dicarboxylic acids in the stabilizer, apparently, as noted above, accelerates the Association between the stabilizer and the IFC product of condensation. To accelerate this Association carboxyl groups are normally in the form of the free acid, in order to facilitate the formation of inner salts. However, in other cases, the appropriate Association, for example, the condensation can be achieved when groups of carboxylic acids are in the form of groups of short-chained alkyl esters Ethylenediamine carboxylic acids, such as C1-C4the lower alkyl(meth)acrylate groups.

In General, suitable stabilizers are additive copolymers containing both hydrophobic and hydrophilic parts in such relation that they are placed at the interface between the oil and water phases. Desirable group of the side frames being in the choice of monomers, but preferably less) groups of the side frame end stabilizer can be achieved by contient distribution To between hexane and deionized water at 20oWith water-insoluble neironnykh monomers should be at least 5 and preferably at least 10. Suitable hydrophobic monomers include the higher alkyl esters , -Ethylenediamine carboxylic acids, such as dodecylamine, dodecylammonium, tridecylamine, tridecylamine, tetradecylammonium, octadecylamine, octadecylammonium, ethyl palefire maleic anhydride, diethylmaleate and other alkyl esters resulting from the reaction of an alcohol having from 4 to 20, preferably from 8 to 20, carbon atoms, with ethyleneamines carboxylic acid, such as acrylic acid, methacrylic acid, fumaric acid, taconova acid and konitova acid. Other suitable hydrophobic monomers include styrene, alkylthiol, such as methylsterol, vinyl esters, including vinyl acetate, vinylchloride, Acrylonitrile, Methacrylonitrile, ethylene, butylene, butadiene and other olefinic and allylic ethers, non-ionic ethoxylated surfactants.

Suitable hydrophilic units include all water-soluble Ethylenediamine monomers, put propanesulfonic acid, taconova acid, maleic acid, fumaric acid; Ethylenediamine Quaternary compounds, such as dimethylaminoethylacrylate or methyl acrylate, quaternion chloride stands, diallyldimethylammoniumchloride, vinyl or arylsulfonate, vinyl or allylamine, hydroxy lower alkyl esters Ethylenediamine acids and other acylaminoalkyl(meth)acrylates and (meth)acrylamide.

In particular, it is desirable to use polycarboxylic acids, especially dicarboxylic acids such as maleic acid (used as either an acid or anhydride) or taconova acid as part or all of the acid components (e.g., at least 20 wt.% acids, often at least 50%).

In addition, you can also enter other Ethylenediamine comonomers in order to change the solubility parameters of stabilizers to accelerate deposition and locate at the interface between the oil and water phase.

Suitable monomers are short-chained alkyl esters Ethylenediamine carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, taconova acid and konitova Ki is acrylat, the acrylate or methacrylate.

The ratio of hydrophobic and hydrophilic monomers may be in the range between 90 weight parts of the hydrophobic monomer and 10 weight parts of a hydrophilic monomer and 20 weight parts of hydrophobic monomer and 80 weight parts of a hydrophilic monomer.

When you enable short-chained esters they replace the hydrophobic monomer in the copolymer and the proportion of short-chained complex ester based on the dry weight does not exceed 50 parts. You can include minor amounts of other non-interfering monomers, such as bifunctional, or other polyfunctional monomers.

The optimal mixture of monomers and, thus, the optimum stabilizer in any given process will depend, among other things, the choice is not miscible with water and liquid substances kernel and IFC reagents and proportions of each of them.

The molecular weight of the stabilizer (determined according to gel chromatography) is usually from more than 2000, and more preferably 10000 to 100000 or 200000.

The selection of a suitable mixture and molecular weight can be done by conducting IFC polymerization in emulsion of water-in-Mac the help of water and oil phases.

The aqueous phase containing water-soluble IFC reactant is placed in a layer in the vessel. Placed on top of the oil phase with a minimum of stirring at the selected reaction temperature, and this oil phase contains the selected number of IFC reagent. It will be found that the quality of a formed at the interface of the film is changed in accordance with the contents of the two phases, for example, from polymeric stabilizer and its quantity. Once found the combination of the phases, which is obtained satisfactory dispersion of the water-in-oil film by the above test, you can predict what will happen in the education of acceptable wall. This way you can choose a combination of substances for use in the second aspect of the present invention.

The test is preferably used for optimization of the stabilizer. Accordingly, as soon as found the monomer concentration and the concentration of the stabilizer, which gives an acceptable film, stabilizer and its quantity can be changed in successful tests and to observe its effect on the quality of the film.

When the stabilizer is replaced or supplemented by a significant number of conventional polimernogo emulsifier of water-in-oil, the quality of the film may essential the Aubin to accelerate the emulsification of the phases and accelerate precipitating polymerization in the oil phase due to the formation of oil-phase hydrophilic micelles, while the stabilizer is able to accelerate the emulsification of the phases and concentrated polymerization at the interface.

The polymerization is preferably carried out mainly in the absence (for example, less than 3%, preferably less than 1% and preferably at zero or near zero) polimernogo emulsifier of water-in-oil or any other substance that prevents satisfactory course of this process.

IFC reagents are chosen so that to obtain the desired condensation polymer. Particularly preferably, the condensate was the polyamide, but other condensates, which can be formed in this invention are polyesters, polyurethanes, polyureas and epoxies. Especially useful polyamide capsules for detergents. When the condensate is a polyamide, it is best to get it to the reaction of the diamine (or higher amine) with a dicarboxylic acid (or higher carboxylic acid), usually in the form of gelegenheid or anhydride. The amine is preferably substantially water-soluble IFC reagent and may be one of various aliphatic polyamines such as Ethylenediamine, hexamine or preferably Diethylenetriamine.

The acid component is preferably oil-soluble IFC reagent and may be in the form of gelegenheid. It can be, for example, adipic, sebacic or fallholiday or acid chloride dodecadienol acid, but preferably it is terephthaloylchloride.

It should be noted that water-soluble reagent may have some solubility in the oil phase, so that it can react with the oil-soluble amphipatic polymeric stabilizer in the oil phase. For example, preferred amine in free base form, which is usually slightly soluble in the oil phase.

When the condensation polymer is a polyester, it can be obtained by the reaction of, for example, between any acid or derivatives of the acids mentioned above as oil-soluble IFC, with a water-soluble polyol such as ethylene glycol, butanediol, polycaprolactones or bisphenol A.

When the condensation polymer is poliuretano can be obtained by the reaction between a suitable hydroxy - or aminoguanidinium selected from any of the above, as water-soluble IFC reactant, and oil-soluble isocyanate reagent, such as tolua the polyurethane can be obtained by using oil-soluble oligomeric isocyanate. He interacts with water at the interface with formation of amino groups, which interact with isocyanate groups in the oil phase, with the formation of the IFC film at the interface.

When the condensation polymer is an epoxy, it can be obtained by the reaction between, for example, Ethylenediamine or other water-soluble amino - or hydroxidealuminum, with epoxy resin, in the form of oil-soluble IFC reactant.

The method of the present invention preferably includes the formation of a dispersion of water-in-oil aqueous phase kernel is not miscible with water liquid containing as a stabilizer polymer, free from the first group of condensation, the interaction of the polymer with polimernym the first reagent, which is significantly soluble in water-immiscible liquid to interact with the polymer and then dispersing the second oil-soluble IFC reactant in dispersion and conducting condensation. This reaction can occur substantially spontaneously when the temperature of the mixing or the usual accelerate the reaction by heating the entire dispersion, for example, to a temperature in the range from 30 - 90oC. will Probably want the reagent and/or to heat or cool the reagent (often dissolved in a solvent before adding to this dispersion. Oil-soluble reagent can be added in pure form, but to facilitate mixing of oil-soluble reagent with a pre-formed dispersion of the reagent is preferably added in the form of a solution in a suitable, for example organic solvent. This solvent will become part of not mixing with the water of the liquid phase dispersion.

Generally, it is desirable to mix the dispersion during the reaction. Although, apparently, the reaction is completed in significantly quite rapidly, for example within five minutes after addition of oil-soluble, the second IFC reactant, it is often desirable to continue stirring at the selected reaction temperature for at least ten minutes to an hour or more, usually about half an hour, in order to give the maximum possibility of occurrence of a complete reaction. After this mixing, you can stop and use the resulting composition itself or the usual to expose her dehydration and preferably replacing the solvent with the General methods described above.

Although this process can be done by adding the second reagent to the dispersion, preferably the process is carried out by Pach who was largely constant during the mixing process, for example, so that it did not change by more than a factor of about 1.5 or 2 during this process. Preferably the process is carried out line by mixing two downloads, one contains the variance, and the other contains a second reagent. Thus, the ratio of the second reactant and the first reactant can be maintained substantially constant during the process and, consequently, it is possible to install more of the same degree of interaction between the second reagent and the groups of the first condensation in the dispersion.

The substance from which the core of the capsules, is usually hydrophilic and is normally introduced into the process in the form of an aqueous composition. It may consist of an aqueous solution or dispersion of the active ingredient, which should be placed in capsules. For example, the material of the core may include any active ingredient, which is mainly distributed in the aqueous phase of this process. Preferably the active ingredient must have a high molecular weight in order to minimize the risk of migration through the shell. For example, it may be in the form of a crystal or complex of a large molecular size. The active ingredient may constitute, for example, with the active ingredient, flavouring or biologically active substance such as an enzyme. Other suitable active ingredients include optical brighteners, fotoatelier, proteins, substrate for the enzyme or the enzyme stabilizer. May be suitable combination of such ingredients, such as enzyme and its stabilizer.

As the active ingredient can be used paints (including various compositions of the dye or pigment) and chemically reactive materials, which require separate storage from other substances to rupture or other release mechanism.

Preferred active ingredients include enzymes. The enzyme can be entered, for example, in the form of a purified enzyme or extract (such as fermentative broth) containing parts of the cells and/or other by-products of the initial receipt of the enzyme. The most suitable enzymes include enzymes such types that are suitable for use in detergents, as well as the types of enzymes used in industrial processes (for example, in krahmalprodukty industry, in the processing of tissue or protein industry).

Relevant in the context of real numbers enzymes (EC), which are here referred to, are in accordance with the Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology, Academic Press Inc., 1992].

Protease (i.e., peptidases, KF 3.4), such as protease,

obtained from animals, plants, or especially from microorganisms (especially bacteria or fungi), and mutants of these proteases obtained by chemical modification or genetic engineering. Suitable commercially available proteases include AlkalaseTM, SavinaseTM, EverlaseTM, DurazymTM, EsperaseTMand FlavourzymeTM(all available from Novo Nordisk A/S, Denmark), MaxataseTM, MaxacalTM, MaxapemTMand ProperaseTM(available from Gist-Brocades), PurafectTMand PurafectTMSUPP (available from Genencor International), as well as OpticleanTMand OptimaseTM(available from Solvay Ensymes).

Lipase (e.g., triacylglycerol lipase, EC 3.1.1.3), such as derived from animals (e.g. mammals, plants, or especially microorganisms (especially bacteria or fungi), and mutants of such lipases obtained by chemical modification or genetic engineering. In this regard included the lipase of the types that are in the literature referred to as "cutinase" (similar to what Paul is Ronski available lipases include LipolaseTMand Lipolase UltraTM(available from Novo Nordisk A/S, Denmark), LipomaxTM, LumafastTMand Ml LipaseTM(available from Genencor International), and Lipase P "Amano" (available from Amano Pharmaceutical Co. Ltd.).

Amylase [for example, -amylase EC 3.2.1.1, -amylase, EC 3.2.1.2, and amyloglucosidase (glucoamylase), EC 3.2.1.3], such as amylase derived from microorganisms (especially bacteria or fungi), and mutants of such amylases obtained by chemical modification or genetic engineering. Acceptable commercially available amylases include TermarnylTMTHAT BANTM, DuramyiTM, FungarnylTMand AMGTM(all available from Novo Nordisk A/S, Denmark) and RapidaseTMand MaxamylTMP (available from Genencor International).

Cellulase (for example, ADO-1,4-glucanase, EC 3.2.1.4), such as cellulase derived from microorganisms (especially bacteria or fungi), and mutants of such cellulases obtained by chemical modification or genetic engineering. Acceptable commercially available cellulase include CelluzymeTM, CelluclastTM, CellusoftTMand DenimaxTM(available from Novo Nordisk A/S, Denmark), and CAS-500(C)TM(available from Kao Corporation).

The oxidoreductase [EC 1, including phenoloxidase, such as laccase (economony under EC 1.11.1.7], such as oxidoreductase, derived from plants or microorganisms (especially bacteria or fungi), as well as mutants such oxidoreductase obtained by chemical modification or genetic engineering. Suitable laccase include a laccase derived from fungal species of genera such as Aspergillus, Neurospora, Podospora, Botrytis, Collybia, Fomes, Lentinus, Pleurotus, Trametes, Polyporus, Rhizoctonia, Coprinus, Psatyre-lla, Myceliophthora, Schytalidium, Phlebia, Coriolus, Pyriculana or Rigidoporus, such as laccase, obtained from Trametes villosa (also known previously, inter alia, as Polyporus pinsitus), or from Myceliophthora thermophilia. Suitable peroxidases include derived from plants peroxidase, such as horseradish peroxidase, or soybean peroxidase, and peroxidase derived from fungal species of genera such as Fusarium, Humicola, Trichoderma, Myrothecium, Verticillium, Arthromyces, Caldariomyces, Ulocladium, Embellizopus or Mucor, or from a bacterial species of genera such as Streptomyces, Streptoverticillium, Bacillus, Rhodobacter, Rhodomonas, Streptococcus, Pseudomonas or Myxococcus. Other sources of potentially useful peroxidases precisley in B. C. Saunders et al, Peroxsidase, London, 1964, S. 41-43. Especially useful peroxidases include obtained from species of Coprinus, such as C. cinerius or C. macrorhizus (as described, for example, W0 92/16634).

Other appropriate in the context of Nerevarine D-glucose to D-fructose (for example, in the production of fruit syrups in the starch-making industry).

As noted above, the core may include an enzyme stabilizer.

The water composition of the core preferably includes an aqueous solution or emulsion of the polymer or polymerized substances capable of forming a polymer matrix. The active ingredient is preferably substantially uniformly distributed in the aqueous composition in the form of dispersion or solution, but may be distributed unevenly.

The polymer can be introduced in the form of an emulsion of water-insoluble polymer, or it may be administered in the form of soluble derivative, which insolubilizing during subsequent dehydration, as, for example, described in EP 356239, or WO 92/20771, or WB 9526668.0. It can be any copolymer of a hydrophobic monomer with an ionic monomer in the form of the free acid or free base, which is injected in the form of soluble salts. For example, it may be a copolymer with aminomalonate in free base form, are introduced in the form of a salt with acetic acid or other salt, which is then sublime, while receiving insoluble copolymer. Another way it can b the market drying. May occur polymerization or crosslinking by any suitable mechanism of the polymerization reaction or crosslinking, for example during subsequent drying.

Potentially soluble polymers that can be included in this method include substances such as polyvinylpyrrolidone, polyacrylic acid (usually in the form of sodium or other salts), polyacrylamide, or calculatively sulphonate polymer. You can use natural or modified natural polymers, such as resin or carbohydrates.

The polymer preferably is a polymer, causing the release of the active ingredient in a joint interaction with water, which penetrates from the flushing water through the shell due to osmosis, expands and stretches the shell, as described in our application submitted at the same time the link PRL03621WO, claiming priority from WB 9526706.8, filed December 29, 1995.

The ratio of IFC reagents and the total weight of the polymer shell can be selected in accordance with desired for the shell properties. Typically, the shell is from 2-50%, often about 10-30% by weight of the total dry weight of the encapsulated substance (i.e., shell and dehydrating IFC reagents are typically in the range from 10:1 to 1: 10. For example, the molar ratio of water-soluble reagent : oil-soluble reagent may range from 10:1 to 1:3, usually from 5:1 to 1:1.

The amount of polymeric stabilizer is typically in the range from 0.1 to 10%, usually about 0.5-3% by weight of stabilizer based on the total weight of the dispersion, in which the formation of particles. Number, based on the dry weight of the particles, as a rule, is in the range from 0.5 to 30%, usually about 3-10% by weight.

The aqueous compositions of the core and a water-soluble IFC reactant is usually at least 5 to 10% by weight, preferably at least 25% by weight water dispersion, but usually not more than 60 or 70%.

The dry weight of the nucleus in the aqueous dispersion is typically at least 2 to 5% by weight and preferably at least 10%. He often does not exceed 40 or 50% by weight.

The release of active ingredient from the core of the particles at any desired site can be accessed through these methods release as the physical destruction under the action of pressure, or by other means or when the expansion of swelling of the material inside the nucleus, which stretches or breaks the shell, thus allowing penetration through the shell.

All new products of the present invention and the products of new methods of the present invention have the advantage to provide education IFC wall, which is more homogeneous and less prone to premature release of substances in the nucleus compared with the case where to get capsules using known methods. In particular, IFC polymer typically is deposited almost exclusively on the boundary around each of the droplets, often forming ionic or covalent associates with the polymer stabilizer at the interface.

Examples of the invention. All parts are by weight.

In the context of the present invention proteolytic activity is expressed in kilo NOVO Protease units (KNPU). Activity was determined relative to the standard enzyme (SAVINASETM), and the definition was based on the absorption of a proteolytic enzyme solution dimethylketene under standard conditions, i.e. at 50oC, pH 8.3, reaction time of 9 minutes, the measurement time of 3 minutes. The brochure further Podrobnosti the th Novo Nordisk A/S, proteolytic activity 44 KNPU/g (777 g) was mixed with 45% solution of polyvinylpyrrolidone K60 (190 g) and added to this mixture, 32,4 g Diethylenetriamine (DETA).

An oil phase was prepared by mixing 221 g 21% amphipatic stabilizer emulsion with 208 g of volatile hydrocarbon solvent, isopar.

To the above oil phase was added an aqueous mixture of the enzyme containing DETA, and homogenized using mixer Silverson high shear forces with the formation of a dispersion of water-in-oil with an average size of droplets of about 3 m During this stage the temperature of the dispersion was maintained below 40oC. After the formation of the emulsion to dilute dispersion/M added an additional 571 g of volatile solvent.

The resulting dispersion was subjected to mechanical stirring and heated to 37oC. was Prepared oil-monomer phase, dissolving 34 g of terephthaloylchloride (TFH) 966 g of volatile solvent. This oil-monomer phase was added to the warm dispersion for 5 minutes to initiate the reaction of formation of the wall. Around small water droplets of the enzyme is formed of polyamide membrane. To complete the polymerization at the interface of the reaction mixture is left peremeci suspension.

Then this suspension dehydration by distillation and subjected to the process of replacing solvent-non-ionic surface-active agent substantially as described in example 1 W0 94/25560, to obtain a substantially stable non-ionic surface-active substance dispersion of particles with an average size of about 3 m Proteolytic activity of this suspension is approximately 40 KNPU/g

The formation of the shell by this method is satisfactory and stable dispersion of monoparticles is formed first, and after replacing the solvent and adding to the concentrate of the detergent, when the stabilizer is any of the following copolymers.

The copolymer of styrene/octadecylsilane/methacrylic acid in a weight ratio of 30/30/40.

Octadecylammonium/methacrylic acid 66/34.

Octadecylammonium/methyl methacrylate/acrylic acid 50/25/25.

Octadecylammonium/methacrylic acid 64/36.

Octadecylammonium/methyl methacrylate/acrylic acid/methacrylic acid 40/50/5/5.

Acrylonitrile/laurelcrest/acrylic acid 25/35/40.

Laurenmarie/styrene/acrylic colorectal/methyl methacrylate/metacresol Aya acid 35/10/45/10.

When we repeat this method using nonionic blockcopolymer, available under the trade name Nosegneg 246, the method was not so satisfactory.

Example 2 (comparative).

Prepared aqueous phase consisting of Savinase concentrate (water protease activity 36 KNPU/g), an aqueous solution of polyvinylpyrrolidone (K60, 90 parts), Diethylenetriamine (13 parts), glacial acetic acid (15 parts) and water (22 parts).

This aqueous phase was added at pH 7 under stirring with a large transverse force to the oil phase, consisting of emulsifier (Span 85; 10 parts), dissolved in a volatile hydrocarbon solvent (280 parts). The resulting dispersion of water-in-oil (1,85:1) diluted more volatile hydrocarbon solvent (240 parts) to 1.0:1.0 V/M

the pH of the aqueous phase increased, adding a concentrated solution of sodium hydroxide (46%;10 parts), and continued grinding at less than 40oC for 2 minutes. This alkaline emulsion was stirred at 20oS, while for 15 minutes was added a solution of reagent oil phase (terephthaloyl chloride; 13 parts) in a volatile hydrocarbon solvent (490 parts).

By the end of this period the reaction mixture more Elki dispersed phase, but there were no walls, and there was only a gel-like polymer attached to the surface, exhibiting negligible formation of capsules.

Example 3 . Getting DETA-substituted stabilizer.

The solution amphipatic polymer M/stabilizer (I) (10 parts) in a hydrocarbon solvent (90 parts) was treated with a single addition of Diethylenetriamine (DETA; 10 parts) at room temperature for 5 minutes with vigorous stirring. After that, between amphipatic polymer and the excess DETA has been some Association (mixture II).

Amphipathicity polymer can be selected from

Octadecylsilane/methyl methacrylate/acrylic acid 50/25/25.

Octadecylsilane/methyl methacrylate/acrylic acid/methacrylic acid 40/50/5/5.

Octadecylsilane/vinyl acetate/methyl methacrylate/methacrylic acid 35/10/45/10.

Example 4. Getting In/M microcapsules with DATA-substituted stabilizer as coreagent.

An aqueous solution of the active ingredient (110 parts) to grind in a mixture of II from Example 3 (110 parts), receiving a variance/M (III) with an average size of water droplets of about 10 microns. Homogenises) in a hydrocarbon solvent (200 parts). This solution was added to the above dispersion/M under stirring for 5 minutes at 25oC. After this learning visible under the microscope clearly showed the presence of discrete capsules, free from aggregates and clods. The average size of the particles with the average particle size of the intermediate emulsion/M (III).

Example 5.

Repeated the process described in Example 4, except that the variance of V/M (III) is brought into contact with a solution of terephthalic chloride using the built-in stationary mixer. This mixing of the two phases was continued for 15 minutes, while stirring in a proportional mixer lasted only a few seconds. The flow from the mixer collected in the receiving vessel without further mechanical agitation.

Thus obtained capsules on all aspects were identical capsules of Example 4, except that the experiments demonstrate the strength of membrane films showed that the method of mixing leads on average to a more durable membrane than the batch mixing.

Example 6.

This example presents two different ways of encapsulating the enzyme, where Fe is their ingredients, the number of which is specified in grams. The polymer is a copolymer of 75 weight. % acrylamide and 25% acrylic acid, in the form of sodium salts medium (for example, 150000) molecular weight. DETA is Diethylenetriamine. The stabilizer is a copolymer of styrene, sterilisability and acrylic acid. Isopar is a trading name of volatile hydrocarbons. TFH is terephthaloylchloride (see tab.1).

The capsules obtained by dissolving the stabilizer in the first portion of Isopar and subsequent emulsification of DEATH metal in this Isopar using within 2 minutes of homogenization using a Silverson homogenizer (trade name) at full speed with cooling in an ice bath for 2 minutes.

Separately concentrate enzyme, borax, polymer and sodium sulfate (if any) prepared in aqueous phase enzyme. In the process, And the solution seemed clear, and in the process he seemed to be turbid as a result of precipitation of the enzyme.

The aqueous phase enzyme slowly added to the oil phase containing DETA, stabilizer and Isopar, and the addition was emulsified using a Silverson for 10 minutes. Then added the second portion of Isopar, and emulsification with espore 20oC in a water bath.

Accordingly, in this process of DEATH metal was subjected to emulsification in the presence of the stabilizer, at least within 14 minutes.

The solution TFH was heated to 50oAnd quickly added with vigorous stirring. The product was stirred for at least 30 minutes, while the temperature was maintained at 20oC. Received a suspension of capsules in Isopar.

Optionally, you can add a nonionic surfactant (Dobanol 25-7) and to drive away after that, Isopar, receiving a variance in the surface-active substance. Alternative you can use the dispersion in Isopar.

The storage stability of the enzyme encapsulated protease a and b and the liquid lipase in the presence of capsules protease was determined in a commercially available U.S. liquid detergent (WISK Free Clear), the pH is set at 10,1.

The compositions.

I: 2% Savinase 4.8 l, 1% Lipolase 100 l, 97% of the U.S. liquid detergent.

II: 1% capsules A Savinase, 1% Lipolase 100 l, 98% of U.S. liquid detergent.

III: I % capsules In Savinase, I % Lipolase 100 l, 98% of U.S. liquid detergent.

IV: 1% Lipolase 100 l, 99% of US liquid detergent.

Compositions I to IV left when the 30oWith 0, 4 and 8 days and measured residual is II (without sulfate) is weaker than the resistance of the liquid protease (due to the increase in the concentration of active protease inside the capsules). Deposition protease sulfate (capsules, part III) significantly improves the stability during storage as compared with capsules as well As liquid protease (see table. 3).

Sustainability Lipolase during storage significantly improved by the deposition of protease sulfate. However, compared to other systems stability during storage neozhidannoy composition (A) was also satisfactory.

Improved results were obtained when the polymer was replaced with the use of homopolymer polyacrylate sodium the same molecular weight and, in particular, when the stabilizer was replaced by a copolymer of styrene, sterilisability and maleic anhydride.

Example 7.

This example presents the receipt of the immobilized enzyme and, in particular, immobilized amyloglucosidase (AMG). The obtained particles useful as an encapsulated enzyme for industrial use, as they allow the diffusion of the reactants and products of reaction through the wall of the capsule, but do not allow the outward diffusion of the enzyme.

4,47 grams of DETA was emulsiable in which organisator Silverson at full speed for 2 minutes with cooling in an ice bath. Slowly added 120 grams of 18.4% concentrate of the enzyme (188 AGU/g) with additional emulsification for 10 minutes. After that, when 50oWith the rapidly gained 187 grams of a 3% solution of terephthaloylchloride in Isopar and continued emulsification within 5 minutes. The thus obtained dispersion of water in oil left to mix for 30 minutes at 20oC. Then added 170 grams of Dobanol 25-7 and drove the water and Isopar in vacuum (up to 95oWith under 20 mbar).

To check the quality of products made getting the following buffers and samples, and tests.

The buffers.

Buffer A:0.1 M acetate, pH of 4.3.

Buffer B: 0.1 M borax, pH was not installed.

The substrate is 0.1% p-nitrophenyl-alpha-D-glucopyranoside (NBS Biologycals) in the buffer AND

Specimen preparation.

I) 0,774 g AMG capsules + 1,624 Dobanol 25-7 + 47,61 g buffer.

II) 0,271 g concentrate AMG + 1,968 g of Dobanol 25-7 + 47,78 g buffer A.

III) 1,507 g of Dobanol 25-7 + 48,52 g buffer A.

The samples (with the enzymatic activity of 1.0 AGU/g) was vigorously stirred for one hour.

There were prepared the following sample:

IV) 2 ml (I + 4 ml of the substrate;

V), 2 ml of I, filtered through a filter of 0.45 micron*;

(Millipore) + 4 ml of the substrate;

VI) 2 ml II all capsules.

Samples IV and VI and deaf left mixed at 25oC for one hour, added 6 ml of buffer and left samples mixed for about five minutes and was filtered through a filter of 0.2 micron. He measured the absorbance at 400 nm.

The reaction between the substrate and the enzyme leads to the formation of glucose and p-NITROPHENOL gives yellow liquid in alkaline conditions, which are obtained with the use of buffer C. the Obtained color proportional to the concentration of DMG. Colis measured on the spectrophotometer at 400 nm (OD400).

Results

The sample is the absorbance at 400 nm

IV - 0,644

V - 0,011

VI - 0,762

Deaf - 0,005

Leakage of the enzyme from capsules (sample V) is approximately

100.(0,011-0,005)/(0,762-0,005)~1%

The effectiveness of the encapsulated enzyme (sample IV) relative to the substrate is approximately

100.(0,644-0,005)/(0,762-0,005)~84%

Thus, from capsules spilled a very small amount of enzyme, but the enzyme is almost as effective against the substrate, as not encapsulated enzyme.

1. The composition is in the form of particles containing particles with hydrophilic core inside the shell containing the membrane, including product Assoc the first reagent interfacial condensation, selected from isocyanate, epoxy and dicarboxylic acids (or higher digisat) or its derivative, which is or halogenerator, or anhydride having at least two first condensing group, and mainly water-soluble second reagent interfacial condensation, selected from a diamine (or tertiary diamines) or polyol, soluble in water, having at least two second condensation groups, and (b) oil-soluble or swelling in oil amphipatic polymer stabilizer, which will focus on the interface between oil and water and which has a repeating hydrophobic group and a repeating reactive hydrophilic groups that are associated with the second condensation groups.

2. The composition according to p. 1, wherein the Association includes the reaction of condensation.

3. Composition under item 1 or 2, characterized in that the stabilizer carboxyl group, and the second reagent interfacial condensation of an amine.

4. Composition according to any one of the preceding paragraphs, characterized in that the stabilizer is a copolymer of monomers comprising ethylene-unsaturated dick from the preceding paragraphs, characterized in that the stabilizer is a statistical polymer formed by copolymerization of a mixture of hydrophilic and hydrophobic monomers.

6. Composition according to any one of the preceding paragraphs, characterized in that the stabilizer is a statistical copolymer of a mixture of hydrophobic monomers selected from styrene and alkyl(meth)acrylates and hydrophilic monomers containing Ethylenediamine polycarboxylic acid, and the second reagent is Diethylenetriamine or other aliphatic polyamines.

7. Composition according to any one of the preceding paragraphs, characterized in that the core contains a polymeric substance.

8. Composition according to any one of the preceding paragraphs, characterized in that the core contains an active ingredient selected from pharmaceutically active ingredients, agricultural active ingredients, optical brighteners, fotohuvilistele, proteins, aromatic substances, dyes and enzymes.

9. Composition according to any one of the preceding paragraphs in the form of a dispersion of particles is not miscible with water, liquids or miscible with water, liquid, characterized in that 95 weight. % of the total weight of the particles have a size less than 30 microns.

10. Kompoziciy have an aqueous core within a polymeric shell.

11. The composition according to p. 10, wherein the polymeric shell is formed by interfacial condensation.

12. A method of obtaining particles with hydrophilic core inside the shell produced by interfacial polycondensation in a substantially oil-soluble first reagent interfacial condensation, selected from isocyanate, epoxy and dicarboxylic acids (or higher digisat) or its derivative, which is or halogenerator, or anhydride having at least two first condensing group, mainly water-soluble second reagent interfacial condensation, selected from a diamine (or tertiary diamines) and water-soluble polyol having at least two second condensation groups, which receive the dispersion of water-in-oil water composition of the nucleus, containing the substance of the nucleus and the second reagent interfacial condensation in not miscible with water fluids containing oil-soluble or maconaughey polymer stabilizer, mixing the dispersion with the first reagent interfacial condensation and carry out the reaction with the first and second reagents interfacial condensation with getting this shell, and in which the polymer stabilizer is chionophobia hydrophilic group, and reactive hydrophilic group associated with the second condensation groups of the second reagent interfacial condensation to mix with the first reagent interfacial condensation.

13. The method according to p. 12, characterized in that the polymeric stabilizer comprises a lateral carboxyl group, a second reagent interfacial condensation of an amine and a dispersion of water in oil homogenized before being mixed with the first reagent interfacial condensation.

14. The method according to p. 12, characterized in that the polymeric stabilizer is a statistical copolymer formed by copolymerization of a mixture ethyleneamines hydrophilic and Ethylenediamine hydrophobic monomers.

15. The method according to p. 12, characterized in that the mixing is carried out by mixing the dispersion and the first reagent under conditions in which the weight ratio of the variance and the first reagent remains largely constant during the mixing process.

16. The method according to p. 12, characterized in that the mixing is carried out by continuous mixing of the boot that contains the variance, and load containing the first reagent.

17. The method according to p. 12, characterized in that add miscible with water, the liquid (and optionally distilled water from kernel) to obtain the dispersion of the particles in the blending of water and organic liquids.

18. The method according to any of paragraphs. 12-17, characterized in that is not miscible with water, the liquid is a hydrocarbon liquid, essentially free from halogen-substituted hydrocarbon.

19. The method according to p. 18, characterized in that the polymeric stabilizer is a statistical copolymer of at least one ion ethyleneamines monomer with at least one non-ionic water-soluble ethyleneamines monomer.

20. The method according to p. 19, characterized in that the ionic monomer selected from acrylic acid, methacrylic acid and maleic acid (or anhydride), and non-ionic monomer selected from sterols and fatty alilovic esters ethyleneamines carboxylic acid.

21. The method according to any of paragraphs. 11-20, wherein the water-soluble reagent interfacial condensation of an amine, an oil-soluble reagent interfacial condensation of an acid or acid derivative, and the condensation polymer is a polyamide.

22. The method according to any of paragraphs. 12-21, wherein the water-soluble reagent interfacial condensation is Diethylenetriamine.

23. The method according to any of the preceding items, characterized those whom any of paragraphs. 12-23, characterized in that the aqueous compositions of the core and a water-soluble reagent interfacial condensation is 10-70%, preferably 25-60% by weight water dispersion containing an oil-soluble reagent interfacial condensation.

25. The method according to any of paragraphs. 12-24, characterized in that the dry weight of the core is 5 to 40% of the dry weight water dispersion.

26. The method according to any of paragraphs. 12-25, characterized in that the amount of the polymer shell is from 2 to 50% of the dry weight of the core plus shell.

27. The method according to any of paragraphs. 12-26, characterized in that the substance kernel contains a polymer or substance capable of polymerizates with the formation of the polymer matrix.

28. The method according to p. 27, characterized in that the aqueous composition engine includes an aqueous solution or emulsion of a polymeric substance.

29. The method according to any of paragraphs. 12-28, characterized in that the substance kernel contains the enzyme.

30. The method according to any of paragraphs. 12-29, characterized in that it is carried out substantially in the absence of emulsifier of water-in-oil.

Priorities for items:

18.04.1996 on PP. 1, 8, 11-23;

28.05.1996 on PP. 9, 10, 24-30.

 

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