Microcapsules with acetylene carbamide-polyurea polymers and compositions thereof for regular release

FIELD: chemistry.

SUBSTANCE: invention relates to microcapsules used in agrochemical compositions as part of any type of composition used to in agriculture, as well for microencapsulation of pharmaceutical and medical compounds, flame-retardants, phase transition materials, thermosetting materials, ink and catalysts. The microcapsules contain a material with water solubility of less than 750 mg/l at 20°C. The wall of the microcapsules is formed via interphase polymerisation of materials which form the wall: (a) aliphatic isocyanate(s), and (b) aromatic isocyanate(s), and (c) compound(s) of formula (I), acetylene carbamide derivatives

,

where R₁, R₃, R₅, R₇ independently denote methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butylene, tert-butyl; R₂, R₄, R₆, R₈ independently denote hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl; R₉, R₁₀ denote hydrogen or hydroxymethyl; including oligomeric forms of compounds (I), where the number of moles of compounds (I) ranges from 2 to 10; and the microcapsules have average diameter from 0.3 to 25 mcm when using a conventional laser diffraction analyser to measure particle size with preliminary conventional dissolution in water while stirring. The invention also describes a method of producing an agrochemical composition of a typical encapsulated suspension, containing said microcapsules, and versions of using said microcapsules.

EFFECT: obtaining microcapsules with possibility of controlling the speed of release of the microencapsulated material, and improvement of the toxicological profile of the microcapsules and compositions containing said microcapsules.

12 cl, 12 ex, 13 dwg

This invention relates to an alternative method interphase polymerization of microcapsules, microcapsules, he received microencapsulated agrochemicals, pharmaceuticals, catalysts and materials with phase transition and their compositions, by means of microcapsules and source materials with much lower toxicity profile than conventional microencapsulated materials, and share acetylanthranilic derivatives in the final structure of the wall of the microcapsules.

The scope of the invention

This invention relates to polymeric microcapsules for controlled release of active ingredients and compositions containing microcapsules.

Prior art

The problem faced by the present invention is to provide an alternative way of microcapsules and received microcapsules for the controlled delivery of agrochemicals (or other compounds with structures related to all the different types of structures of agrochemicals for any acceptable way, also materials phase transformations, RSM, ink, thermosetting materials and catalysts) in such a way that hazards associated with the receipt and the product reduced (by materials forming the wall, with a lower toxicity on sravnenie the existing industrial methods), while the microcapsules obtained by this method (and formulated microcapsules), regulate the rate of release acceptable way for proper functionality.

Methods microcapsules for the delivery of agrochemicals known since the 40's. Physical methods, phase separation and phase transfer reaction are the three main methods of microcapsules. The most successful inter-phase polymerization to microcapsulation agrochemicals developed in the early ' 70s Scher and others (Stauffer Chemical Company), and group Stauffer (first Zeneca, then ICI, now Syngenta) has obtained many patents based on modifications of the same basic concept, namely the formation of the polyurea walls of the microcapsules to activate the chemicals.

The invention includes several aspects. In this case, the synergistic or combined effects of many parameters on the basis of reagents, it is necessary encapsulation materials to final modifications to the final industrial application of the compositions, especially in agriculture, for the final proper functionality.

i) Disclosed the industrial method of microcapsulation never before presented, which includes the use of at least an aromatic isocyanate, at least, aliphatic isocyanate and at least producing the CSOs acetylene carbamide (ACD) of the formula (I) as materials, forming the wall.

ii) Prisoners in these microcapsules materials have a specific rate of release, which in some embodiments is more profitable than existing commercial products, and in some embodiments, the implementation of an alternative (lower toxicity) in the existing methods, ranging from quick release (for example, lambda cigalotrin)supported releases (for example, verklaren, clomazone), to virtually no release, for example (wax phase transformations).

iii) Agrochemical compositions described herein are new and functionally applicable, what it means, can be applied in the field, as used available microencapsulated composition at the present time, with these devices, precautions, and techniques that are used agricultural producer, or with the same used in the fabrics and coatings for RSM (materials phase transformations), or the same application in reactions for microencapsulated catalysts, as available microencapsulated catalysts.

iv) Dry composition of the microcapsules can be applied to microcapsules RSM by incorporating in the wax oil phase or oil with melting points in the range from 0 to 50°C (which can be only m is Slany solvent or dispersion of the solid materials in an acceptable oil phase, for catalysts and thermosetting materials.

Note that we will focus on the derivative acetylenecarbonic with the acronym ACD. We will focus on the compositions of microcapsules in agriculture, on any form of agrochemical compositions containing microcapsules, and not only about the conventional compositions capsule suspension (CS). Non-limiting examples, the term "microcapsule composition" are suspoemulsions and dispersible in water granules (WG compositions containing microcapsules, oil suspensions, where the oils are mixtures of agrochemicals (at least one microencapsulated), etc. Also, it is obvious that this invention allows the combination of microcapsules containing one or more active ingredient with other nemikrocelularni active ingredients in the same composition.

This invention differs from the prior art as follows. There is an additional integral tool of cross-polymerization, which gives the microcapsules unique parameters, namely, the derivatives of acetylenecarbonic (ACD). ACD cause radical changes in the permeability of the walls of the capsule at low concentrations (from 0.05 to 5% of the entire composition). Polymer wall is not a wall of polyurea (already stated in many other patents), but rather Stanko is of polyurea - derived acetylenecarbonic (never described earlier). This wall is an additional parameter, relative to the prior art, for regulating the permeability of the walls of the microcapsules, namely, the ratio of ACD/isocyanates determined experimentally.

There is a need (not necessarily) add the first catalyst to form connections polyurea, because the microcapsules are limited to the use of aliphatic isocyanates and aromatic isocyanates (which are less reactive capable), preferably dialkylamino ether fatty acids. Eliminates toxic isocyanates, as described in previous patents (as TDI), thanks to a new combination of less toxic isocyanates, are able to form the polyurea wall, ACD cross-linkers and catalysts adapted for this method, and the ability of end functional groups of isocyanate, not participating in the reaction. A variety of materials to be capsulerebel, the reaction products, catalysts and consider the chemical composition, time and temperature of reaction are all characteristic features. This way you can capsulerebel any chemical, which by nature does not react with functional groups of wall materials, belong to any structural chemical is a mini-type does not react with the material forming the wall, and has a reasonable molecular size, the ability to dissolve dispergirujutsja or used purity.

The usual and common used materials microcapsules for many agricultural compositions (sold all over the world in large quantities, for example, Karate® Zeon, Syngenta) is used as part of a wall of highly toxic and carcinogenic to humans the compound 2,4-colorvision (TDI)CAS# [584-84-9]. In preferred embodiments of this invention are applied isocyanates with greatly reduced toxicity profiles than those mentioned TDI, for example m-TMXDI, CAS# [2778-42-9], known in the market as TMXDI® production Cytec. It should be noted that TMXDI was never reflected in a significant, if not not reflected, industrial application in the field of microcapsules liquids or agrochemicals, as well as for other microcapsules. As you can read on the website CYTEC "resin TMXDI are generally applicable in the tool industry for encapsulation and protection of electronics, coatings of printed circuit boards and filters with sticky seal". It is a combination of isocyanates with ACD brand new and not obvious.

Below is the comparative table of Toxicological differences between TMXDI and TDI (according to the MSDS (material safety) from Sigma-Aldrich and CYTEC).

Thus, to solve the problem of making microcapsules to control the speed of release of chemicals in this invention an improved Toxicological profile of the microcapsules (and their compositions). It is important to note that the known methods of microcapsules usually not fully completed, then the unreacted residue of the isocyanate harms the health of consumers. The content of unreacted isocyanate is reduced not only by the application of ACD. At the same time, any unreacted isocyanate present during the application microcapsule composition, or in the wall, or dispersed/dissolved directly in the composition, has a much lower toxicity (for example, TMXDI compared to TDI).

U.S. patent 4285720 (originally filed in 1973 Scher and others, Stauffer)that are included in this description by reference, represents the main way the interphase of microcapsules. Other recent patents do not report more than in this document, with respect to this invention. In U.S. patent 4285720 the claimed method microcapsules with polyurea capsules without the addition of the second reagent, which provide the organic phase, with nesm the requested water material, subject to microencapsulation, and with an organic polyisocyanate in an aqueous phase containing a solution of water, surfactant and protective colloid, heated, after which the specified water-immiscible material capsulebuy in discrete polyurea capsular membrane. ACD is not mentioned. Moreover, the catalyst can optionally be added to accelerate the reaction, and the specified catalyst is an alkyl tin acetate. In this invention the necessary catalyst of the type alkyl tin ether (preferably disutility ether).

In U.S. patent 4874832 described method of microcapsulation with aliphatic isocyanate, but combined with polyester polyols for the formation of polyurethanes. U.S. patents 4417916 and 4874832 explain in detail microcapsulation with aliphatic isocyanates, but not combined with derivative acetylenecarbonic. In U.S. patent 5925595 disclosed the use of TMD (trimethylhexamethylenediamines) and PAPI (polyacrylonitrile), and the impact of TMXDI on the rate of release when the latter is included in the mixture of isocyanates. However, according to the U.S. patent 5952595, mainly, the materials forming the wall, need application polyamine (indicated in the description, and options for implementation, which always applies Amin): this invention is effective with any application required polyamine to the formation of the deposits of the polyurea wall, the main difference of the present invention lies in the chemical method, and in the final structure of the microcapsules. Moreover, U.S. patent 5925595 does not mention the use of ACD.

One significant new and inventive aspect of the present invention is the application for the synthesis of the wall of the microcapsules ACD. The existence of brochures on ACD (e.g., Powderlink® 1174 from CYTEC) explain, on the basis of using them in the way of microcapsules, on the basis of their low reactivity and needs special initiators and temperature requirements, and the need for additional hydroxyl groups for their reactions.

In international publication WO 92/13448 (equivalent to European patent 571396 and U.S. patent 5332584) stated that aminoplast polymers for use in microcapsules can be performed with different types of connections, namely: modelinformation, melamineformaldehyde, benzoquinonediimine and acetylenecarbonic(glycoluril-)formaldehyde. However, this document does not mentioned fully referred to the use of any isocyanate compounds for part of the wall of the microcapsules in combination with any urea, melamine, benzoguanamine glycoluril formaldehyde, as is done in the present invention (independent claim 1 and dependent claim 4 of the European paten is and 571396 B1 relate only to the application of aminobutanoic compounds without isocyanates).

The study found that far from what was disclosed in the prior art and in an extremely suppressive ways that you can enter the ACD in the polyurea wall, at the same time, using a combination of isocyanates (in the preferred embodiment, PAPI and TMXDI), is less toxic than the traditional mixture of PAPI and TDI.

There are documents that are far from the solution of the present invention. Additionally, the prior art is illustrated by U.S. patent 5563224. There is disclosed the use of compounds (including the ACD) for fixed defenses against ultraviolet radiation to obtain plastic that needs ACD (for reactivity fixing these protective agents against UV-radiation) with the use of sulfuric acid. In the same patent States that acetylpenicillamine monomers for reactivity must be in strong acidic conditions with heating. Probably for the method according to this invention the chemical potential required to activate ACD, provided the excited state of the isocyanate and/or strengthening local temperature exothermic reaction of the isocyanate. It should be stated that the U.S. patent 5563224 not mention any case of the use of polymers in concrete, and very specific area of microcapsules. In this image the shadow do not apply strong acids and strong heating (which can destroy the active ingredients for encapsulation).

The following documents cited in the extended European search report, and discussed in relation to novelty and inventive step, prior to this invention. In patent DD 108760 (Makower and others, 1974) revealed ACD, which with great restraint (ethoxylates) can provide some of the compounds (I) according to this invention, and, moreover, in areas distant from microcapsules, for example, large pieces of plastic materials. Not mentioned combination for the formation of the polyurea microcapsules. In international publication WO 92/13450 (ICI, 1992) in item 1 revealed only the polyurea compounds formed by way of the reaction of isocyanates for the formation of the polyurea walls without adding the second reagent, therefore, explanations are far from enabling ACD. U.S. patent 4889719 (Ohtsubo and others, 1989) discloses microencapsulated insecticidal composition comprising organophosphorus insecticide, encapsulated in a wall formed from a polyurea; however, no mention of the formation of composite polymer with ACD. In addition, U.S. patent 4889719 far from combinations of aromatic isocyanate and an aliphatic isocyanate according to this invention (column 1, lines 38-40: a mixture of aromatic and aliphatic isocyanates are preferred, because the difference in response speed between them is not POS is s easy to obtain a homogeneous wall). Found that this does not occur in this invention, since this invention is very uniform wall, and, moreover, a very homogeneous particle size of the microcapsules. U.S. patent 4458036 (Fesman and others 1984) relates to polyurethanes with the inclusion of ACD in a remote area as flame retardants in the foam, and not in the microscopic structure as microcapsules. May perform thousands of reactions for the formation of plastics or foams (U.S. patent 4458036, mattresses, upholstery, pillow), but this document does not specify that the ACD can be combined with polimochevinnykh for the formation of microcapsules. Macroscopic structure of the polymers disclosed in U.S. patent 4458036, does not lead to homogeneous fields of polymers, polyurea and ACD is not notified of any use of the mentioned polymers in the field of microcapsules. U.S. patent 3766204 (Mathew C., and others, US, 1973) also applies to remote areas, such as polyesters, alkyd resins and polyurethanes, lubricants and surface-active products. Moreover, ACD disclosed there is absolutely differ from those stated in this invention. There is no mention, why should not be taken into account ethoxylated chain compounds disclosed in U.S. patent 3766204 to get stated in ACD, and a lot less to choose them as an integral part of the wall of the imagewin and ACD for microcapsules. It is noteworthy that in this area there is increasing interest in microcapsules, ACD has never been described for use in the microcapsules (despite the fact that it's such a simple feature).

It should be noted that the heat required for the ways of microcapsules (including the method according to this invention)can sometimes exceed the maximum limit of stability of chemicals subject to capsulerebel. This occurs, for example, with specific pyrethroids, where some unwanted enantiomeric, or diastereoisomers, or isomeric forms occur due to temperature. In such cases, to prevent isomerization can be added antioxidants. First, it is not obvious that the antioxidant can prevent isomerization (there are many chemical ways in which the molecule can be samaritana), and secondly, the inclusion of antioxidants in the oil phase was never expressed in the case of isomerization of pyrethroids. On the basis of the method according to this invention it is possible to add soluble in oil antioxidants (such as BHT, equivalent, BHA, butylhydroxyanisole, or mixtures thereof) directly in the oil phase according to this invention. In the specific example you can add a 0.05% BHT and 0.01% BHA (relative percentage of the total weight of the entire oil phase) in Solvesso 200, which at the same time assetsarticle in a preferred embodiment, microcapsules superchallenge (number EIT, VNA or other antioxidants can be applied according to the recommendations of the relevant methods). This prevents the isomerization superchallenge, which starts at 40°C in the dark.

The idea of adding additional cross-linking material of low reactivity, such as ACD (when comparing its reactivity with known components of the walls of the microcapsules, for example, isocyanates or aminoplastics resin), the polyurea wall is not obvious. Did not expect that a small percentage of ACD can change the characteristics of the speed of release of the microcapsules in the ranges required for applications in agriculture, or to be applicable for the production of catalysts, thermosetting materials or PCM (recent cases require a higher content of the materials forming the wall until the rate of release is acceptable for every necessary purpose). In addition, the fact that some ADC (e.g., Powderlink 1174) are solid ignored because it is convenient (and the prior art is to use a liquid material as the material forming the wall, in the interphase of microcapsules (included in the oil phase). You can include solid ACD in dispersed form in the oil phase (e.g., using Atlox® LP-1 or LP-5, or LP-6), but there is try, it sometimes leads to excess unreacted ACD.

Even wanting to add a cross-linking agent in the polyurea wall for modification of the well-known walls, the expert would choose any cross-linking agent, more reactionary capable than ACD. Several scientific articles have been written about the chemistry and properties of ACD as cross-linkers, but never mentioned how microcapsulation, only in areas far enough to touch the way microcapsules (for example, fabric processing, coatings for automotive fabrics and so on). Not to be confused hardly describes the features of ACD with their specific new and inventive use of microcapsules, and should understand the complexity of the inclusion in the reaction of cross-linking on the border of the oil and water phases, in situ, two types of isocyanates and ACD far for comparison with the reaction of formation of plastic films or lacquers. Even in the described methods of polymerization in remote technical fields using ACD remaining unpolymerized monomers must be removed or deleted from the final product, the circumstance that have no place in this invention. In particular, polymers with relatively large pores (but not the microcapsules as closed volumes) can be formed with acetylenecarbonic-formaldehyde, but the pic is would imagine that acetylenecarbonic formaldehyde must first be emulsified in the aqueous phase. The chemistry of these ways is very different from the present invention.

A detailed description of the invention

Microcapsulation active ingredient(s) in solution (organic phase) perform ways interphase polymerization, based on the reaction of isocyanates with derivative acetylenecarbonic formula (I). As the polymer, which is microcapsule wall according to this invention is a new, specifically in the field of microcapsules, the claims directed to the actual polymer.

In particular, the above-mentioned polymer can be described as a polymer for microcapsulation water-immiscible material, as primary material for microencapsulation (or a mixture of water-immiscible materials). "Secondary" material for microencapsulation may be a solid material dispersed in the oil phase to be microencapsulation together with water-immiscible material and/or components of the composition for technological purposes (surfactant) or protective purposes (e.g., antioxidants). Obviously, the materials to be microencapsulation, must be compatible and not react undesirable until the final application of the microcapsules.

"Primary" material for microcaps the modeling is not miscible with water, which means in this case, the solubility in water below 750 mg/l at 20°C. the Specified declared the polymer formed by the interphase polymerization reactions and signs of water-immiscible material(s), characterized in that the polymer formed by the reaction of: a Monomeric aliphatic isocyanate prepolymer aromatic isocyanate,

N,N',N",N"'-alkoxyalkyl and/or hydroxyalkyl derivative of acetylenecarbonic or mixture of such compounds, where the alkoxy means methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, ter-butoxy, and alkyl means methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, independently from each other, replaced by nitrogen, and

microcapsules have an average diameter of from 0.3 to 25 μm, preferably from 0.8 to 15, and 90% of the microcapsules have a diameter less than 100 microns, preferably less than 30 μm, when measured conventional laser diffraction analyzer, particle size, with preliminary plain dissolved in water with stirring.

The more hydroxyl groups present in the ACD, the greater its reactivity. Found that an excessive number of hydroxyl groups in the molecule is substituted by an ACD leads to acceleration of the reaction, it is acceptable in some cases, but more challenging to regulate. The only way to choose the right the ACD for a particular purpose is to experimentally verify the result of the reaction and to adapt the response time (for example, by increasing/decreasing the speed at which the emulsification of the oil droplets and/or increasing/reducing catalyst responsible for the formation of the polyurea linkages, and catalyst to activate the cross-linking ACD). It is possible that the alkoxy or alkyl groups of more than carbon atoms. In this case, the capsule wall more permeable due to the larger cross-linking means. The use of compounds of up to 6 carbon atoms for the alkoxy and alkyl groups then must be reduced in a mixture of materials forming the wall to avoid excessively rapid release. Also, a greater number of hydroxyl groups in ACD is increased reactivity that may be acceptable for certain applications requiring more impenetrable wall structure, for example in the case of materials phase transformations (PMC). This invention includes all types of ACD in the range represented by deputies with regard to stereochemistry. Usually, the use of these compounds is limited to commercially available, but can be cleaned a certain stereochemical structure in the future ACD will not restrict the use of such connection in this izobreteny is. A more specific structure of such is included in the polymer ACD (I) the following (Figure 13):

where

a) R₁, R₃, R₅, R₇represent, independently of one another, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and

b) R₂, R₄, R₆, R₈represent, independently of one another, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and

(C) R₉, R₁₀represent hydrogen or hydroxymethyl, more preferably both Deputy are hydrogen,

including the compound (I) all isomeric and stereoisomeric configurations that may be present depending on the radicals, as mentioned, with the exception of the compounds (I) all combinations of radicals, which are not capable of forming polymers of the polyurea derivatives acetylenecarbonic (ACD), when such ACD react, as described in this invention, with a mixture of isocyanates.

ACD is a fundamental part of the wall of the final microcapsules according to this invention. In a typical method has two phases, an oil phase and a water phase, an oil phase to emulsify in aqueous phase at 45-70°C, begin polyurea reaction, the temperature rises to 60 to 90°C., and is added to the catalyst reactivity of the ACD after the start of the reaction polyurea, in the continuous aqueous phase. The exposure time is from about 1 to 4 hours at 50 to 90°C. Then, a unique containing polymer microcapsule wall in water-oil interphase oil drops.

Typical oil phase according to this invention consists of:

Monomeric aliphatic isocyanate (for example, TMXDI),

prepolymer aromatic isocyanate (e.g., PAPI),

Monomeric acetylenecarbonic (for example, Tetra-butoxymethyl

acetylenecarbonic) (referring to "Monomeric acetylene carbamide, when the content of the monomers above 50% of the total commercial acetyltyramine product: in an industrial environment it is difficult to obtain pure Monomeric acetylanthranilic product),

solvent (for example, cyclohexanone for dissolving Tetra-butoxymethyl of acetylenecarbonic),

active ingredient(s) (e.g., superciliaris),

optionally, dispersed solid active ingredients (for example, ground-cypermethrin, with crystal sizes <5 μm and Atlox® LP-1),

optionally, dispersed and/or dissolved antioxidants and/or a protective agent against ultraviolet radiation,

optional (to provide smaller microcapsules) surfactant with a low HLB (hydrophilic-lipophilic balance) (e.g., Atlox® 4912).

The ratio of the composition tipi is but is the following:

Monomeric aliphatic isocyanate to prepolymer aromatic isocyanate from 1:3 to 1:1,

prepolymer aromatic isocyanates to the Monomeric acetylenecarbonic from 9:1 to 4:1,

Monomeric aliphatic isocyanates to the Monomeric acetylenecarbonic from 2:1 to 5:1,

the most preferred ratio of Monomeric aliphatic isocyanate to prepolymer aromatic isocyanates to the Monomeric acetylenecarbonic is 3:6:1.

The oil phase before emulsification is always contained in dehydrated atmosphere (by chemical or physical means, for example, drying or absorption, or secretion, and also possible treatment in inert atmosphere with gases, preferably CO₂N₂He, or only by regulating the relative humidity of the area of the reaction).

The aqueous phase typically contains:

water,

the primary surfactant (for example, alkyl ethoxylated/propoxycarbonyl copolymer type Symperonic®),

water soluble or dispersible polymer(s) (e.g., polyvinylpyrrolidone PVP-30),

the hydrocolloid(s) (e.g., guar gum),

lignosulfonate(s) (e.g., type Kraftsperse®).

At this stage during the method of dispersion of the organic phase emulsify in aqueous phase at a temperature of about 45-70°C. the Primary particle size of the dispersed phase must be in the range of the Ohe 1-25 microns. As soon as reaches the target particle size, stirrer with high shear is stopped and the main stirrer (anchor) is adjusted to the smallest size to reduce shear stresses during the heating period as structuring.

The presence of a catalyst in the organic phase initiates the reaction of formation of the wall, which will be further enhanced by heating to about 60-90°C. Then add the catalyst to enable ACD in the polyurea wall (for example p-toluensulfonate acid, dissolved in alcohol with a chain longer than 8 carbon atoms; if used substituted sulfonamide, then the reaction temperature must be increased). Microcapsules leave on time from one to about two hours at 50-90°C for full expenditure of isocyanate residues. Then the mixture was allowed to cool, typically to room temperature.

The pH value of seasoned microcapsule suspension adjust to pH, more acceptable for the stability and the desired properties of the agrochemical, 50% aqueous sodium hydroxide solution.

Finally, add a viscosity modifier type clays (for example, inert zeolites) and hydrocolloids (e.g., xanthan gum), aluminum sulfate and sodium tripolyphosphate to prevent separation of the particles from the water during prolonged storage due to their different densities. Use b the atmospheric system (preferably, to save, based on the sodium carbonate or citric acid) to maintain the composition of the required pH. It is also noted that for solutions under alkaline conditions using sodium carbonate (or any other source of carbonate ions), because the absorbed carbon dioxide formed in the reaction of residual isocyanate with water during storage, thus preventing any increase of pressure in the tanks with the final product, the situation is expected only in exceptional cases, when the party is not stored correctly.

Add some biocide to protect the composition from biological impact during the product's shelf life (preferably type imidazolidinyl urea or other traditional bacteriostatic, bacteriocide or microbicide).

Way, as explained, begins with the dissolution of aliphatic and aromatic isocyanates and the active ingredient, in the end, surfactant, or a protective agent against ultraviolet radiation or antioxidant, water-immiscible solvent. The solvent is present to dissolve the active ingredient(s), and. and. if and. I. solid, or only to ensure the oil phase, and where. I. present. In certain cases, if the number and. I. high enough and all the materials that form tenku, able to dissolve, "solvent" is mainly replaced by and. I., which acts as as. and. and as a solvent (which is an exceptional situation). ACD is included in the oil phase through the second solvent when necessary. Additional oil phase contains the catalyst, which initiates the reaction of formation of the wall (in the presence of water). Also, the solid active ingredients can be dispersed in the oil phase. The aqueous phase is medium-medium (continuous phase) of microcapsules containing the active ingredient(s), but the aqueous phase may also contain dispersed or dissolved active ingredients (e.g., glyphosate or Diquat for use in agriculture). The aqueous phase is prepared by adding emulsifiers, protective colloids and other components of the composition, which is able to emulsify the oil drops, which will be located in the nucleus of the final microcapsules, and also optional are the final components of the composition required for proper functionality of the final composition.

Preferred materials forming the wall

Of the ACD is preferable to use type commercial products Powderlink® 1174 and Cymel®, more preferably Cymel® 1711 and Cymel® 1170. The use of prepolymers type Cymel leads to more devil is radocea the course of the reaction in comparison with the use of Powderlink® 1174 in specific experiments according to this invention. Thus, the most preferred ACD is Powderlink® 1174. It should be noted that commercial products may have some other connection than the monomers mentioned on marking sign (e.g., Powderlink® 1174 may contain oligomers).

Polyfunctional isocyanate system one preferred aliphatic isocyanate and one aromatic isocyanate, an aliphatic preferred in the case when the-NCO group is not attached directly to the aromatic ring). The density of the polymer can be varied by changing the ratio of the polyfunctional (for example, preprimary aliphatic PAPI) up a polyfunctional aliphatic isocyanate (for example, Cythane® 3174, TMXDI, the latter is preferred aliphatic isocyanate according to this invention). The higher the ratio, the greater the cross-linking leads to a higher diffusion coefficient and higher permeability. When the ACD, the complexity of the reactions of cross-linking makes the prediction of the final speed of release, which can be measured in experimental tests with the formed microcapsules.

Preferred aromatic isocyanate according to this invention is PAPI® and series from Dow®. Below is shown the preferred compounds

,

where n= from 0 to 6.

For n=1, PAPI, CAS# [009016-87-9], the commercial name Specflex® NE 138.

Preferred aliphatic isocyanates are TMXDI and Cythane® 3174 represented by the formulas below:

The NCO content(weight/weight)~34,4	Cythane® 3174 - prepolymer in butyl acetate
	The NCO content(weight/weight)~10,2

It is obvious that the benefits included derivative acetylenecarbonic wall formed TDI and PAPI, can be observed, however, in this case, the method of obtaining and the capsules occurs a problem of significant toxicity TDI, in other words, the use of derivatives acetylenecarbonic and TDI, and PAPI is a significant subject of discussion of the present invention, and any conventional combination of isocyanates for the formation of the polyurea walls. There is an experience that ACD can be included in many types of polyurea walls, getting polyurea polymers-ACD.

Also, found that the inclusion of aromatic isocyanates, is different from the corresponding formula above gives a fully functional wall of the microcapsules.

Application aligations the x isocyanates (NCO groups are not directly connected to aromatic ring) involves the use of a catalyst to start the reaction due to their low reactivity. Due to the hidden lack of reactivity they are not used in industrial applications commercially viable microencapsulated compositions.

Apply such catalysts (oil phase) as tin octoate, dibutylamine dilaurate, potassium acetate, potassium octoate, dibutylamine mercaptide, dibutylamine dicarboxylate, finalstate propionate, lead octoate, salts of alkali metals (K₂CO₃, NaHCO₃and Na₂CO₃), ferric acetylacetonate.

When using a combination of tertiary amine catalysts for a long time have found that using ACD and in the absence of amines, the reaction not only flows, but it is a very convenient way. According to experience, specifically of the type mono- (di-, tri-, Tetra-) fatty acid alkyl ether element 4 groups or 14 group fatty acid ester, and the preferred alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl (and all their isomeric forms of the chain), and the preferred metals are the transition metals of Sn, Ti, In, Sb, Pb, Ge, Pd, Pt, Au, Zn, Fe, Cu. The most preferred catalyst for the type of microcapsule, popular currently on the market agrochemicals, cost, specific to the needs of fashion and ecotoxicological reasons is dibutyltin is at. Compared the use of triethylenediamine with dibutylamine the laurate with catalyst from dibutylamine the laurate and received a better regulation of the reaction and modification of properties of the wall when using only dibutylamine laurate. However, the method can be adapted (particularly the reaction time and temperature) for other acceptable catalysts mentioned above, for specific applications, especially agrochemicals with a certain tendency to react with the material forming the wall.

To enable the ACD to the wall, apply a second catalyst, is placed in the aqueous phase, most preferably p-toluensulfonate acid, or the type of sulfonamide (for example, methylcellulose), or type Cycat™ 600, or Cycat™ 500.

As the preferred system of polymerization using an aliphatic isocyanate (m-TMXDI as monomer) in combination with aromatic isocyanate PAPI, which is less reactive than the two aromatic isocyanates, for example, PAPI/TDI. In addition, aliphatic isocyanates get without phosgene and without nitrosamines. These types of isocyanates favorable toxicity profile, which makes working with them easier and more safe in comparison with other accepted isocyanates, for example, microcapsule type products Syngenta, and the selection of the type of a pair of isocyanates in real industrial applications the AI brand new (with a higher degree of novelty in combination with ACD and the selection of only one ORGANOMETALLIC catalyst).

The most preferred functionality of lignosulfonates (which you can also get other equivalent commercial products, which can replace Kraftsperse, not being a lignosulfonate, but are not the first choice) is achieved by treatment according to this invention a mixture of the compounds mentioned below, heat treatment at 70°C for 10 minutes, called LignoGAT™.

Other lignosulfonates and modified sulfonates of choice are Reax®, Polyfon®, Kraftsperse®, Borresperse®, Ultrazine®, Ufoxane®, Marasperse®, Diwatex®, Morwet® in any of their versions.

Other acceptable hydrocolloids are agar, alginates, Cartagena, Gellan gum, pectin, cellulose, exudate gum (Arabian gum, tragakant, gum, Ceratonia siliqua and/or gum karaya), tragacanth, saponins, xanthan gum, and derivatives and/or mixtures of these compounds.

Soluble in water dispersible polymers of choice are the I, in addition to the most preferred polyvinylpyrrolidone (up to 100 mol monomer) and polyvinyl acetate, copolymers of PVP and methyl methacrylate, copolymers of PVP and vinyl acetate (VA), polyvinyl alcohol (PVA), copolymers of PVA and crotonic acid, copolymers of PVA and maleic anhydride, hydroxypropylcellulose, hydroxypropyl guar gum, sodium polystyrenesulfonate, tripolymer PVP/ethyl methacrylate/methacrylic acid, a copolymer of vinyl acetate/crotonic acid/vinyl neodecanoate, the copolymer octylacrylamide/acrylates, monotropy ester of poly(methyl vinyl ether maleic acid), copolymers of octylacrylamide/acrylate/butylaminoethyl methacrylate, copolymers of acrylic acid/t-butyl acrylate, tripolymer dimethylaminoethyl methacrylate/isobutyl methacrylate/2-ethylhexyl-methacrylate, copolymers of t-butyl acrylate/acrylic acid and silicone grafted tripolymer, for example, t-butyl acrylate/acrylic acid/PDMS and mixtures thereof.

Surfactant for the formation of emulsions of oil in water you can choose from a wide range of conventional surfactants, provided that their hydrophilic-lipophilic balance of from 12 to 18 (e.g., ethoxylated and/or propoxycarbonyl alcohols).

Typical polyisocyanates acceptable for this method, selected from the first group and the second group (mixture of two isocyanates as the material that forms the corresponding wall, except acetylenecarbonic should be taken one isocyanate from each group must always be at least one isocyanate from each group, because of the confusing terminology in this field you specify a different classification than a simple division into "aromatic and aliphatic").

Group 1 [called "aromatic" in this invention], with NCO groups directly linked with (substituted) benzene ring: 1,3 - and/or 1,4-phenylene diisocyanate, 2,4-, 2,6-toolen the diisocyanates (TDI), crude TDI, 2,4'-, 4,4'-diphenyl methane diisocyanate (MDI), crude MDI, 4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4-4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4 diisocyanate the difenilmetana, naftilan-1,5-diisocyanate, triphenylmethane-4,4', 4"-triisocyanate, m - and p-isocyanate phenylsulfonyl isocyanate, polyacrylonitrile (PAPI), difenilmetana-4,4'-diisocyanate (PMDI), derivatives and prepolymers of isocyanates group 1.

Group 2 [all of them are called "aliphatic" in this invention], with NCO groups are not directly associated with (substituted) benzene ring.

Aliphatic isocyanates include ethylene diisocyanate, hexamethylenediisocyanate (HDI), tetramethylene diisocyanate, dodecamethyl diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexane-methylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis(2-isocyanate ethyl)femara is, bis(2-isocyanate ethyl)carbonate, 2-isocyanate ethyl-2,6-diisocyanate of hexanoate, trimethylhexamethylenediamine (TMDI), dimer acid diisocyanate (DDI).

Alicyclic polyisocyanates: isophorone diisocyanate (IPDI), DICYCLOHEXYL diisocyanate, dicyclohexylmethane diisocyanate (H-MDI), cyclohexyl diisocyanate, hydrogenomonas tolylenediisocyanate (HTDI), bis(2-isocyanate ethyl)-4-cyclohexen-1,2, in primary forms, 2,5 - and/or 2,6 norbornane diisocyanate.

Analiticheskie the polyisocyanates having 8 to 15 carbon atoms: m - and/or p-Xylen diisocyanate (XDI), alpha, alpha, alpha, alpha-tetramethyl Xilin diisocyanate (TMXDI).

Alicyclic polyisocyanates include ethylene diisocyanate, hexamethylenediisocyanate (HDI), tetramethylene diisocyanate, dodecamethyl diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexane methylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, bis(2-isocyanate ethyl)fumarate, bis(2-isocyanate ethyl)carbonate, 2-isocyanate ethyl-2,6-diisocyanate of hexanoate, trimethylhexamethylenediamine (TMDI), dimer acid diisocyanate (DDI), and derivatives and prepolymers of isocyanates group 2.

The following components of the compositions of this invention can be found on str-230 books (mentioned pages are included in this description in their entirety by reference) Peter A. Lovell and Mohamed S. El-Aasser, Emulsion Polymerization and emulsion polymers, John Wiley and Sons, ISBN 0-471-96746-7, 1997, West Sussex.

The rate of release of microcapsules mainly regulated by:

the size of microcapsules,

the degree of cross-linking,

the choice of the type of polymer,

wall thickness

the mobility of the oil phase.

The average radius of the particles (and therefore surface area) is usually installed in the narrow limits to meet the examination method and physical stability. The preferred average particle size of the droplets of water-immiscible liquid containing the active ingredient is 0.1-200 μm, preferably from 0.3 to 50 μm and more preferably 0.5 to 20 μm, depending on the purpose. Particle size may also be below 0.1 μm. These particles, called nanoparticles, and you can get them acceptable emulsifier (especially when they are in the oil phase) with enhanced speed voltage is placed offset, while undergoing emulsification. It should be understood that the application of the polymer material of the present invention in the nanocapsules is an obvious application of this invention.

The particle size can be adjusted according to the end use of microcapsules by regulating the speed and time of stirring and by the choice of surfactants and quantity of the used surfactants.

The difference of concentration on opposite sides of the wall, as I believe, usually continuously, when the microcapsule gets on the foliage, water, or soil environment. Foliage or the soil act as receiver of the pesticide, and therefore, pesticide exists in very low concentarte on the outer surface of the microcapsules. Particularly interesting is the use of microcapsules in lakes or reservoirs for release of insecticides against mosquitoes (for example, pyriproxifen, methoprene, hexaflumuron), where the water is referred to as "receiver".

If the rate of release from the microcapsules should be changed by orders of magnitude, the most practical way to accomplish this is to change the permeability of the walls of the microcapsules. Permeability is defined as the product of the factor of diffusion coefficient and solubility. For this pesticide, the diffusion coefficient can be changed by varying the wall thickness and by ranged the project density of cross-linking wall; the variation of the chemical composition of the wall can change the solubility. Moreover, the chemical structure of the employed solvent for the active ingredient affects permeability/mobility and speed of release.

The amount of organic MDI and ACD used in the method will determine the weight of the wall formed microcapsules. In General, the amount of material forming the wall, usually from about 2 to about 75% by weight of the microcapsule. Most preferably, the wall will be from about 4 to about 15% by weight of the microcapsule.

In the case of this invention, the amount of material forming the wall is about 2-20% of an oil phase. For the preferred amount of 6% of the wall material wall thickness for microparticles with an average diameter of 10 μm can be calculated and it will be in the range of 100 nm.

For applications where the desired microcapsules especially of small size (for example, from 0.5 μm to 10 μm average particle size, most preferably from 1 μm to 5 μm), found that soluble in oil surfactant type Atlox® 4912 added to the oil phase before phase emulsification greatly reduces the size of the particles. You can apply other copolymers, preferably consisting of polyglycol (for example, polypropylenglycol) and hydroxylated floor the fatty acids.

The preferred concentration in the oil phase is from about 5 to 25% by weight of the amount of material forming the wall.

It is impossible to fully describe in a limited description of the patent as any composition can be achieved using the method according to this invention. The person skilled in the art will have to do some experimental work to complete the present invention. The disclosure of the description and examples is in the number of granted patent document, more details describing how to obtain microcapsules in the range of the claimed compounds. With respect to compositions of microcapsules, note that this type of songs (capsule suspension, CS, and suspoemulsions, SE) on the merits is extremely complex. Documents that provide basic and advanced information technologies songs that will allow the person skilled in the art to reproduce the invention with unnecessary difficulties are: The e-Pesticide Handbook, British Crop Protection Council; Asaji Kondo. Microcapsules. (1970) Nikkan Kogyo Shinbun Ltd.; and Kondo et al. Microcapsules (1977) Sankyo Publishing Co., Ltd; Asaji Kondo. Microcapsule processing and technology (1979) Marcel Dekker Inc.; N. Cardarelli. Controlled release pesticide formulations. CRC Press (1976).

Technology microcapsulation you cannot deny the complexity, the complexity added to the field of compositions of microcapsules. The critical stages are stage emulsifier and, which can lead to a phase transition, if the equipment (ultraturrax, anchor stirrers, pumps) not very well known to the user, also critical is the management of low relative humidity, reaction time and temperature, adapted for vessels, where examples of re-perform, etc. for Example, in Example 1 was applied to the reactor at 2000 l to repeat the same example in a laboratory reactor it is necessary to apply knowledge of chemical engineering to play the reaction in the same way in a small reactor (e.g., 500 ml), conditions of heat transfer, turbulence and shear stress, obtained in 2000 l the reactor.

This invention is primarily devoted to agrochemical compositions, but thanks to the advantage of the type of wall material (polyurea+acetylenecarbonic) microcapsules have a glass transition temperature in the range from room temperature to 200°C. thus, the material for the capsule wall of the obtained microcapsules shows the response to heat, and they are acceptable for forming heat-sensitive recording materials and all applications coming from this (ink, fabric and so on). The use of microcapsules according to this invention in the field of materials phase transformations like that already described. In this case, preferred are the two which is the final product with the dried microcapsules, it is easy to reach by traditional spray drying of the microcapsules according to this invention. In this case, no matter the presence of specific emulsifiers or hydrocolloids for dissolution in water of the composition of the microcapsules upon subsequent application (as happens in most of the agrochemical compositions). In the case of applying the present invention for materials phase transformations the main difference is that the oil phase consists mostly of wax or oil, for example, hydrogensource vegetable oil, which is able to store and generate heat (usually with a melting point of from 0 to 50°C), together with the materials forming the wall, a catalyst (preferably dibutylamine laurate) and, eventually, additional solvent with a high boiling point and low vapor pressure, to facilitate microcapsulation wax.

It is important to note that for the adaptation of the microcapsules according to this invention for such applications (for example, dry microcapsules for shoes, gloves, foam for seats, all equipment, clothing) need, therefore, to avoid the release of the active ingredient (for example, wax with a melting point of 37°C). The aqueous phase, as explained in the description above is only medium-medium containing dispersing agents, protective colloids, etc. that neo is well to obtain acceptable dry compositions of microcapsules (not water phase, contains the components of the composition for the final applications in agriculture, most of the components of the composition, aimed at drying by spraying or other means to remove water and obtain a liquid composition of the microcapsules). Of course, agricultural compositions containing microcapsules according to this invention, in the dry state is very acceptable with the microcapsules according to this invention, but then the aqueous phase must be performed in a known dispersing agents, moisturizers, etc. to function in the field, but this is not necessary for the microencapsulation of catalysts or PCM.

You should not go into this aspect, because the method of obtaining dry microcapsules are well known to the person skilled in the art, this invention does not contain any innovations in this respect. However, this invention is a new type of microcapsules containing such PCM (or heat-sensitive recording materials or catalysts). For this use of the materials forming the wall should be about 5-10 times more (keeping the same ratios) to limit the release of compounds and extending the existence of the microcapsules. It really regulates the rate of release, but to achieve the slowest possible speed vysvobozhdeny is. "Cuatro dedos" cross-linking enable ACD according to this invention (one "finger" for each of the substituted nitrogen) provides greater flexibility microcapsules for resistance load pressure in such applications with PCM (which in turn is also advantageous for applications in agriculture with the load at the time of receipt, packaging, composition and final use by agricultural workers in the field, for example, the pressure in the nozzles of the sprayer).

If microcapsulation catalysts, it is obvious that the dispersed catalyst in the oil phase (for example, by applying Atlox® LP-5 or other oil dispersant) can be used as nuclear liquid dispersion for encapsulation. Already stated is known catalysts (e.g. platinum or palladium catalysts or the OS tetroxide) are obvious application of this invention, namely, for use of the advantages or features of the wall in this invention, is made of ACD and polyureas, compared with the conventional polyurea-microcapsulating catalysts. Everything mentioned in this document, particularly the walls of the ACD and polyurea compared with the walls of polyurea can be applied for such catalysts.

Thus, the examples are directed to the more complex area of agrochemical compositions,a clear proof, this target agrochemical composition according to this invention, on the basis of chemical and physicochemical characteristics (due to the unique characteristics of acetyltyramine monomer and characteristics of the way), performs its task, because it is possible to choose a suitable quantity of isocyanates (in this application for the first time disclosed the actual use and good functionality reactions using less toxic and reactive isocyanates such as TMXDI) and additional new parameter in this invention, acetylanthranilic monomer, to meet any requirement based on the size of particles, speed of release, and other components of the composition are selected to meet the required density, viscosity and other chemical and physico-chemical characteristics, by routine errors and preliminary tests or traditional techniques and methods of technology microcapsulation.

If the specialist in this field will want to repeat this invention, it does not matter what material is microcapsular. In the case of agrochemicals the only limitation is that it must not react with the material forming the wall that can evaluate chemist by considering relevant functional groups of the material forming the x wall, and agrochemicals. Those with which combinations are acceptable, it should be mentioned in the briefing book incompatibility of agrochemicals or brochures of the manufacturers of agrochemicals. Methods of grinding and dispersion of materials in the oil phase are well known, and known to the inclusion of solid agricultural chemicals, insoluble in water, in the aqueous phase (for example, by fine grinding). As soon as agrochemicals for microencapsulation selected, you need to choose the materials forming the wall. As the first choice recommended compounds and proportions mentioned in the description and examples, as well as certain ratio. If you want to include the material forming the wall, not directly disclosed in the examples, it should come primarily from similar reactivity with regard to the above comments. If the reaction of isocyanates does not occur, it is necessary to increase the temperature and/or increase the catalyst, the catalyst is first choice - dibutyrate laurate. If it's still not enough, then you should consider the reactivity of each isocyanate and exclude combinations of isocyanates, which due to their low reactivity (data available from the manufacturers) will not react. In principle, all reported ACD is able to react with a combination of aromatic and alifaticheskii the isocyanates, but again, if this does not occur, it is necessary to raise the reaction temperature and/or the number and type of catalyst for the ACD (for example, to replace R-ethylsulfonyl stronger p-toluensulfonate acid), or modify by mistake and the experience (there is not a separate theory on this issue in the public books) ratio of materials forming the wall, in the presented ranges. Emulsification is a critical stage, and in the case of phase transitions should be adapted to shear stress to the volume and geometry of the tanks. In addition, for microcapsules with low content material of the wall should be carefully taken too high shear stress during the formation of oil drops (can be destroyed quickly formed a wall of prepolymers polyurea before switching ACD).

Speed release, the normal information for the chemist, specializing in compositions with controlled release, enough for selecting the appropriate isocyanates and ACD. Obviously, ACD longer alkoxy or hydroxyalkyl groups will give a more rapid release, because the pores more. Therefore, smaller particles (obtained higher shear stress and the use of surfactants in the oil phase) will lead to a greater rate of release. Also, a larger number is on the sidewall material in wt.% relative to the weight of the entire filled microcapsules will slow down the release.

If microcapsulation RSM, it is obvious that you want an impenetrable wall that follows from the above instructions, and the use of more material wall than for applications in agriculture. It is interesting the use of ACD with alkilirovannami in medium circuits (for example, N,N'-diethoxylate, N",N"'-dimethylacetophenone), because, although it may increase the size of the pores, on the one hand, relatively common in this area the polyurea walls, on the other hand, increases the flexibility of the microcapsules and resistance to pressure, which is usually in traditional applications of RSM (special fabrics or foams).

In the case of encapsulation of catalysts ACD provides a unique rate of release, which should be adapted to the intended use of the catalyst: for example, in the hydrogenation with microencapsulated polyurea-ACD palladium when the pressure is conveniently achieved a higher percent of ACD in the wall. In contrast, for applications in biotechnology reactions catalyzed by osmium-tetroxide, need larger pores, suitable ACD with relatively highly alkylated chains (for example, tetrabutoxide acetylenecarbonic).

The specific details disclosed mentioned materials forming the wall, ACD in some embodiments, implementation of lechyutsya fact, that where the number of substituents R₂, R₄, R₆, R₈denoting hydrogen, in the same individual compound (I) is limited to one or two.

The aromatic isocyanate may be Monomeric aromatic isocyanate or prepolymer aromatic isocyanate, most preferably prepolymer aromatic isocyanate.

Aliphatic isocyanate may be Monomeric aliphatic isocyanate or prepolymer aliphatic isocyanate, more preferably Monomeric aliphatic isocyanate.

Preferred aromatic isocyanate has the formula (II) and on the chemical structure relates to oligomeric compounds of mono-, di - and triisocyanate, substituted toluene

where n= from 0 to 6, most preferably n=1.

Preferred aromatic isocyanate is a difenilmetana-4-4'-diisocyanate and, optionally, mixtures of isomers and homologues.

Preferred aliphatic isocyanate is an m-tetramethylene diisocyanate.

Aliphatic isocyanate (even singular) should be understood as, optionally, a mixture of different aliphatic isocyanates, respectively, the same for aromatic isocyanates.

The inventive polymer formed by the reaction of the materials forming the wall,where the ACD is a mixture of different compounds with different substituents at the stated formula (I).

Relatively oligomeric ADC, there is a mixture of compounds (I) in the form of oligomers up to 10 mol per mole, and the total amount of monomers, dimers, trimers and tetramers, at least 75% wt.% the whole mixture ACD in wt.%.

Applied ACD may be a compound represented by the formula (I).

ACD can consist of substituted acetylenecarbonic, Monomeric and/or low oligomeric (from 2 to 10 monomers per molecule), and/or unpolymerized compounds (I), and the content of highly polymerized monomers, more than 100 monomer molecule, below 10% in wt.% regarding the content of monomers in weight percent, preferably less than 0.5% in wt.%.

Also interestingly, if 100% solution mixed ACD consists of Monomeric substituted derivative of acetylenecarbonic (I)at least one substituent R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈different from the others.

The inventive polymer characterized in that the compound is a derivative of acetylenecarbonic with low content of hydroxyalkyl groups (up to 50%), thus, the degree of polymerization due to the hydroxyalkyl groups are not too high, which ensures convenient for the regulated release of the pores of the walls of the microcapsules formed from a polymer, and the expression "the suitability of Regulus is one of release" will be clear to the expert in the chemistry when considering commercially acceptable products.

The polymer according to the claimed invention differs in that the compound (I) is selected as a separate ACD compound in Monomeric and/or dimeric and/or trimeric form, and not as a mixture of various compounds included in formula (I).

A mixture of compound(s) (I) may contain hydroxymethyl up to 40%, in particular, the total number of groups R₂, R₄, R₆, R₈compounds (i) (C) or a mixture of compounds (i) (C), where the group mean hydrogen does not exceed 40% of the total amount of all types of groups R₂, R₄, R₆, R₈in the compound or mixture of compounds.

Can be applied to any of the above-mentioned polymer, characterized in that the solution mainly as industrial obtaining the compounds (I) it consists of Monomeric compounds (I), where all substituents R₁, R₂, R₃, R₄the identical, R₅, R₆, R₇, R₈the same among themselves, a R₉and R₁₀represent hydrogen atoms.

Preferred ACD are N,N',N",N"'-tetrabutoxide acetylenecarbonic, N,N',N",N"'-tetramethoxy acetylenecarbonic (Powderlink 1174), N,N',N",N"'-tetramethoxy acetylenecarbonic, N,N',N",N"'-tetrapropoxide acetylenecarbonic, N,N',N",N"'-tetrapropoxide acetylenecarbonic.

The most preferred compounds (I) are N,N',N Is The',N"'-tetramethoxy acetylenecarbonic and N-N',N",N"'-tetrabutoxide acetylenecarbonic for use separately or in combination.

The compound (I) or a mixture of compounds (I) can even be applied in solid form at 20°C or more by dissolving or dispersing in an oil phase. In this case, the compound (I) or a mixture of compounds (I) are dissolved and/or dispersed in an acceptable organic solvent to allow the inclusion of solids in a liquid mixture of materials forming polymer, for example, gamma-butyrolactone or naftovod solvent (Solvesso 100, 150 ND 200 ND).

Applying the method as described above, but for a more detailed explanation is given next.

In short, the disclosed method of microcapsulation by interphase polymerization, where the continuous phase is water and the discrete phase is water-immiscible phase, subject to conclusion in microcapsules, and this method made the usual uid reaction polymerization, characterized in that microcapsule wall formed by the reaction:

aromatic isocyanate,

aliphatic isocyanate,

substituted acetyltyramine compound or mixture of compounds of formula (I).

More detail is described a method of obtaining a microencapsulated composition including one or more substance that remains inside the microcapsules after receipt of such compositions, characterized in that:

I) prepare two phases:

a) m is kanou phase is prepared by mixing, by dissolving and/or dispersing one or more active material and mixing, dissolving and/or dispersing the following components:

A.1) forming the polymer materials;

A.2) soluble or dispersible in the oil, the catalyst suitable for the formation of a polymer of substituted polyurea of acetylenecarbonic;

A.3) finally, the solvent or dispersant;

A.4) finally, soluble in oil surfactant;

A.5) the active ingredient or mixture of active ingredients, which in the case of application in agriculture are active pesticides and related chemicals, in other areas, respectively, the materials phase transformations, ink, thermosetting materials or such that the person skilled in the art considers the active ingredient, mainly for microcapsules, each specific use.

A.6) finally, additional active ingredients are dissolved or dispersed in the oil phase, the components of the composition for the stability of water-immiscible or water-soluble materials, the stability of the other components of the composition, the stability of the microcapsules, the stability of any component to the light by organic compounds, heat, and/or the load pressure, and/or microbiological zag is yasneniyu, or stability of the composition as a whole;

b) the aqueous phase is prepared by mixing, dissolving and/or dispersing

b.1)water;

b.2) a separate emulsifier or mixture of emulsifiers;

b.3) polymer type PVA or PVP or any of its derivatives, or any mixtures of these polymers;

b.4) lignosulfonate or a mixture of lignosulfonate;

b.5) optional, moisturizer;

b.6) finally, additional components of the composition for regulating the pH to 6-7 or to improve the stability of water-immiscible or water-soluble materials, the stability of the other components of the composition, the stability of the microcapsules, the stability of any component to the light, especially active ingredient(s), heat, and/or load pressure, and/or microbiological contamination, or stability of the composition as a whole;

II) an oil phase include in the aqueous phase at about 45-70°C, under stirring, the temperature depends on the reactivity and the choice of catalyst in the oil phase, and a final period of high shear stress is a few minutes;

III) provoke the emulsification of the oil phase in the aqueous phase, and at the same time begins the formation microcapsule wall at a temperature of from 60 to 90°C;

(IV) then add the catalyst, which causes the formation the of the walls of the microcapsules mixed polymer substituted polyurea of acetylenecarbonic;

(V) shake formed the reaction solution with a very low voltage offset, low enough not to damage the microcapsules, for about 1-4 hours;

(VI) does not necessarily increase the temperature of 70-90°C for stage V);

VII) optionally, add the components of the composition for the final regulation of pH (3 to 12), viscosity modifiers, humectants, antifreeze means, an antimicrobial agent, a protective agent against light and any other component of the composition, is acceptable for microencapsulated compositions, and may not necessarily add all these connections, or some of them in the water or oil phase, as previously described.

Also describes how, unitary with the scope of the present invention, as a method of obtaining a composition, typical capsule suspension containing dispersed water-immiscible material or a number of water-immiscible materials, characterized in that the material is microcapsulated in discrete polyurea microcapsules-acetyltyramine copolymer, in which:

(a) provide at temperatures from 45°C to 70°C, preferably from 40°to 60° and most preferably from 40°C to 55°C, the variance

(i) a water-immiscible phase comprising active agricultural water-immiscible material and the materials, be capsulerebel, an aromatic isocyanate, an aliphatic isocyanate and ACD, ultimately, acceptable solvent for the dissolution of any previous connection, which may be in solid form, ultimately, a dispersant, if the active connection is solid, and eventually also surfactant;

(ii) an aqueous phase comprising a solution of water, surfactant, or mixtures thereof, a protective colloid or a mixture thereof, the polymer having the properties and surfactant and protective colloid; and

(b) heat and maintain the specified variance in the temperature range from 60°C to 90°C, after which the specified water-immiscible material capsulebuy in discrete microcapsule shell of substituted polyurea of acetylenecarbonic;

(c) once the microcapsules are formed, and forming the polymer materials crypto mostly spent, optional add an aqueous solution containing the components of the composition required to functionally acceptable agricultural composition that includes a viscosity modifier, clay or similar mesoporous materials, preferably thick or zeolite, hydrocolloids, an antimicrobial agent, a protective agent against ultraviolet radiation, moisturizers, additional surfactants.

Connection A.4) or b.2) m which can be (meta)acrylic graft copolymer and/or selected from the group of surfactants: ethoxylated alcohols, ethoxy and/or propoxy block copolymers, polyvinyl alcohol, polyvinyl pyrrolidone and any derivatives or graft copolymers of the above surfactants, selected from the group of ethoxylated alcohols, ethoxy and/or propoxy blockcopolymer, polyvinyl alcohol, polyvinyl pyrrolidone and any derivatives or graft copolymers of the above surfactants, preferably polyvinyl ester of a fatty acid or polyalkyl(meta)crylate with a molecular weight of from about 100,000 to 200,000 daltons.

The surfactant added to the aqueous phase, is polietilenglikolya ether polyhydroxystearic acid with a molecular weight of from about 10,000 to 25,000 daltons.

Preferred fatty acid surfactant is stearic acid.

The patented mixture of lignosulfonate claimed a method of producing microcapsules characterized in that the solution (I) (b) contains the complex contained in the mixture in weight percent, 15-25% of lignosulfonate, 5-15% of polyvinyl alcohol and 100% of the water connections are selected in such a way that the lignosulfonate and the polyvinyl alcohol is completely dissolved in water, and this solution is heated to 60-90°C for 5-20 minutes before use in the method of microcapsulation.

As an important application of the microcapsules according to this invention claims a method of obtaining the agricultural HDMI is the type of the suspension concentrate, characterized in that:

i) preparing an aqueous suspension of microcapsules;

ii) suspension concentrate in an aqueous medium is prepared with the required active ingredients or near them (provided they are chemically compatible in this environment and are useful in agriculture) in the usual way, by grinding, and provide the necessary components of the composition and, optionally, further provide additional water-soluble active ingredient or a number of them (if all the active ingredients are chemically compatible and useful in agriculture) and the necessary components of the composition;

iii) mixing the suspension of (i) and (ii) if a mixture of active ingredients useful in agriculture;

iv) finally, add the components of the composition in the mixture for stability and functionality of the composition if such components of the composition are not yet present, or present in insufficient quantities in the mixture formed before this stage, or, optionally, they were already added in the previous steps in the required quantity to be present in the final composition;

v) finally, filter the mixture (iii) or (iv)to remove any unwanted residue that can damage the correct functionality of the suspension concentrate in order to avoid blocking of nozzles filters the filters during the final application of the suspension concentrate in the field.

Preferred agricultural compositions of microcapsules (in any type of composition comprising microcapsules) are the following active ingredients or mixtures thereof (although practically you can microcapsulating any agrochemicals, because it is soluble, dispersible and stable in the oil phase): verklaren, PYRETHROID and/or natural origin pyrethrin or mixtures thereof, lambda cigalotrin, gamma cigalotrin, supercialis, alpha-cypermethrin, clomazone, the combination of flurochloridone, and/or lambda-cyhalothrin, and/or clomazone, and/or metazachlor, and/or alachlor with other pesticides or agrochemicals, including antidotes, catenary, anti annelids, and/or semiochemical, tefluthrin and/or phenothrin, alachlor and/or acetochlor, pendimethalin, trifluralin, organophosphates, chlorpyrifos, endosulfan, fenoxaprop, triazole fungicides, propiconazole, ketoconazole, triadimenol, epoxiconazole, tebuconazole (optional, where the oil phase contains customary in agriculture solvent type substituted alkylate or N,N-dimethylacrylamide), fluroxypyr.

Due to the removal of toxic isocyanates or at least reduce the number and Toxicological profile of the microcapsules according to this invention may be applied to the microencapsulated farmaceuticas is their preparations for their application in medicine.

To better understand the complexity of the invention and to reproduce the invention to a person skilled in the field will help the examples below.

Example 1

Disclosed is a method of obtaining microencapsulated compositions of verkleiden at a concentration of 25% (weight/weight).

LignoGAT™ is a patented solution disclosed here, comprising water, Celvol™ 205 and Kraftsperse™ 25M, the ratio of which varies according to (respectively): 60-70%:5-15%:5-30%. In this particular case, the ratio is 65:5:30.

When both phases are well mixed in a separate reactors [it is important to note that some heating is necessary to enable the solid crystals of cis-verkleiden with a melting point of about 71°C], the oil phase include slowly at about 50°C in the aqueous phase (at 35°C and pH adjusted to 6.5 with citric acid), amblyraja the organic phase into small droplets in a continuous aqueous phase with a stirrer with a high shear at about 2500 rpm (in the usual cylindrical 2,000 l reactor) for 15 minutes. Then the mixer with a high shear is stopped and anchor stirrer regulate up to 50 Rev/min Material forming the wall, presents in the organic phase (isolan who you and acetylanthranilic monomer), reacts with water at the boundary of the oil/water for forming the preliminary wall of the capsule around the oil droplets containing the active ingredient verkleiden. The temperature was raised to 50°C at the beginning of the reaction. Then add to 0.15% (weight/weight) p-toluensulfonate acid (dissolved in isopropanol) for termination of polymerization in the side of the aqueous phase and reactions of the formation wall. Next, the mixture is maintained at about 48°C for five hours. Thus, it avoids any sediment isocyanates and/or free acetylanthranilic monomers. Then allow the mixture to cool. Measure the pH and adjust it from 9.5 to 10 with 50% aqueous NaOH solution. Finally, in order to stabilize add the following solution:

The resulting composition is homogenized anchor stirrer at 100 rpm, and then filtered through a 100 μm nylon sieve.

Example 2

Get microcapsules according to the method of Example 1 and compared with the commercial ftoruglerodam CS 250 g/l (Racer™).

The microcapsules of Example 1 are presented in Figure 1.

Formed by the method of Example 1, microcapsules have the following options:

It is noted that verkleiden has two isomers (cis and trans) with different melting points, and the invention allows the free capsulation and solid and liquid materials (even adsorbed/absorbed/soluble gaseous materials in solid or liquid basis).

Infrared analysis Racer™ CS shows that the capsule wall consists of TDI and PAPI, while the present invention TDI replaced with a much less toxic and less reactive able TMXDI. Special conditions crypto according to this invention allows to perfectly match the physico-chemical and chemical (on the application in agriculture) characteristics Racer™, with different composition of the capsule wall, a protective colloid (using LC-MS (liquid chromatography-mass spectrometry) is defined as the type of Daxad™ 23 Racer™), a primary emulsifier (using LC-MS th the manufacture of chemical sample, defined in Racer™ as type Pluronic™ L64) and other components of the composition.

Observe that the microcapsules according to the method of the present invention are spherical three-dimensional structure, however, areas sometimes have a dent (DEP) on the surface, shown in Figures 1 and 2 arrows (sometimes the concave surface area is almost half the entire surface of the capsule), which is not found in other commercial microencapsulated pesticides or microcapsules for other purposes. I believe that the reason for this effect is a specific reaction TMXDI + PAPI + acetylanthranilic monomer.

Definition decapsulating active ingredient perform the following way (this is presented in the rest of the examples).

Filtration of the sample composition, suspended in water:

100 mg CS sample is suspended in 15 ml of a mixture of water and dipropyleneglycol;

- filtered through a glass fiber filter;

- washed with 2×5 ml of a mixture of water with dipropyleneglycol;

- define and. I. in the filtrate by analysis of HPLC-UV (high performance liquid chromatography using ultraviolet rays) or GC-FID (gas chromatography with flame ionization definition).

Conditions of use of the HPLC are usually the following: Lichrospher 100 CN - 5 μm, 250×4 mm; column thermostat: 32°C; volume injected: 10 μl; mobile phase: 97% (the volume of/the volume) n-hexane, 3% (vol/vol) isopropanol; flow rate: 1 ml/min; detector: at 240 nm; analysis time: 35,0 minutes.

Example 3

Composition is prepared as described in Example 1, in which the material forming the wall, substituted prepolymerisation etherified urea resins, Beetle™ 80, and prepolymerisation based on the method mentioned in U.S. patent 6485736. Then the total number of tetramethoxysilane acetylene urea and isocyanate substituted, respectively, of the material forming the wall, and gamma-butyrolactone are removed from the formula. Detail of the microcapsules present in the composition of verkleiden only after the end of the way, precisely made according to example 1 (with the above modifications) (detail in Figure 3), and the particle size varies, and more microcapsules and immediately release the contents in the aqueous phase. The average particle size is of 29.3 μm, and the 90 percentile is 71,64 microns, making microcapsules inappropriately large and too fragile.

Example 4

In the laboratory will receive the following composition in Example 3, with the same ratio wt.%, as in Example 1, but 1 litre of final composition. Consistently used the 14 reactors with cooling and heating.

After the final emulsification regulate the appropriate pH and final add solution d is I stability, shake and allow the final mixture to reach room temperature, immediately measure the particle size, get statistic "90 percentile (10% of the microcapsules have an average diameter greater than this value).

Neopalimovsky active ingredient measured by centrifugation of the microcapsules, and then analyzing the supernatant by GC-FID generally accepted analytical method. The emulsion stability was analyzed according to the definition by FAO/WHO (food standards) for the stability of the emulsion lambda-cyhalothrin CS (composition of the same type (capsule suspension)), this document is included in this description by reference. Only values with a mark of "very good emulsion stability" meet the separation requirements oil/destroyed emulsion and the formation of crystals in the emulsified composition in water. Crystallization was evaluated subjectively (but consistently with the estimates from different samples) according to the survey, 5 samples of the undiluted composition under a microscope with lenses ×10 and ×40. The Figure 4 presents the crystals in PR-1 through 240 hours storage at 35°C.

The following results are obtained

You may notice that the only acceptable compositions are formulated with ACD, these commercial compounds containing a significant amount of monomers (or dimers or trimers) (PR-11, 4-12, 4-13 and 1)give the best results. However, these acetylpenicillamine cross-linkers that contain a lower amount of monomers, give larger particles. PR-8, based on benzoguanamine resin, is interesting in that the particle size of the microcapsules is very acceptable, is very good emulsifying properties, but only with the help of surveillance capsules under a microscope it is possible to understand that a significant part of them are destroyed. All connections melamine and urea indicate a bad characteristic with high quantities decapsulating of verkleiden and the subsequent formation of crystals. In examples 4-8 can be observed reversible agglomeration, as shown in Figure 5.

Example 4

The following example was used by other primary emulsifier and a protective colloid. As in the previous examples, Example 1 as a model, run some modifications. The solution LignoGAT™, based on polymer reaction product containing lignosulfonates, replaced (and in the same quantities is) on Agrimer™ AL10 and PVP 15 ratio (in wt.% 1:1). In this way was microcapsulated quizalofop-p-ethyl, dissolved in Solvesso 100 at 50% (warm).

To reduce the size of the particles (which is expected to be more because LignoGAT™ replaced by this new mix) speed stirrer with high shear stress increased to 3500 rpm for 5 minutes. The average particle size of the formed microcapsules is 5.1 μm at 90 percentile of 8.3 μm. The emulsification properties (5% of the composition in water in a 100 ml measuring cylinder) does not show phase separation after 2 hours, the formation of the crystals are missing. The wet residue screening, 150 μm, amounted to 0.03%, and the dispersibility and suspenderbelt were, respectively, 81% and 89%.

Example 5

This example was microcapsulated in Example 1 with the same components and proportions (for 1 liter of the composition) with the following exception:

PR-1: isocyanate mixture TMXDI and PAPI and Powderlink™ 1174 [just like in App.1].

PR-2: isocyanate mixture of TDI and PAPI.

In both experiments were capsulerebel fenvalerate, also dissolved in the solvent-based hydrocarbon at 50% (Marcol™) with advanced soft heated to 50°C and mix, then let the mixture cool. The final composition is esfenvalerate 250 g/l capsule suspension (allowable density = 1 g/cm³).

The results are presented in the following table:

As can be seen, the reaction with TDA and PAPI gives the applicable particle size of the formed capsules, however, the number decapsulating material is too high (32%), were analyzed using centrifugation and HPLC-UV supernatant. Observed that the reaction took place with the active selection WITH₂and noted the sudden increase in temperature (2 l reactor was heated up to 75°C in PR. 5-2, while in PR-1 recorded maximum temperature of 58°C). Examination under the microscope showed that the number of microscopic pieces of wall material reacted without forming wall (thus, the microencapsulated material was absent). All this indicates that ways is more reactive TDI was unregulated (not enough time was allowed for good emulsification and at the same time for forming the material of the wall), namely, the way TDI with less predictable and less amenable to adjustment than the method with TMXDI + PAPI + ACD.

Example 6

The composition of the lambda-cyhalothrin prepared according to the following formula (500 l). Components divided by their functionality. The First Table Etc. 6.1 refers to the aqueous phase and the oil phase prior to emulsification/crypto necessary materials. In The Table Etc. 6.2 shows the connections that are responsible for the stability of the composition. Bring to 100% of the composition.

Conditions crypto above-mentioned components:

the emulsification perform very slowly (according to the total volume) in order to avoid the phase transition anchor stirrer at 100 rpm and a Cowless mixer at 1500 rpm;

the reaction temperature: 50°C;

stirrer high shear stress at 6000 rpm for 5 minutes during the encapsulation (MDH), adding Cycat 4040;

the aging time of the microcapsules at 55°C - 4 hours.

The characteristics of this composition are as follows (all measured parameters are standardized according to FAO definitions and/or methods CIPAC (international Council on cooperation in the field of analytical journal the Oh chemistry of pesticides):

lambda cigalotrin: of 10.05 g/l,

the ability to suspendibility (CIPAC MT.161): 99 wt.%,

the range of pH (CIPAC MT,2): 6,4+/-0,5,

the particle size measured by laser analyzer Mastersizer Micro 2.18: D[v, 0.5]would=to 1.05 μm,

D[v, 0.9]=2,28 μm,

the viscosity, measured Haake Rheowin Pro 2,67: η (viscosity in PA·s when τ₁(1,0)=2,73,

η (viscosity in PA·s when τ₁₀(10,0)=0,08,

the exit point (τ₀in PA at γ=0=7,41,

density at 20°C (A.Paar DMA 38): 1,0318+/-0,0012 g/ml.

Example 7

How microcapsules according to this invention differs from all published patents used on an industrial scale worldwide for agrochemicals included on the main chemical components, the nature and structure of the wall and physico-chemical characteristics of the microcapsules. However, in order to be able to apply this invention, a further requirement is the ability to achieve the speed of release and chemical equivalence of inert ingredients to already registered products on the market (to allow the sale). According to this invention have found that with proper selection of an appropriate acetylanthranilic compounds, surfactant and stabilization system and the reaction conditions of this invention can be achieved physico-chemical characteristics of commercial compositions as a whole (namely, parameters otnositel the laws, such as 91/414 EEC, determine the FAO/WHO etc) by, quite different from that known in the prior art. This is the exact choice glycoluril with low reactivity, mild reaction conditions (temperature much lower than in the documents of the prior art), the avoidance of additional amine or sulfur compounds as catalysts or materials forming the wall, and the conclusion reached by organic acids, which allows us to produce the composition according to the order outlined by the rate of release (or rapid, or prolonged) and biological efficiency.

For this demonstration, performed a comparison of the method of production according to this invention to obtain commercial song lambda-cyhalothrin according to 91/414 EEC. The control material is a sample of Karate™ Zeon 10 CS.

Capsulati GAT lambda-cyhalothrin 10 CS (GAT-lCy) performed according to the method described in PR (including detailed explanations of the way, he fully disclosed in the previous examples and/or in the description). The above values were the values of 10 different samples, and statistical differences were assessed by analysis of t-student with an appropriate transformation to normalize the data using arcsin(sqrt(x)) for percentage values.

In Figure 7 you can see that the particle size of the composition in this image the structure is distributed equally, with minor differences, or in the middle, or at the 90th percentile, and both products meet the FAO definitions.

Regarding the ability to suspendibility FAO defines at least 80% lambda-cyhalothrin found in suspension after 30 minutes in water D standard CIPAC. Both products far exceed the minimum GAT-lCy and KZ show the same 99,2% ability to suspendibility, without significant differences by analysis of t-student test.

Spontaneity of dispersion [%]was determined by CIPAC MT 160. FAO defines at least 90% lambda-cyhalothrin in suspension after 5 minutes in the water D standard CIPAC at 30±2°C. GAT-lCy represents 92% of the variance, while KZ is 94%, but no significant differences in the analysis of the t-student test.

The flow in [%] was determined according to CIPAC MT 148. Regularly viscosity was measured in the laboratory for assumptions, what will be the fluidity (faster, cheaper and easier to measure viscosity), but definitions FAO indicate only that the analysis of turnover, because the "real" effect of viscosity on the product is difficult to work by hand, in particular, to remove agrochemicals from the package or bottle, and washing bottles for environmental reasons. FAO defines the maximum "residue" of 1.5%. Fluidity GAT-lCy equivalent yield KZ and meets the definition of FAO 463/CS (2003) for the "remainder after washing". Values (no significant statistical settled their differences) the following:

the rest and residue after washing, respectively, for GAT-lCy: 2,6% and 0.3%;

same for KZ: 2,1% and 0.3%, without significant statistical differences.

The stable foam in [ml] after 1 minute was determined according to CIPAC MT 47,2, and no samples from any stable foam after 1 minute.

Both samples meet the definition of FAO and statistically not differ on any value.

Example 8

The rate of release of GAT-lCy and KZ.

For speed of release was used Directive OECD (Organisation for economic cooperation and development) for the analysis of chemicals No. 428. The analyzed compositions were (in pairs) GAT-lCy 10 g/l and GAT-lCy 5 g/l (obtained from example 6) in comparison with similar products Syngenta (KZ 10 g/l and KZ 5 g/l). For each sample performed one experimental experience.

The results are presented in Figure 8 and 9. It is clear that GAT-lCy initially has a faster release in both types of samples (partly because of wider pores in the particles originating from the applied chetyrehpaltsevye of acetylenecarbonic). However, when the conditions of the analysis of the contents of the lambda-cyhalothrin in the receptor cells in the case of KZ (5 CS 10 CS) lower.

Example 9

Got suspoemulsions containing 250 g/l of metazachlor and 33.3 g/l clomazone. In suspoemulsions solid finely chopped or diperkirakan the th emulsified or the active ingredient is in a continuous aqueous phase, while the discrete phase is represented by the microcapsules. In this example explains how to prepare microcapsule part of suspoemulsions, namely, the microcapsules of clomazone. Suspension concentrate, which is part of the composition is a concentrate of crushed and dispersed metazachlor (technically was obtained according to the void the German patent 2849442, more precisely according to the example, revealing the monoclinal suspension of metazachlor). Metazachlor can also be obtained according to European patent 12216 according to examples 2 (a) or (b) or examples 4 (a)or (b)or (C).

Formula capsule suspension clomazone consists of the following ingredients, in a way similar to the one used for microcapsulation lambda-cyhalothrin:

Suspension concentrate metazachlor separately prepared according to the following recipe:

Then suspended metazachlor mixed with the capsule suspension clomazone as follows:

This composition has the characteristics presented in Figure 11 (particle size) and Figure 12 (viscosity). The image of microcapsules are presented in Figure 6.

Example 10

Slow burning material (antimony oxide) was microcapsulated according to this invention together with the material of the phase change (PCM) perpendiculum, according to the method of the present invention. Then the aqueous phase was spray dried to obtain a liquid composition of microcapsules.

Example 11

The following have served microcapsulation of fluroxypyr by the formula capsule suspension clomazone of example 9 and the aqueous phase of example 6. Comparative analysis was performed microcapsulation prior art using TDI and PAPI that showed the average particle size 2,73 μm and 90 percentile 15,79 microns.

Measurement of each sample pre is presented in Figure 10 and is made according to the microcapsules.

The analyzed material forming the wall includes:

Specflex NE 138 - 2.25 part,

TMXDI - 1,12 part.

ACD is as follows:

Example 11-1 trimethoxysilyl manometry acetylenecarbonic 0,80 part,

Example 11-2 tetraethoxide acetylenecarbonic 0,80 part,

Example 11-3 tetraethoxide acetylenecarbonic 0,90 part,

Example 11-4 tetrabutoxide acetylenecarbonic 0,50 part,

Example 11-5 tetramethoxysilane acetylenecarbonic 1,00 part.

The results are shown in Figure 12, where differences were assessed by type and number derived acetylenecarbonic.

Example 12

Did two songs: one from example 6 (PR-1) and the same composition, but with the replacement of the material forming the wall, TMXDI on TXDI, and with the removal of 3% tetraethoxide of acetylenecarbonic (PR-2).

The residual isocyanate was analyzed by derivatization of the sample with 1-(9-anthracenedione)piperazine and determined using HPLC-UV at 254 nm. Since the aim of the analysis was to compare, quantify, in weight percent was not met. However, tested AU units of absorption of ultraviolet rays (for equally put 10 μl of solutions of 50 mg/ml in acetonitrile samples) to compare the amount of residual TDI, TMXDI and PAPI (because they suiryudan at the same time). The results showed that P-1 has a value of AU 641 mV (enter the detection limit), while PR-2 is set to AU 11 mV (below detection limit). Thus, the use of ACD is prevented by the presence of residual isocyanate in agrochemical compositions.

1. Microcapsules containing material with a solubility in water below 750 mg/l at 20°C, characterized in that the wall of the microcapsules formed by the reaction between phase polymerization of the materials forming the wall:
(a) aliphatic isocyanate(s), and
(b) an aromatic isocyanate(s), and
(c) the compound(ia) of the formula (I), acetylpenicillamine derivatives

where R₁, R₃, R₅, R₇represent independently from each other methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butylene, tert-butyl;
R₂, R₄, R₆, R₈represent independently from each other hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl;
R₉, R₁₀represent hydrogen or hydroxymethyl;
including oligomeric forms of the compounds (I)where the number of moles of the compounds (I) is from 2 to 10; and
microcapsules have an average diameter of from 0.3 to 25 μm in the measurement of conventional laser diffraction analyzer particle sizes with advanced conventional dissolved in water with stirring.

2. Microcapsules according to claim 1, where the aromatic isocyanates according to claim 1 (a) and eat formula (II):

where n= from 0 to 6.

3. Microcapsules according to claim 1, where the aromatic isocyanate is a difenilmetana-4-4'-diisocyanate, or a mixture of its position or stereochemical isomers, or PAPI (polyacrylonitrile).

4. Microcapsules according to claim 1, where the aliphatic isocyanate is an m-tetramethylene diisocyanate or TMXDI (trimethylhexamethylenediamines).

5. Microcapsules according to claim 1, characterized in that the compound (I) selected from the group of N,N',N",N"'-tetrabutoxide acetylenecarbonic, N,N',N",N"'-tetramethoxy acetylenecarbonic, N,N',N",N"'-tetramethoxy acetylenecarbonic, N,N',N",N"'-tetraethoxide acetylenecarbonic or N,N',N",N"'-tetrapropoxide acetylenecarbonic or mixtures thereof.

6. Microcapsules according to claim 1, characterized in that part of the agrochemical composition, and material selected from the group: verklaren, pyrethroids, natural pyrethrins, or mixtures thereof, lambda cigalotrin, gamma cigalotrin, supercialis, deltamethrin, alpha-cypermethrin, clomazone, tefluthrin, phenothrin, alachlor, acetochlor, pendimethalin, trifluralin, organophosphates, chlorpyrifos, endosulfan, fenoxaprop, triazole fungicides, tebuconazole, propiconazole, ketoconazole, triadimenol, epoxiconazol, fluroxypyr.

7. Microcapsules according to claim 1, characterized in, h what about the part of agrochemical compositions, and the material contains a combination of flurochloridone, and/or lambda-cyhalothrin, and/or clomazone, and/or metazachlor, and/or alachlor with other pesticides or agrochemicals, including antidotes, catenary, anti annelids and/or semiochemical.

8. The method of obtaining the agrochemical composition of a typical capsule suspension comprising microcapsules according to claim 1, in which
(a) provide at temperatures from 45°C to 70°C variance
(i) a water-immiscible phase comprising active agricultural water-immiscible material or materials to be capsulerebel, an aromatic isocyanate, an aliphatic isocyanate and the compound (I), in the end, an acceptable solvent for the dissolution of any previous connection, which may be in solid form, ultimately, a dispersant, if the active connection is solid, and, ultimately, surfactant,
(ii) an aqueous phase comprising a solution of water, surfactant, or mixtures thereof, a protective colloid or a mixture thereof, the polymer having the properties of a surfactant and a protective colloid; and
(b) heat and maintain the specified variance in the temperature range from 20°C to 90°C, after which the specified water-immiscible material capsulebuy in discrete microcapsule shell of substituted polyurea-acetylenecarbonic who were of mixed polymers;
(c) once the microcapsules are formed, and the material forming the wall, mostly spent, optional add an aqueous solution containing the components of the composition required to functionally suitable agricultural compositions, such as viscosity modifiers, clay or similar mesoporous materials, hydrocolloids, an antimicrobial agent, a protective agent against ultraviolet radiation, moisturizers, additional surfactants.

9. Microcapsules according to claim 1 in agrochemical compositions, where the microencapsulated material is used in the agrochemical suspension capsules, i.e. in CS composition, or in capsule suspension and suspension concentrate, i.e. ZC composition, or dispersible in water, the granules, i.e. WG composition.

10. Microcapsules according to claim 1, where the herbicide clomazone microcapsular for the formation of a capsule suspension, and this capsule suspension formulated together with the suspension concentrate metazachlor to obtain ZC composition type of metazachlor and clomazone.

11. Microcapsules according to claim 1, where the microcapsules comprise any type of composition that is acceptable for use in agriculture.

12. Microcapsules according to claim 1, where they are used to microcapsulation pharmaceutical or m the health connections, flame retardants, materials, phase transformations, thermosetting materials, inks, catalysts.