The present invention relates to microcapsules as a core-shell-particles, comprising a polymeric shell, a method of making them, a dispersion of those microcapsules in a liquid medium and the use thereof. The microcapsules comprise a core that contains a hydrophobic component.

Microcapsules are spherical objects which consist of a core and a wall material surrounding the core, wherein the core in principal can be a solid, liquid or gaseous component which is surrounded by the solid wall material. For many applications the wall is formed by a polymer material. Microcapsules usually have a volume average diameter from 1 to 1000 μηη.

A multitude of shell materials is known for producing the wall of microcapsules. The shell can consist either of natural, semisynthetic or synthetic materials. Natural shell materials are, for example, gum arabic, agar agar, agarose, maltodextrins, alginic acid or its salts, e.g. sodium alginate or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides, such as starch or dextran, polypeptides, protein hydrolyzates, sucrose and waxes. Semisynthetic shell materials are inter alia chemically modified celluloses, in particular cellulose esters and cellulose ethers, e.g. cellulose acetate, ethyl cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethyl- cellulose, and also starch derivatives, in particular starch ethers and starch esters. Synthetic shell materials are, for example, polymers, such as polyacrylates, polyamides, polyvinyl alcohols, polyvinylpyrrolidones or polyureas.

Depending on the type of shell material and the production process, microcapsules are formed in each case with different properties, such as diameter, size distribution and physical and/or chemical properties.

Polyurea core-shell microcapsules obtained by reaction of at least one diisocyanate and at least one polyamine are well known in the art, for example from WO 201 1/161229 or

WO 201 1/160733. According to WO 201 1/161229 or WO 201 1/160733 the polyurea

microcapsules are prepared in presence of polyvinylpyrrolidone (PVP) as a protective colloid.

The development of biodegradable microcapsules was carried out mainly for drug transport and in-vivo release applications. Attention toward biodegradable capsules was increased since environmental aspects of polymers started to be discussed in the public and efforts were made to reduce environmental pollution.

Generally polyurethanes are prepared by reacting a polyisocyanate with a polyol component. Typical polyols employed in the preparation of polyurethanes are polyether polyols or polyester polyols. There is still a demand for polyurethanes that are suitable as polymeric shell material in microcapsules. For certain applications it would be advantageous that said shell material apart from having good application properties is also biodegradable.

WO 2006/044305 relates to an isocyanate-terminated prepolymer composition obtained by reaction of methylene diphenylisocyanate with a polycaprolactone polyol. The obtained prepolymer is used in the manufacture of polyurethane or polyurea elastomers.

WO 2008/033224 relates to isocyanate-terminated polycaprolactone polyurethane prepolymers obtained by reaction of toluene diisocyanate and a polyol composition. The obtained prepolymer can reacted with an amine chain extender resulting in polyurethane elastomers.

WO 03/061817 relates to substrates coated with polymers, containing microcapsules in the polymer layer, wherein the polymers includes for example polyurethanes, polyurethaneureas, polyacrylonitriles or copolymers of styrene.

US 4,379,071 relates to a process for the production of microcapsules, wherein a diol or polyol which has a molecular weight of 400 to 10000 g/mol reacts with phosgene or a diisocyanate which contains at least two chloroformic acid esters or isocyanate groups per molecule. The resulting reaction product of those components is mixed with the desiered core material and a chain lengthening agent which is at least bifunctional.

EP 0780154 relates to a process for preparing biodegradable microcapsules wherein the microcapsules are made by the addition reaction between polyamines, in particular aliphatic primary or secundary di- or polyamines, and polyisocyanate components containing at least one bifunctional isocyanate with an average of at least one ester and/or amide group in the main chain.

However, there continues to be a need for microcapsules, wherein the size of the micropasules can be controlled in a wide range and that are capable of releasing an encapsulated ingredient under controlled conditions. There is also a demand for microcapsules which have at least one encapsulated hydrophobic component, wherein the microcapsules have enhanced stability against leacking of the encapsulated components from the capsules. Delayed release of the encapsulated active ingredients for crop protection, personal care compositions or

pharmaceutical compositions, is also of interest.

It is an object of the present invention to provide a microcapsule, wherein the shell comprises a polymer containing polyurethane and/or polyurea groups, which can be prepared by reactive microencapsulation, in particular by in situ radical polymerization, polyaddition or

polycondensation. It is a further object of the present invention to provide such microcapsules wherein the shell of the microcapsules has the afore-mentioned desired properties and containing a hydrophobic component as core material. Depending on the desired field of application in one variant the microcapsules should be provided as a "normal" dispersion, comprising microcapsules containing at least one hydrophobic core material in an aqueous medium as the continuous phase. Further, it is an object of the present invention to provide microcapsules for the use as or in a personal care composition, as or in a composition used for industrial or institutional or hospital desinfection, as or in a material protection composition, as or in a pharmaceutical composition, as or in a plant protection composition, as or in home care products. Last but not least, it is an object of the present invention to provide a microcapsule compositions having biodegradable segments embeded in the capsule wall.

Surprisingly, these objects could be achieved by microcapsules, wherein the core comprises at least one hydrohilic or at least one hydrophobic component and wherein the shell of the microcapsules comprises polyurea and/or polyurethane linkages. In particular, the shell material of the microcapsules according to the invention comprises a poly(ester-urethane) in

polymerized form.

The present invention relates to microcapsule comprising a capsule core and a polymeric shell, wherein the core essentially contains only hydrophobic components and the shell comprises in polymerized form

A) at least one poly(ester-urethane) containing at least 2 isocyanate groups, obtainable by reacting at least one polyester-polyol containing at least 2 OH groups with at least one polyisocyanate containing at least 2 NCO groups, and

B1 ) at least one polymeric polyamine having a weight average molecular weight of at least 300 g/mol and containing at least 3 amino groups reactive towards NCO groups,

B2) optionally at least one compound different from B1 ) which comprises at least 2 terminal groups which are reactive towards isocyanate-groups, which are selected from OH, NHR, or SH, wherein R is selected from hydrogen, alkyl, cycloalkyl or aryl.

The present invention further relates to microcapsule dispersion, comprising microcapsules wherein the capsule core contains essentially hydrophobic components, obtainable by a) providing a premix (lb) comprising the hydrophobic component(s) to be encapsulated (Cb), optionally a hydrophobic medium that is liquid at 20°C and 1023 mbar different from (Cb), and at least one component (A) as defined above and below, and

b) mixing the premix (lb) provided in step a) with an hydrophilic medium comprising at least one hydrophilic protective colloid, at least one component (B1 ) as defined which is defined above and below, and reacting the resulting mixture to form microcapsules dispersed in the hydrophilic medium.

The present invention further relates to a process for the preparation of the microcapsule dispersion, comprising microcapsules according to the invention, wherein the capsule core contains essentially hydrophobic components, obtainable by

a) providing a premix (lb) comprising the hydrophobic component(s) to be encapsulated (Cb), optionally a hydrophobic medium that is liquid at 20°C and 1023 mbar different from

(Cb), and at least one component (A) as defined above and below,

b) mixing the premix (lb) provided in step a) with an hydrophilic medium comprising at least one hydrophilic protective colloid, at least one component (B1 ) as defined above and below, and reacting the resulting mixture to form microcapsules dispersed in the hydrophilic medium.

The present invention further relates to a microcapsule obtained by the processes according to the invention. The present invention further relates to microcapsules obtained by the processes according to the invention in dry form. The present invention further relates to the use of microcapsules or microcapsules according to the invention or obtained by the processes according to the invention in a personal care composition, or a home care composition, or a composition used for industrial or institutional or hospital applications, or a material protection composition, or a pharmaceutical composition, or a plant protection composition. The present invention further relates to the use of the microcapsules according to the invention or obtained by the processes according to the invention in a cosmetic composition, a hygiene composition, a composition for industrial or institutional or hospital cleaning or disinfection, laundry detergents, fabric softeners, dishwashing liquids, household cleaners, industrial cleaners, oil recovery, adhesives, coatings, or constructions, or agro formulations.

The microcapsules according to the invention have the following advantages:

Small particle size and narrow particle size distribution

Good tightness and mechanical stability

- Sprayable

Partially made out of biodegradable building blocks

The terms "biodegradation" or "biodegradability" are synonyms and mean in the sense of the invention that the polymers decompose in an appropriate and demonstrable period of time when exposed to the effects of the environment. The degradation mechanism can be hydrolytic and/or oxidative, and is based mainly on exposure to microorganisms, such as bacteria, yeasts, fungi, and algae. An example of a method for determining biodegradability mixes the polymer with compost and stores it for a particular time. According to ASTM D5338, ASTM D6400,

EN 13432, and DIN V 54900, CC ree air, by way of example, is passed through ripened compost during the composting process, and this compost is subjected to a defined

temperature program. Biodegradability is defined here by way of the ratio of the netto amount of CO2 liberated from the specimen (after deducting the amount of CO2 liberated by the compost without the specimen) to the maximum possible amount of CO2 liberated by the specimen (calculated from the carbon content of the specimen). Even after a few days of composting, biodegradable polymers generally show marked signs of degradation, for example fungal growth, cracking, and perforation.

In another method of determining biodegradability, the polymer is incubated with a certain amount of a suitable enzyme at a certain temperature for a defined period, and then the concentration of the organic degradation products dissolved in the incubation medium is determined. By way of example, by analogy with Y. Tokiwa et al., American Chemical Society Symposium 1990, Chapter 12, "Biodegradation of Synthetic Polymers Containing Ester Bonds" the polymer can be incubated for a number of hours at from 30 to 37°C with a predetermined amount of a lipase, for example from Rhizopus arrhizus, Rhizopus delemar, Achromobacter sp., or Candida cylindracea, and the DOC value (dissolved organic carbon) can then be measured on the reaction mixture freed from insoluble constituents. For the purposes of the present invention, biodegradable polymers are those which after enzymatic treatment with a lipase from Rhizopus arrhizus for 16 h at 35°C give a DOC value which is at least 10 times higher than that for the same polymer which has not been treated with the enzyme.

The term "functionality" represents, here and subsequently, the average number of the respective functional groups per molecule or per polymer chain.

The term "dispersion" is a system of at least two phases, wherein one of these phases is the continuous phase and at least one phase is dispersed. Dispersion is a generic term, which encompasses e.g. emulsions, wherein the continuous phase is liquid and the dispersed phase is liquid, suspensions wherein the continuous phase is liquid and the dispersed phase is solid, solid aerosole, wherein continuous phase is gas and the dispersed phase is solid.

In the context of the present invention, the expression "alkyl" comprises straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, e.g. straight-chain or branched Ci- C ₇ alkyl, preferably C1-C6 alkyl and particularly preferable C1-C4 alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1 ,2-dimethylpropyl, 1 ,1-dimethylpropyl, 2,2-dimethylpropyl, 1- ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,3-dimethylbutyl, 1 ,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1 -ethyl-2-methylpropyl, n- heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1 -propylbutyl, octyl, and the like. Suitable long-chain Cs- C30 alkyl or C8-C30 alkenyl groups are straight-chain and branched alkyl or alkenyl groups. In this connection, they are preferably mainly linear alkyl residues, such as those also present in natural or synthetic fatty acids and fatty alcohols and also oxo alcohols, which, if appropriate, in addition can be mono-, di- or polyunsaturated. These include, e.g., n-hexyl(ene), n-heptyl(ene), n-octyl(ene), n-nonyl(ene), n-decyl(ene), n-undecyl(ene), n-dodecyl(ene), n-tridecyl(ene), n-tetradecyl(ene), n-pentadecyl(ene), n-hexadecyl(ene), n-heptadecyl(ene), n-octadecyl(ene), n-nonadecyl(ene), and the like.

Cycloalkyl preferably represents Cs-Cs cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Aryl comprises unsubstituted and substituted aryl groups and preferably represents phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl, tolyl, xylyl or mesityl.

The volume average particle size can be measured by light scattering measurements using a Malvern 2000S instrument and the Mie scattering theory.

Microcapsule

A first aspect of the invention relates to microcapsules per se. One important parameter of the microcapsules of the invention is the shell weight of the capsules in relation to the total weight of the capsules. It is expressed as percentage of the shell weight with reference to the total weight of the capsules (= encapsulated lipophilic component + shell material).

The percentage of the shell weight with reference to the total weight of the capsules is of 5% to 40%, particularly 5% to 25%, and more particularly 10% to 20%. The microcapsules of the microcapsule composition typically have core/shell ratios (w/w) from 20:1 to 1 :10, preferably from 10:1 to 5:1 and in particular from 4:1 to 3:1.

A microcapsules of the microcapsule composition typically have the mean particle size d(0.5) is from 0.5 μηη to 50 μηη, preferably from 0.7 μηη to 30 μηη, and in particular from 1 μηη to 10 μηη.

Within the context of the present invention, the microcapsules have a shell that is prepared by reacting at least one poly(ester-urethane) containing isocyanate groups (A) with at least one compound (B) (= variant 1 ) or with at least one compound (B1 ) and optionally with at least one compound (B2) (= variant 2), wherein compounds (B), (B1 ) and (B2) comprise terminal groups which are reactive toward isocyanate-groups, and optionally further components capable of being incorporated into the shell. The reaction is a polyaddition between the isocyanate groups and a compound having at least one terminal group which is reactive toward isocyanate group, and optional further groups, capable of reacting with NCO groups, which leads to the formation of polyurethane and/or polyurea linkages. The compounds B), B1 ) and B2) may, in addition to at least one primary or secondary amino group, contain at least one further group, capable of reacting with NCO groups, e.g. at least one OH group. Further components, capable of being incorporated into the shell are in principle all compounds which contain at least one active hydrogen atom per molecule. Reaction of NCO groups with amine groups leads to the formation of urea groups. Reaction of NCO groups with OH groups leads to the formation of urethane groups. Compounds containing only one active hydrogen atom per molecule lead to a termination of the polymer chain and can be employed as regulators. Compounds containing more than two active hydrogen atoms per molecule lead to the formation of branched polyureas. The compounds which contain at least one active hydrogen atom per molecule are usually employed in a molar excess of active hydrogen atoms relative to the NCO groups of the polyisocyanate. The amount of component B which is introduced is usually in a molar excess, relative to the stoichiometric amount needed to convert the free isocyanate groups. Suitable polyesters, polyisocyanates, polyfunctional amines, and optional components that take part in the polyaddition or polycondensation, e.g. reaction, hydrohilic or hydrophobic components, protective colloids, stabilizing agent and further additives, are mentioned below. Component (A): poly(ester-urethane) containing isocyanate groups

The term "polyurethane" comprises, in the context of this invention, not only polymers whose repeat units are bonded to one another via urethane groups but very generally polymers which can be obtained by reaction of at least one polyisocyanate with at least one compound exhibiting at least one group which is reactive with regard to isocyanate groups. These include polymers whose repeat units, in addition to urethane groups, are also connected by urea, allophanate, biuret, carbodiimide, amide, uretonimine, uretdione, isocyanurate or oxazolidone (oxazolidinone) groups (see, for example, Plastics Handbook, Saechtling, 26th edition, p. 491 seq., Carl Hanser Verlag, Munich, 1995). The term "polyurethane" comprises in particular polymers comprising urethane and/or urea groups.

The poly(ester-urethane) used according to the invention is preferably a reaction product of at least one polyester-polyol containing at least 2 hydroxyl groups (OH groups) with at least one polyisocyanate containing at least 2 isocyanate groups (NCO groups). The poly(ester-urethane) used according to the invention contains at least 2 isocyanate groups that are capable of reacting with complementary groups containing active hydrogen atoms.

The polyester-polyol typically has a OH functionality of greater than 1 , preferably from 2 to 6, more preferably from 2 to 5, e.g. 2, 3 or 4.

In a special embodiment, the polyester-polyol is selected from aliphatic polyester-polyols.

The polyester-polyol preferably has a weight-average molecular weight of from 200 to 3000, more preferably from 205 to 2000, e.g. from 240 to 1240 g/mol.

The polyester-polyol typically has a hydroxyl value of from 20 to 800 mg KOH/g, preferably 30 to 600 mg KOH/g, more preferably 40 to 550 mg KOH/g. The polyester-polyol typically has an acid number of from 0 to 15, preferably from 0 to 10, in particular 0 to 5.

The polyester-polyol typically has a viscosity at 60°C of from 40 to 1 100 mPa-s preferably from 100 to 500 mPa-s.

The polyester-polyol typically has at least 2, preferably 4, in particular 7 repeating units connected by ester groups.

Suitable polyesters-polyols include but not limited, for example, polyesters comprising in polymerized form trimethylene carbonate, ε-caprolactone, p-dioxanone, glycolide, lactide, 1 ,5- dioxepan-2-one, or the poyesters polybutylene adipate, polyethylene adipate, polyethylene terephthalate, and combinations thereof. In embodiments the polyester may comprise in polymerized form lactide, glycolide, ε-caprolactone, and/or combinations thereof. Suitable polyester-polyols for the preparation of microcapsules according to the invention exhibit two or more than two (e.g., 3, 4, 5, 6, and the like) hydroxyl groups. In this connection, the hydroxyl groups can also be partially or completely replaced by mercapto groups.

Preferably, the polyester-polyol used for the preparation of the at least one poly(ester-urethane) A) contains in polymerized form

(a1 ) at least one polyol, and

(a2) at least one polycarboxylic acid, and/or

(a3) at least one hydroxycarboxylic acid.

More preferably, the polyester-polyol used for the preparation of the at least one poly(ester- urethane) A) contains in polymerized form at least one polyol (a1 ), and at least one

hydroxycarboxylic acid (a3). Suitable polyols (a1) are diols, polyols containing more than 2 OH groups and mixtures thereof. The term "polyols containing more than 2 OH groups" usually refers to polyols having at least 3 OH groups.

Suitable polyols containing more than 2 OH groups, and suitable polyols having at least 3 OH groups are triols and high molecular weight polyols (also called polymeric polyols), wherein triols are preferred. Preferred polyols (a1 ) are diols and triols, wherein triols are preferred. In particular polyols (a1 ) are selected from glycerol (propane-1 ,2,3-triol), butane-1 ,2,4-triol, n- pentane-1 ,2,5-triol, n-pentane-1 ,3,5-triol, n-hexane-1 ,2,6-triol, n-hexane-1 ,2,5-triol,

(1 ,1 ,1 )-trimethylolpropane (TMP) and trimethylolbutane.

Suitable diols are straight-chain and branched aliphatic and cycloaliphatic alcohols with generally approximately 2 to 30, preferably approximately 2 to 20, carbon atoms. These include

1.2- ethanediol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3-butanediol, 1 ,4-butanediol,

2.3- butanediol, 1 ,2-pentanediol, 1 ,3-pentanediol, 1 ,4-pentanediol, 1 ,5-pentanediol, 2,3- pentanediol, 2,4-pentanediol 1 ,2-hexanediol, 1 ,3-hexanediol, 1 ,4-hexanediol, 1 ,5-hexanediol, 1 ,6-hexanediol, 2,5-hexanediol, 1 ,2-heptanediol, 1 ,7-heptanediol, 1 ,2-octanediol, 1 ,8- octanediol, 1 ,2-nonanediol, 1 ,9-nonanediol, 1 ,2-decanediol, 1 ,10-decanediol, 1 ,12- dodecanediol, 2-methyl-1 ,3-propanediol, 2-methyl-2-butyl-1 ,3-propanediol, 2,2-dimethyl-1 ,3- propanediol, 2, 2-dimethyl-1 ,4-butanediol, pinacol, 2-ethyl-2-butyl-1 ,3-propanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyalkylene glycols, cyclopentanediols, cyclohexanediols, and the like.

Suitable triols are, e.g., glycerol (propane-1 ,2,3-triol), butane-1 ,2,4-triol, n-pentane-1 , 2, 5-triol, n- pentane-1 ,3,5-triol, n-hexane-1 ,2,6-triol, n-hexane-1 , 2, 5-triol, (1 ,1 ,1 )-trimethylolpropane (TMP) and trimethylolbutane.

Suitable triols are furthermore the triesters of hydroxycarboxylic acids with trivalent alcohols. Preferably, in this connection, they are triglycerides of hydroxycarboxylic acids, such as, e.g., lactic acid, hydroxystearic acid and ricinoleic acid. Naturally occurring mixtures comprising hydroxycarboxylic acid triglycerides, in particular castor oil, are also suitable.

Suitable polyols of higher valency are, e.g., sugar alcohols and their derivatives, such as erythritol, pentaerythritol, dipentaerythritol, threitol, inositol and sorbitol. Reaction products of the polyols with alkylene oxides, such as ethylene oxide and/or propylene oxide, are also suitable.

Relatively high molecular weight polyols (also called herein polymeric polyols) with a number- average molecular weight in the range of approximately 400 to 6000 g/mol, preferably 500 to 4000 g/mol, can also be used. These include, e.g., polyalkylenglycoles (PEGs) such as polyethylene glycol (PEG) diol, and a copolymer diol of polyethylene glycol (PEG) diol and polypropylene glycol (PPG) diol or polybutylene glycol (PBG) diol. These furthermore include polytetrahydrofurandiols which can be obtained, e.g., by acid-catalyzed polymerization of tetrahydrofuran.

These furthermore include polylactonepolyols which are obtainable (preferably can be obtained) e.g. by ring-opening addition polymerization of a hydroxyl-terminated compound (e.g. diol or triol) and a monomer that includes a lactone ring (e.g., ε-caprolactone or 3-methyl-5- valerolactone).

These furthermore include polylactonediols which can be obtained, e.g., by polylactonediol obtained by ring-opening addition polymerization of a hydroxyl-terminated compound (e.g., polyol or polyester polyol) and a monomer that includes a lactone ring (e.g., ε-caprolactone or β- methyl-5-valerolactone).

These furthermore include polyesterols based on aliphatic, cycloaliphatic and/or aromatic di-, tri- and/or polycarboxylic acids with di-, tri- and/or polyols, and also the polyesterols based on lactone. These furthermore include polyetherols which can be obtained, e.g., by polymerization of cyclic ethers or by reaction of alkylene oxides with an initiator molecule. These furthermore also include conventional polycarbonates with terminal hydroxyl groups known to a person skilled in the art which can be obtained by reaction of the diols described above or also bisphenols, such as bisphenol A, with phosgene or carbonic diesters. α,ω-Polyamidols, poly(methyl (meth)acrylate) α,ω-diols and/or poly(butyl (meth)acrylate α,ω-diols, such as, e.g., MD-1000 and BD-1000 from Goldschmidt, are also suitable.

In a preferred embodiment the poly(ester-urethane) A) is obtainable by reacting at least one polylacton polyol containing at least 2 OH groups with at least one polyisocyanate containing at least 2 NCO groups. In other words, the polyester-polyol used for the preparation of the poly(ester-urethane) A) is a polylactonpolyol.

Preferably, the polylactonpolyol contains 2 or 3 OH groups. In particular, the polylactonpolyol is a polycaprolactonediol or a polycaprolactontriol. Preferably, polylactonpolyol is a polycaprolactonediol or a polylactontriol having a number- average molecular weight of from 200 to 5000 g/mol, more preferably 250 to 3000 g/mol.

Preferably, the polyester-polyol is selected from compounds of the formulae (1 ), (2), (3), (4), (5) and mixtures thereof

(1 ) (2)

(3) (4) (5)

wherein

R ^a is a divalent aliphatic or cycloaliphatic radical,

R ^b is a trivalent aliphatic or cycloaliphatic radical

I, m and n are independently an integer of 1 to 100, with the proviso that

in the formula (1 ) n is an integer of 2 to 100,

in the formula (2) n + m is an integer of 2 to 100,

in the formula (3) n is an integer of 2 to 100,

in the formula (4) n + m is an integer of 2 to 100,

in the formula (5) n + m + I is an integer of 2 to 100. Suitable radicals R ^a are linear or branched Ci-Cio-alkylene groups that are optionally interrupted by 1 , 2, 3, 4 or 5 non-neighboring oxygen atoms and C3-C2o-cycloaliphatic radicals having 3 to 10 ring carbon atoms.

Suitable radicals R ^b are linear or branched Ci-Cio-alkantriyl groups that are optionally interrupted by 1 , 2, 3, 4 or 5 non-neighboring oxygen atoms. Preferred radicals R ^a are methylene, 1 ,2-ethylene, 1 ,2-propylene, 1 ,3-propylene, 1 ,2-butylene, 1 ,3-butylene, 1 ,4-butylene, 1 ,1-dimethyl-1 ,2-ethylene, 1 ,2-dimethyl-1 ,2-ethylene, 1 ,5-pentylene, 1 ,6-hexylene, 1 ,8-octylene, 1 ,10-decylene, 1 ,12-dodecylene,

-CH2-O-CH2, -CH2-CH2-O-CH2-CH2- and -CH2-CH2-O-CH2-CH2-O-CH2-CH2-.

More preferred radicals R ^a are 1 ,2-ethylene, 1 ,2-propylene, 1 ,3-propylene, 1 ,2-butylene, 1 ,3- butylene, 1 ,4-butylene, -CH2-CH2-O-CH2-CH2- and

-CH2-CH2-O-CH2-CH2-O-CH2-CH2-. Preferred radicals R ^b are

More preferably, the polyester-polyol is selected from compounds of the formulae (2), (5) and mixtures thereof, wherein compounds of the formulae (5) are in particular preferred.

In particular, the polyester-polyol is selected from compounds of the formulae (2), (5) and mixtures thereof (in particular from formula (5)), wherein

R ^a is selected from linear or branched Ci-Cio-alkylene group and C3-C2o-cycloaliphatic radicals having 3 to 10 ring carbon atoms,

R ^b is a linear or branched Ci-Cio-alkantriyl group,

I, m and n are independently an integer of 1 to 100,

with the proviso that

in the formula (2) n + m is an integer of 2 to 100,

in the formula (5) n + m + I is an integer of 2 to 100.

In one preferred embodiment, the polyester-polyol containing at least 2 OH groups is obtainable (preferably it is obtained) by reaction of at least one diol and/or polyalkylenglycol with at least one polylacton, in particular the polyester-polyol containing at least 2 OH groups is obtained by reaction of diethylenglycol and poly-e-caprolacton.

In another preferred embodiment, the polyester-polyol containing at least 2 OH groups is obtainable (preferably it is obtained) by reaction of at least one polyol having at least 3 OH groups with at least one polylacton, in particular the polyester-polyol containing at least 2 OH groups is obtained by reaction of trimethylolpropane and/or glycerol and poly-e-caprolacton.

In another preferred embodiment, the polyester-polyol containing at least 2 OH groups is obtainable (preferably it is obtained) by reaction of at least one polyol having at least 3 OH groups selected from glycerol, butane-1 ,2,4-triol, n-pentane-1 ,2,5-triol, n-pentane-1 ,3,5-triol, n- hexane-1 ,2,6-triol, n-hexane-1 ,2,5-triol, (1 ,1 ,1 )-trimethylolpropane and trimethylolbutane with at least one polylacton.

One embodiement relates to microcapsules as defined above and below, wherein the polyester- polyol containing at least 2 OH groups is obtainable (preferably it is obtained) by reaction of at least one diol and/or polyalkylenglycol with at least one polylacton.

Another embodiement relates to microcapsules as defined above and below, wherein the polyester-polyol containing at least 2 OH groups is obtainable (preferably it is obtained) by reaction of at least one polyol having at least 3 OH groups and/or polymeric polyol having at least 3 OH with at least one polylacton.

Suitable non-limiting examples of commercially available polyester-polyols are Caproper™ PD4- 05 (a polycaprolactonediol), the LUPRAPHEN® brands available from BASF SE (e.g.

Lupraphen 6601/3 a difunctional, aliphatic polyester-polyol) and (Tri-iso) Capa 3031 available from Perstorp.

One isocyanate group is supposed to react with a terminal hydroxyl group of the polyester- polyol and whilst the other isocyanate group of the diisocyanate is preserved. To avoid polymerization of high molecular weight chains, at least the mole equivalent of diisocyanate compared to hydroxyl groups has to be used in the reaction mixture. Once the functionalization is completed poly(ester-urethane)-diisocyanates are obtained as macromonomers.

The reaction progress is monitored by the frequent determination of the isocyanate content of the solution. The functionalization is complete after the conversion of 50% of the isocyanate groups. The isocyanate (NCO) content is declared in grams of NCO per 100 g reaction mixture.

Isocyanates are N-substituted organic derivatives (R-N=C=0) of isocyanic acid (HNCO) tautomeric in the free state with cyanic acid. Organic isocyanates are compounds in which the isocyanate group (-N=C=0) is bonded to an organic radical. Polyfunctional isocyanates are compounds with two or more (e.g. 3, 4, 5, etc.) isocyanate groups in the molecule.

Preferably, the polyisocyanate according to the incention comprises at least one difunctional isocyanate. In a special embodiment, the polyisocyanate is exclusively selected from

difunctional isocyanates, the allophanates, isocyan urates, uretdiones or carbodiimides of difunctional isocyanates and mixtures thereof.

In general, suitable polyisocyanates are all aromatic, alicyclic and aliphatic polyisocyanates, provided they have at least two reactive isocyanate groups. Preferably, the polyisocyanate component has an avarage content of 2 to 4 NCO groups. Preference is given to using diisocyanates, i.e. esters of isocyanic acid with the general structure 0=C=N-R'-N=C=0, where R' is an aliphatic, alicyclic or aromatic radical. Suitable polyisocyanates are chosen from compounds with 2 to 5 isocyanate groups, isocyanate prepolymers with an average number of from 2 to 5 isocyanate groups and mixtures thereof. These include, for example, aliphatic, cycloaliphatic and aromatic di-, tri- and higher polyisocyanates.

Preferably, the polyisocyanates comprise only a minor amount of compounds with aromatic rings. In particular, not more than 5 wt% of the polyisocyanates, based on the complete amount of the polyisocyanates, comprises an aromatic ring. In a special embodiment the polyisocyanate is selected only from aliphatic polyisocyanates. The term "aliphatic polyisocyanate" in the sense of the invention encompasses also non-aromatic cyclic polyisocyanates, e.g. isophorone diisocyanate.

Preferably, the polyisocyanate is selected from ethylene diisocyanate, tetramethylene diisocyanate, 1 ,5-pentamethylene diisocyanate, hexamethylene diisocyanate(1 ,6- diisocyanatohexane, HDI), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, 4-isocyanatomethyl-1 ,8- octamethylene diisocyanate, 1 ,6-diisocyanato-2,2,4-trimethylhexane, 1 ,6-diisocyanato-2,4,4- trimethylhexane, 2,3,3-trimethylhexamethylene diisocyanate, tetramethylhexane diisocyanate, lysine diisocyanate, isophorone diisocyanate (= 3-lsocyanatmethyl-3,5,5- trimethylcyclohexylisocyanat, 1 -lsocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexan, IPDI), 1 ,4-cyclohexylene diisocyanate, 1 ,3-cyclohexylene diisocyanate, 1 ,2-cyclohexylene diisocyanate, 4,4'-di(isocyanatocyclohexyl)methane, or 2,4'-di(isocyanatocyclohexyl)methane,

1 .3- bis(isocyanatomethyl)cyclohexane, 1 ,4-bis(isocyanatomethyl)cyclohexane, 1 -methyl-2,4- diisocyanatocyclohexane, 1 -methyl-2,6-diisocyanatocyclohexane, 1 ,3-phenylene diisocyanate,

1 .4- phenylene diisocyanate, 2,4- and 2,6-toluylene diisocyanate and isomer mixtures thereof,

1 .5- naphthylene diisocyanate, 2,4'- and 4,4'-diphenylmethane diisocyanate (MDI), mixtures of diphenylmethane diisocyanates and more highly polycyclic homologs of diphenylmethane diisocyanate (polymeric MDI), hydrogenated 4,4'-diphenylmethane diisocyanate (H12MDI), xylylene diisocyanate (XDI), tetramethylxylol diisocyanate (TMXDI), 4,4'-dibenzyl diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, di-and tetraalkyldiphenylmethandiisocyanat.es, triphenylmethane-4,4',4"-triisocyanate, dimer fatty acid diisocyanates, chlorinated and brominated diisocyanates, 4,4'-diisocyanatophenylperfluoroethane, tetramethoxybutane-1 ,4- diisocyanate, phosphorus-containing diisocyanates, sulfur-containing diisocyanares, anionically modified polyisocyanates, polyethylene oxide-containing isocyanate, oligomers of the aforementioned polyisocyanates that contain urethane, allophanate, isocyanurate, uretdione, carbodiimide or biuret groups, and mixtures thereof.

Suitable chlorinated and brominated polyisocyanates comprise polyisocyanates with reactive halogen atoms. Preferably, the chlorinated and brominated polyisocyanate is selected from 1- chloromethylphenyl 2,4-diisocyanate, 1-bromomethylphenyl 2,6-diisocyanate, 3,3- bischloromethyl ether 4,4'-diphenyldiisocyanate. Suitable sulfur-containing polyisocyanates are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxydihexyl sulfide. The polyisocyanate preferably comprises at least one aliphatic diisocyanate, selected from tetramethylene diisocyanate, 1 ,5-pentamethylene diisocyanate, hexamethylene

diisocyanate(1 ,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene

diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, lysine diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate,

1 ,4-diisocyanatocyclohexane, 1 ,3-diisocyanatocyclohexane, 1 ,2-diisocyanatocyclohexane, 4,4'- di(isocyanatocyclohexyl)methane, 2,4'-di(isocyanatocyclohexyl)methane, isophorone diisocyanate, 1 ,3-bis(isocyanatomethyl)cyclohexane, 1 ,4-bis(isocyanatomethyl)cyclohexane, 2,4-diisocyanato-1 -methylcyclohexane and 2,6-diisocyanato-1 -methylcyclohexane.

The polyisocyanate preferably comprises at least one polyisocyanate, selected from

hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 2,4- and 2,6-toluylene diisocyanate and isomer mixtures thereof, 2,4'- and 4,4'-diphenylmethane diisocyanate, the biurets, allophanates and/or isocyanurates of the aforementioned polyisocyanates, anionically modified polyisocyanates, and mixtures thereof.

Preferably, polyisocyanates are selected from hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 2,4- and 2,6-toluylene diisocyanate and isomer mixtures thereof, 2,4'- and 4,4'-diphenylmethane diisocyanate and isomer mixtures thereof, the biurets, allophanates and/or isocyanurates of the afore-mentioned polyisocyanates or mixtures thereof.

In particular, the polyisocyanates are selected from hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, the isocyanurate of hexamethylene diisocyanate or mixtures thereof.

Especially, the polyisocyante is isophorone diisocyanate.

Component B, (B1 ) and (B2)

The shell comprises in polymerized form B1 ) at least one polymeric polyamine (B1 ) having a weight average molecular weight of at least 300 g/mol and containing at least 3 amino groups reactive towards NCO groups, and

B2) optionally at least one compound (B2), which is different from B1 ) and which comprises at least 2 terminal groups which are reactive towards isocyanate-groups, which are selected from OH, NHR, or SH, wherein R is selected from hydrogen, alkyl, cycloalkyl or aryl. Suitable polymeric polyamines (B1) are in principle linear or branched polymers that have at least two primary or secondary amino groups. Additionally, these polymers can have tertiary amino groups in the polymer chain. Preference is given to polymeric polyamines having a weight-average molecular weight of at least 300 g/mol. More preferred are polymeric polyamines having a weight-average molecular weight of from 350 to 3000, in particular from 375 to 2500, especially from 400 to 2000, more especially from 500 to 1500. Furthermore, polymeric polyamines typically has at least 3, preferably 4, in particular 5 repeating units.

The polymeric polyamine is preferably selected from polyaminosaccharides, polyamidoamines, polyesteramines, polyetheramines, polyvinylamines, polyaminoacids polyaminoacids, and combinations thereof. Preferably, the polymeric polyamine comprises a polyamidoamines, in particular polylysine.

More preferably, the polymeric polyamine comprises polylysine which has a average molecular weight from of 300 to 4000 g/mol, preferably from 500 to 3000 g/mol.

Preferred polyesteramines are in the context of the present invention, very generally polymeric compounds exhibiting ester groups and amino groups in the chain, amino groups not being part of an amide group. In principle, at least divalent compounds exhibiting one amino group, preferably no longer available for a subsequent reaction, and at least two additional functional groups, capable of an addition or condensation reaction, can be used. These include, for example, N-alkyl-N-(hydroxyalkyl)aminoalkanecarboxylic acids and carboxylic acid derivatives, N,N-di(hydroxyalkyl)aminoalkanecarboxylic acids and carboxylic acid derivatives, N-alkyl-N- (aminoalkyl)aminoalkanecarboxylic acids and carboxylic acid derivatives, N,N- di(aminoalkyl)aminoalkanecarboxylic acids and carboxylic acid derivatives, and the like. In addition to these monomers, the polyesteramines used according to the invention can comprise additional polyfunctional compounds incorporated exhibiting two or more than two (e.g., 3, 4, 5, 6, and the like) functional groups. These include the above-described polycarboxylic acids, polyfunctional amines, polyfunctional alcohols and polyfunctional aminoalcohols, reference to which is made here in their entirety.

Preferred polyamidoamines are dendrimer which is made of repetitively branched subunits of amide and amine functionality. Preferred polyamidoamines are polylysine, which is

homopolymers from lysine. It is prepared from amino acid lysine, which contains two amino groups, one at the ocarbon and one at the ε-carbon. Either can be the location of

polymerization, resulting in opolylysine or ε-polylysine. Preference is given to polylysine which have a average molecular weight from of 300 to 4000 g/mol, preferably from 400 to 3000 g/mol, more preferably, 500 to 1500 g/mol. Furthermore, polylysine according to the invention has at least 3, preferaly 4, in particuar 5 repeating units. Preferred polyaminosaccharides are sugar molecule in which a hydroxyl group has been replaced with an amine group. Preferred are chitosan composed of randomly distributed β-(1 -4)- linked D-glucosamine (deacetylated unit) and N-acetyl-D-glucosamine (acetylated unit). Preferred polyvinylamines (polyaminoethylene) are known products obtained by homo- or copolymerization of N-vinylformamide followed by partial or complete hydrolysis.

Preferred polyetheramines are the reaction products of at least one polyol with at least one C2- C18 alkylene oxide, to form an alkoxylated polyol and aminating the alkoxylated polyol with ammonia.

Preferred polyamino acids usually consist of repeating units of amino acids, wherein the homopolyamino acid is made from up of a single amino acid as a repeating unit, and the co- polyamino acid is a polymer made from at least two or more different amino acids as repeating units. Polyamino acids contain both an amino and a carboxylic acid functional group. Preferred polyamino acids are selected from the group consisting of poly-D,L-ornithine, poly-D,L- homoarginine, poly-D,L-arginine, poly-D,L-glutamic acid, poly-D,L-glutamic acid, poly-D,L- glutamic acid, poly-D,L-aspartic acid. Preferred are also polyethyleneimines, which are selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, ethylenepropylenetriamine, trisaminopropylamine and higher polyethyleneimines. Preferably the polyethyleneimines have a number-average molecular weight of at least 300 g/mol, preferably from 400 to 3000 or 450 to 2500 g/mol and in particular from 450 to 2000 g/mol. In a preferred embodiment, the polymeric polyamine is selected from polyethyleneimines having a weight average molecular weight of at least 300 g/mol. Suitable polyethylenimines contain the following repeat units

I

— (CH ₂ CH ₂ NH) _X — — (CH ₂ CH ₂ N)y— — (CH ₂ CH ₂ NH _2)Z

J

wherein

x is from 8 to 1500, preferably from 10 to 1000;

y is from 0 to 10, preferably from 0 to 5, especially 0;

z is 2+y.

Preferred polyethyleneimines are linear polyethyleneimines, wherein x is from 8 to 1500, y is 0 and z is 2. Preferred commercially available polyethylenimines are sold by BASF SE under the trademark Lupasol™ and the Jeffamine trademarks from Huntsman, particularly Lupasol TM PR8515.

If the core essentially contains only hydrophobic components, preference is given to

hexamethylene diamine, ethylenediamine, N-ethylethylenediamine,

Ν,Ν'-diethylethylenediamine, diethylenetriamine, tetraethylene pentamine, spermine, spermidine, polyvinylamines, polyetheramines, polyesteramines and polyamidoamines. Suitable compounds (B2) are polyfunctional alcohols, polyfunctional amines, or mixtures thereof. Preferably, the compound (B2) comprises a polyfunctional alcohol. In the sense of the invention, the term polyfunctional alcohol denotes alcohols that comprise at least two groups capable of reacting with NCO groups, wherein at least one of the groups capable of reacting with NCO groups is a OH group. When the polyfunctional alcohol contains only one OH group, it will contain one or more additional functional groups that are capable of reacting with NCO groups in a polymerisation reaction. Suitable are in principle active hydrogen atom containing groups. The groups of the polyfunctional alcohol that are reactive toward NCO groups are preferably chosen from hydroxyl groups and primary and secondary amino groups.

Suitable polyfunctional alcohols according to the exhibit two or more than two (e.g., 3, 4, 5, 6, and the like) hydroxyl groups. In this connection, the hydroxyl groups can also be partially or completely replaced by mercapto groups.

Suitable diols are straight-chain and branched aliphatic and cycloaliphatic alcohols with generally approximately 2 to 30, preferably approximately 2 to 20, carbon atoms. These include

1 .2- ethanediol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,2-butanediol,

1 ,3-butanediol, 1 ,4-butanediol, 2,3-butanediol, 1 ,2-pentanediol, 1 ,3-pentanediol,

1 ,4-pentanediol, 1 ,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol 1 ,2-hexanediol,

1 .3- hexanediol, 1 ,4-hexanediol, 1 ,5-hexanediol, 1 ,6-hexanediol, 2,5-hexanediol,

1 ,2-heptanediol, 1 ,7-heptanediol, 1 ,2-octanediol, 1 ,8-octanediol, 1 ,2-nonanediol,

1 ,9-nonanediol, 1 ,2-decanediol, 1 ,10-decanediol, 1 ,12-dodecanediol, 2-methyl-1 ,3-propanediol, 2-methyl-2-butyl-1 ,3-propanediol, 2,2-dimethyl-1 ,3-propanediol,

2,2-dimethyl-1 ,4-butanediol, pinacol, 2-ethyl-2-butyl-1 ,3-propanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyalkylene glycols,

cyclopentanediols, cyclohexanediols, and the like. Suitable triols are, e.g., glycerol, butane-1 ,2,4-triol, n-pentane-1 ,2,5-triol, n-pentane-1 ,3,5-triol, n-hexane-1 ,2,6-triol, n-hexane-1 ,2,5-triol, trimethylolpropane and

trimethylolbutane. Suitable triols are furthermore the triesters of hydroxycarboxylic acids with trivalent alcohols. Preferably, in this connection, they are triglycerides of hydroxycarboxylic acids, such as, e.g., lactic acid, hydroxystearic acid and ricinoleic acid. Naturally occurring mixtures comprising hydroxycarboxylic acid triglycerides, in particular castor oil, are also suitable. Suitable polyols of higher valency are, e.g., sugar alcohols and their derivatives, such as erythritol, pentaerythritol, dipentaerythritol, threitol, inositol and sorbitol. Reaction products of the polyols with alkylene oxides, such as ethylene oxide and/or propylene oxide, are also suitable. Relatively high molecular weight polyols with a number-average molecular weight in the range of approximately 400 to 6000 g/mol, preferably 500 to 4000 g/mol, can also be used.

These include, e.g., polyesterols based on aliphatic, cycloaliphatic and/or aromatic di-, tri- and/or polycarboxylic acids with di-, tri- and/or polyols, and also the polyesterols based on lactone. These furthermore include polyetherols which can be obtained, e.g., by polymerization of cyclic ethers or by reaction of alkylene oxides with an initiator molecule. These furthermore also include conventional polycarbonates with terminal hydroxyl groups known to a person skilled in the art which can be obtained by reaction of the diols described above or also bisphenols, such as bisphenol A, with phosgene or carbonic diesters. α,ω-Polyamidols, poly(methyl (meth)acrylate) α,ω-diols and/or poly(butyl (meth)acrylate α,ω-diols, such as, e.g., MD-1000 and BD-1000 from Goldschmidt, are also suitable.

In the sense of the invention, the term polyfunctional amine denotes amines that comprise at least two groups capable of reacting with NCO groups, wherein at least one of the groups capable of reacting with NCO groups is a primary or secondary amino group. When the polyfunctional amine contains only one primary or secondary amino group, it will contain one or more additional functional groups that are capable of reacting with NCO groups in a

polymerisation reaction. Suitable are in principle active hydrogen atom containing groups. The groups of the polyfunctional amines that are reactive toward NCO groups are preferably chosen from hydroxyl groups and primary and secondary amino groups.

The polyfunctional amine is preferably selected from diamines, aminoalcohols, polymeric polyamines, guanidines, melamines, urea, hydrazines and mixtures thereof. When the compound (B2) comprises a polyfunctinal amine which is a polymeric polyamines, the polymeric polyamine is different from the compound (B1 ).

Suitable diamines are, for example, 1 ,2-ethylenediamine, 1 ,3-propylenediamine,

1 ,4-diaminobutane, 1 ,5-diaminopentane (cadaverine), 1 ,6-diaminohexane, 1 ,3-diamino-1- methylpropane, 1 ,4-diaminocyclohexane, piperazin, N-ethylethylenediamine, Ν,Ν'- diethylethylenediamine and mixtures thereof. Suitable amines which have at least least two primary or secondary amino groups are, for example diethylenetriamine, tetraethylene pentamine, spermine, spermidine and mixtures thereof. Suitable amino alcohols are, for example, 2-aminoethanol, 2-(N-methylamino)ethanol, 3- aminopropanol, 4-aminobutanol, 1 -ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol, 4- methyl-4-aminopentan-2-ol, etc.

In a special embodiment of the invention the polymeric shell material shows biodegradability.

In a preferred embodiment for providing a biodegradable polymeric shell material the poly(ester- urethane) A) is prepared by reacting at least one polycaprolactonediol or a polylactonetriol having a number-average molecular weight of from 250 to 3000 g/mol with at least one polyisocyanate containing at least 2 NCO groups. Core material

Suitable hydrophobic components are mentioned in detail below. In the sense of the invention, the term "hydrophobic component" is understood in a broad sense. It encompasses a single hydrophobic component, a mixture comprising at least two hydrophobic components and a solution of at least one hydrophobic solid compound in a liquid hydrophobic compound. The hydrophobic components used according to the invention have only a limited solubility in water. The solubility of the hydrophobic components (e.g. the pesticide) in water at 20°C and 1013 mbar is preferably≤ 10 mg/mL, more preferably≤ 5 mg/mL, in particular≤ 3 mg/mL.

The term "the core essentially contains only hydrophobic components" usually means that the core contains at least 80 wt%, preferably at least 90 wt%, more preferably at least 95 wt%, and in particular at least 98 wt% of the hydrophobic components.

In a special embodiment of the invention, the microcapsules contain substantially no solvent in the core. According to the process of the invention, it is possible to prepare a microcapsule composition, wherein the encapsulated cores are composed entirely of hydrophobic

components and no solvents. Solvent-free encapsulated hydrophobic components may be employed, in particular, when the hydrophobic components making up the core material are liquid under the condions used for the preparation of the microcapsules. Preferably, at least 60% by weight, more preferably at least 70% by weight, in particular at least 80% by weight and especially at least 90% by weight of hydrohobic components, based on the total weight of the hydrophobic components, have a solubility in water at 20°C and 1013 mbar of ≤ 10 mg/mL, particularly≤ 5 mg/mL, and more particularly≤ 3 mg/mL. The microcapsules contain one or more hydrophobic components. Preferably, the amount of the hydrophobic components (e.g. the pesticide) is in a range of from 5 to 97% by weight, more preferably 10 to 95% by weight, in particular 25 to 93% by weight, based on the total weight of the microcapsules. In a special embodiment, the amount of the hydrophobic components (e.g. the pesticide) is in a range of from 70 to 98% by weight, based on the total weight of the microcapsules.

Advantageously, a large amount of hydrophobic components can be encapsulated in the microcapsules of the invention despite the relatively low shell weight. Preferably, the ratio of the total weight of the hydrophobic components to total weight of the shell material is in a range of from 60% to 95% by weight, more preferably 75% to 80% by weight, and more particularly 80% to 88% by weight. In another form the core-shell ratio (w/w) of the microcapsules is 20:1 to 1 :10, preferably 10:1 to 5:1 and in particular 4:1 to 3:1 . In a preferred form the core-shell ratio (w/w) of the

microcapsules is 20:1 to 1 :1 , preferably 10:1 to 2:1 and in particular 6:1 to 3:1. The core-shell weight ratio may be obtained by weighing an amount of capsules that have been previously washed with water and separated by filtration. The core is then extracted by solvent extraction techniques to give a core weight. The shell weight is obtained from simple mass balance taking into account the initial amount of encapsulating materials in weight%. Hydrophobic components that are used can be various organic substances. In particular, the hydrophobic component is selected from active ingredients and auxiliaries for cosmetics (e.g. hair and skin cosmetics), pharmaceuticals, hygiene compositions, detergents, cleaning agents, textile treatment compositions, etc., compositions used for industrial or institutional or hospital applications, material protection compositions or plant protection compositions.

Active ingredients are substances which generally develop an effect even at low concentration, e.g. a cosmetic effect on skin and/or hair, a pharmacological effect in an organism, a plant protecting effect, a cleaning and/or disinfecting effect, a modification of a textile substance, e.g. a crease-free finishing, and effect substances which impart a certain property to living things or inanimate substrates, for example colors for make-up, mascara, etc.

Preferably, the hydrophobic component is selected from oil bodies, UV-filters, organic compounds biocides, dyes, emollients, vitamins, cosmetically active ingredients,

pharmaceutically active ingredients, cosmetically and pharmaceutically acceptable auxiliaries, detergents, anti-oxidants, perfumes and fragrances or mixtures thereof.

In one embodiment the hydrophobic component of the microcapsule or microcapsule dispersion as defined above is selected from UV-filters, organic compounds, biocides, dyes, emollients, vitamins, cosmetically active ingredients, pharmaceutically ingredient, detergent composition, anti-oxidant agents, fragrances or mixtures thereof.

A first class of hydrophobic components that can be encapsulated are oil bodies.

Preferably, the hydrophobic components comprise at least one oil body capable to dissolve the polyisocyanates (component (A)). More preferably, these oil body are capable to dissolve the polyisocyanates without extraneous solvents and/or auxiliaries. Should an oil body not ensure adequate solubility of the polyisocyanates, there is the option of overcoming this disadvantage by using suitable solubility promoters. The term oil body in the sense of the invention means vegetable oils, modified vegetable oils, synthetic (tri)glycerides, fatty acid alkyl esters, fatty acid alkyl esters based on said C6-C22 fatty acids, mineral oils, silicone oils, hydrocarbons, saturated or unsaturated C6-C3o-fatty acids, aromatic compounds, waxes, polymers, Guerbet alcohols based on fatty alcohols, esters of linear C6-C22-fatty acids and mixtures thereof. Preferred oil bodies are vegetable oils, modified vegetable oils, synthetic (tri)glycerides, fatty acid alkyl esters, fatty acid alkyl esters based on said C6-C22 fatty acids, mineral oils, hydrocarbons, saturated or unsaturated C6-C3o-fatty acids, aromatic compounds, esters of linear C6-C22-fatty acids and mixtures thereof.

Preferred oils are cosmetical acceptable oils like caprylic/capric triglyceride, myristyl myristate, cetyl oleate.

Within the context of the present invention, preferred oil bodies are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, esters of linear C6-C22-fatty acids with linear or branched C6-C22-fatty alcohols or esters of branched C6-Ci3-carboxylic acids with linear or branched C6-C22-fatty alcohols, such as e.g. myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate.

A further class of hydrophobic components that can be encapsulated are UV filters. Preferably, the hydrophobic components comprise at least one UV filters capable to dissolve the polyisocyanates (component (A)). More preferably, these UV-filters are capable to dissolve the polyisocyanates without extraneous solvents and/or auxiliaries. Should an UV filter not ensure adequate solubility of the polyisocyanates, there is the option of overcoming this disadvantage by using suitable solubility promoters. Typical hydrobhobic UV filters are UV-A filters, UV-B filters or broad-spectrum UV A/B filters are, for example, 3-benzylidenecamphor or 3-benzylidenenorcamphor and derivatives thereof, e.g. 3-(4-methylbenzylidene)-camphor, 3-(4'-trimethylammonium)benzylidenebornan-2-one methylsulfate (Mexoryl SO), 3,3'-(1 ,4-phenylenedimethine)bis(7,7-dimethyl-2-oxobicycle- [2.2.1]heptane-1-methanesulfonic acid) and salts (Mexoryl SX), 3-(4'-sulfo)benzylidenebornan- 2-one and salts (Mexoryl SL), polymer of N-{(2 and 4)-[2-oxoborn-3-ylidene)- methyl}benzyl]acrylamide (Mexoryl SW), 2-(2H-benzotriazol-2-yl)-4-methyl-6-(2-methyl-3-

(1 ,3,3,3-tetramethyl-1-(trimethylsilyloxy)disiloxanyl)propyl)p henol (Mexoryl SL), 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4-(dimethylamino)benzoate,

2-octyl 4-(dimethylamino)benzoate and amyl 4-(dimethylamino)benzoate; esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; triazine derivatives, such as e.g. 2,4,6-trianilino(p-carbo-2'-ethyl-1 '-hexyloxy)-1 ,3,5-triazine and 2,4,6-tris[p-(2- ethylhexyloxycarbonyl)anilino]-1 ,3,5-triazine (Uvinul T 150) or bis(2-ethylhexyl) 4,4'-[(6-[4-((1 ,1- dimethylethyl)aminocarbonyl)phenylamino]-1 ,3,5-triazine-2,4-diyl)diimino]bisbenzoate

(Uvasorb® HEB); 2,2-(methylenebis(6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol (Tinosorb M); 2,4-bis[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-6-(4-methoxyphe nyl)-1 ,3,5-triazine (Tinosorb S); propane-1 ,3-diones, such as e.g. 1-(4-tert-butylphenyl)-3-(4'- methoxyphenyl)propane-1 ,3-dione; ketotricyclo(5.2.1.0)decane derivatives, dimethicodiethyl benzalmalonate (Parsol SLX).

A further class of hydrophobic components that can be encapsulated are biocides. Preferably, the hydrophobic components comprise at least one biocide capable to dissolve the

polyisocyanates (component (A)). More preferably, these biocides are capable to dissolve the polyisocyanates without extraneous solvents and/or auxiliaries. Should a biocide not ensure adequate solubility of the polyisocyanates, there is the option of overcoming this disadvantage by using suitable solubility promoters. A biocide is a chemical substance, capable of killing different forms of living organisms used in fields, such as medicine, agriculture, forestry, and mosquito control. Usually, biocides are divided into two sub-groups:

pesticides which includes fungicides, herbicides, insecticides, algicides, moluscicides, miticides and rodenticides, and

antimicrobials which includes germicides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals and antiparasites. Biocides can also be added to other materials (typically liquids) to protect the material from biological infestation and growth. For example, certain types of quaternary ammonium compounds (quats) can be added to pool water or industrial water systems to act as an algicide, protecting the water from infestation and growth of algae. In a preferred form the hydrophobic component comprises a pesticide and optionally an oil body. In one form suitable pesticides include fungicides, herbicides, insecticides, algicides, moluscicides, miticides and rodenticides. In another form the term pesticide usually refers to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners, biopesticides and/or growth regulators. Preferred pesticides are fungicides, insecticides, herbicides and growth regulators. Especially preferred pesticides are herbicides. Mixtures of pesticides of two or more of the abovementioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 17th Ed. (2015), The British Crop Protection Council, London. Suitable insecticides are insecticides from the class of the carbamates, organophosphates,

organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz,

hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles,

benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid diamides, chloronitriles cyanoacetamide oximes,

cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates, methoxycarbamates,

morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles. Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphenoxy- propionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N- phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas. In another preferred form the hydrophobic component comprises a pesticide and an oil body, which may be an water-immiscible organic solvent. Preferably, the organic solvent has a solubility in water of up to 20 g/l at 20 °C, more preferably of up to 5 g/l and in particular of up to 0.5 g/l. Usually, the organic solvent has a boiling point above 100°C, preferably above 150 °C, and in particular above 180 °C (at 1 bar). Examples for suitable water-immiscible organic solvents are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore oils of vegetable or animal origin, fatty acid glycerides or their methyl or ethyl ester derivatives, commonly called methyl- or ethyl oleate, aliphatic, cyclic and aromatic

hydrocarbons, e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives. Mixtures of water-immiscible organic solvents may also be used. Preferred water-immiscible organic solvents are fatty acid glycerides or their methyl or ethyl ester derivatives, and/or a hydrocarbons (e.g. aromatic hydrocarbons). A further class of hydrophobic components that can be encapsulated are emollients. Preferably, the hydrophobic components comprise at least one emollient capable to dissolve the

polyisocyanates (component (A)). More preferably, these emollients are capable to dissolve the polyisocyanates without extraneous solvents and/or auxiliaries. Should an emollient not ensure adequate solubility of the polyisocyanates, there is the option of overcoming this disadvantage by using suitable solubility promoters. An emollient is a material that softens, soothes, supplies, coats, lubricates, moisturizes, or cleanses the skin. An emollient typically accomplishes several of these objectives such as soothing, moisturizing, and lubricating the skin. A further class of hydrophobic components that can be encapsulated are dyes. Preferably, the hydrophobic components comprise at least one dye capable to dissolve the polyisocyanates (component (A)). More preferably, these dyes are capable to dissolve the polyisocyanates without extraneous solvents and/or auxiliaries. Should an dye not ensure adequate solubility of the polyisocyanates, there is the option of overcoming this disadvantage by using suitable solubility promoters. Preferred dyes according to the invention are dyes suitable and approved for cosmetic purposes. Examples include cochineal red A (C.I. 16255), patent blue V (C.I.

42051 ), indigotin (C.I. 73015), chlorophyllin (C.I. 75810), quinoline yellow (C.I. 47005), titanium dioxide (C.I. 77891 ), indanthrene blue RS (C.I. 69800) and madder lake (C.I. 58000). These dyes are normally used in concentrations of 0.001 to 0.1 % by weight, based on the mixture as a whole.

A further class of hydrophobic components that can be encapsulated are cosmetically active ingredients. Preferably, the hydrophobic components comprise at least one cosmetically active ingredient capable to dissolve the polyisocyanates (component (A). More preferably, these cosmetically active ingredients are capable to dissolve the polyisocyanates without extraneous solvents and/or auxiliaries. Should an cosmetically active ingredients not ensure adequate solubility of the polyisocyanates, there is the option of overcoming this disadvantage by using suitable solubility promoters. Specifically suitable cosmetically compatible oil bodies are described in Karl-Heinz Schrader, Grundlagen und Rezepturen der Kosmetika [Fundamentals and formulations of cosmetics], 2nd edition, Verlag Hiithig, Heidelberg, pp. 319 - 355, to which reference is made here. Suitable cosmetically active ingredients are, for example, skin and hair pigmentation agents, tanning agents, bleaches, keratin-hardening substances, antimicrobial active ingredients, photofilter active ingredients, repellent active ingredients, hyperemic substances, keratolytic and keratoplastic substances, antidandruff active ingredients, antiphlogistics, keratinizing substances, active ingredients which have an antioxidative effect and/or free-radical scavenging effect, skin-moisturizing or -humectant substances, refatting active ingredients, deodorizing active ingredients, sebostatic active ingredients, plant extracts, antierythimatous or antiallergic active ingredients and mixtures thereof. A further class of hydrophobic components that can be encapsulated are pharmaceutically ingredients. Preferably, the hydrophobic components comprise at least one pharmaceutically ingredient capable to dissolve the polyisocyanates (compound (A)). More preferably, these pharmaceutically ingredients are capable to dissolve the polyisocyanates without extraneous solvents and/or auxiliaries. Should a pharmaceutically ingredient not ensure adequate solubility of the polyisocyanates, there is the option of overcoming this disadvantage by using suitable solubility promoters. In principle, all pharmaceutical active substances and prodrugs are suitable for the use of the hydrophobic components according to the invention. These include

benzodiazepines, antihypertensives, vitamins, cytostatics, in particular taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antimycotics, fungicides, chemotherapeutics, urologies, thrombocyte aggregation inhibitors, sulfonamides, spasmolytics, hormones, immunoglobulins, sera, thyroid therapeutic agents, psychopharmacological agents,

antiparkinsonians and other antihyperkinetic agents, ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, narcotics, antilipemics, hepatic therapeutic agents, coronary agents, cardiacs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics, sedatives, gynecological agents, antigouts, fibrinolytic agents, enzyme preparations and transport proteins, enzyme inhibitors, emetics, circulation-promoting agents, diuretics, diagnostics, corticoids, cholinergics, bile duct therapeutics, antiasthmatics, broncholytics, beta- receptor blockers, calcium antagonists, ACE inhibitors, antiarteriosclerotics, antiinflammatories, anticoagulants, antihypotensives, antihypoglycemics, antihypertonics, antifibrinolytics, antiepileptics, antiemetics, antidotes, antidiabetics, antiarrhythmics, antianemics, antiallergics, anthelmintics, analgesics, analeptics, aldosterone antagonists and slimming agents. Examples of suitable pharmaceutical active substances are in particular the active substances mentioned in paragraphs 0105 to 0131 of US 2003/0157170.

The hydrophopbic component preferably comprises a pharmaceutically acceptable auxiliary. Of pharmaceutical acceptability are the auxiliaries that are known for use in the field of pharmacy, food technology and related fields, in particular the auxiliaries listed in relevant pharmacopoeia (e.g. DAB, Ph. Eur., BP, NF), as well as other auxiliaries whose properties do not preclude a physiological use. Suitable cosmetically and pharmaceutically acceptable auxiliaries are also described in in Fiedler, H. P. Lexikon der Hilfsstoffe fur Pharmazie, Kosmetik und angrenzende Gebiete [Lexicon of the auxiliaries for pharmacy, cosmetics and related fields], 4th edition, Aulendorf: ECV-Editio-Kantor-Verlag, 1996.

A further class of hydrophobic components that can be encapsulated are compositions used for industrial or institutional or hospital applications. Preferably, the hydrophobic components comprise at least one composition used for industrial or institutional or hospital applications capable to dissolve the polyisocyanates (component (A)). More preferably, these are

compositions used for industrial or institutional or hospital applications are capable to dissolve the polyisocyanates without extraneous solvents and/or auxiliaries. Should a composition used for industrial or institutional or hospital applications not ensure adequate solubility of the polyisocyanates, there is the option of overcoming this disadvantage by using suitable solubility promoters. Suitable compositions used for industrial or institutional or hospital applications are, for example, chelants of heavy metal and hardness ions (builders), scale inhibiting agents, corrosion inhibiting agents, deflocculating/dispensing agents, stain removal agents, bleach stabilizing agents, protecting agents of peroxygen labile ingredients, photobleaching enhancing agents, thickener/viscosity modifying agents, crystal growth modification agents, sludge modification agents, surface modification agents, processing aids, electrolyte, hydrolytic stability agents, alkalinity agents and the like. The lipophilic components are compounds which are also useful for certain industrial applications, such as acid cleaners, aluminum etching, boiler cleaning, water treatment, bottle washing, cement modification, dairy cleaners, desalination, electrochemical machining, electroplating, metal finishing, paper mill evaporations, oil field water treatment, paper pulp bleaching, pigment dispersion, trace metal carrier for fertilizers, irrigation, circuit cleaning and the like.

A further class of hydrophobic components that can be encapsulated are textile treatment compositions. Preferably, the hydrophobic components comprise at least one textile treatment composition capable to dissolve the polyisocyanates (component (A)). More preferably, these textile treatment compositions are capable to dissolve the polyisocyanates without extraneous solvents and/or auxiliaries. Should a textile treatment composition not ensure adequate solubility of the polyisocyanates, there is the option of overcoming this disadvantage by using suitable solubility promoters. Suitable textile treatment compositions are softening compositions, such as liquid fabric softeners, fabric softening rinses, fabric softening sheets, tissue papers, paper towels, facial tissues, sanitary tissues, toilet paper and the like.

A further class of hydrophobic components that can be encapsulated are vitamins. Suitable water-insoluble vitamins and provitamins are e.g. vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives, such as tocopherol acetate and vitamin K.

A further class of hydrophobic components that can be encapsulated are anti-oxidants. Suitable anti-oxidants includes, for example: alkylated monophenols, alkylthiomethylphenols,

hydroquinones and alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ether, alkylidenebisphenols, benzyl compounds, hydroxybenzylated malonates, hydroxybenzyl aromatics, triazine compounds, benzylphosphonates, acylaminophenols, esters of p-(3,5-di-tert- butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, esters of p-(5-tert- butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, esters of p-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, amides of p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, ascorbic acid (vitamin C) or aminic antioxidants. A further class of hydrophobic components that can be encapsulated are perfumes and fragrances. Suitable fragrances employed according the present invention are conventional ones known in the art. Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos. 4,145,184, Brain and Cummins, issued Mar. 20, 1979; 4,209,417, Whyte, issued Jun. 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; 4,152,272, Young, issued May 1 , 1979; 5,378,468 Suffis et al.; U.S. Pat. No. 5,081 ,000 Akimoto et al., issued Jan. 14, 1992; U.S. Pat. No. 4,994,266 Wells, issued Feb. 19, 1991 ; U.S. Pat. No. 4,524,018 Yemoto et al., issued Jun. 18, 1985; U.S. Pat. No. 3,849,326 Jaggers et al., issued Nov. 19, 1974; U.S. Pat. No. 3,779,932 Jaggers et al., issued Dec. 18, 1973; JP 07-179,328 published Jul. 18, 1995; JP 05-230496 published Sep. 7, 1993; WO 96/38528 published Dec. 5, 1996; WO 96/14827 published May 23, 1996; WO 95/04809 published Feb. 16, 1995; and WO 95/16660 published Jun. 22, 1995; all of said U.S. patents and U.S. references being incorporated herein by reference. In addition, P. M. Muller, D. Lamparsky Perfumes Art, Science, & Technology Blackie Academic & Professional, (New York, 1994) is included herein by reference. Fragrances can be classified according to their volatility. The highly volatile, low boiling, perfume ingredients typically have boiling points of about 250°C or lower. The moderately volatile perfume ingredients are those having boiling of from about 250°C to about 300°C. The less volatile, high boiling, perfume ingredients are those having boiling points of about 300°C or higher. Many of the perfume ingredients as discussed hereinafter along with their odor and/or flavor characters, and their physical and chemical properties, such as boiling point and molecular weight, are given in "Perfume and Flavor Chemicals (Aroma Chemicals)," Steffen Arctander, published by the author, 1969, incorporated herein by reference. The present invention relates also to a process for the preparation of microcapsules or a dispersion of the microcapsules as defined above.

Embodiment (2): the process for the preparation of a microcapsule dispersion, wherein the microcapsules are defined above and the core essentially contains only a hydrophobic component comprising the following steps:

a) roviding a premix (lb) comprising the hydrophobic component(s) to be encapsulated (Cb), optionally a hydrophobic medium that is liquid at 20°C and 1023 mbar different from (Cb), and at least one component (A) as defined above, and

b) mixing the premix (lb) provided in step a) with a hydrophilic medium comprising at least one hydrophilic protective colloid, at least one component (B1 ) as defined above, and reacting the resulting mixture to form microcapsules dispersed in the hydrophilic medium.

In a preferred embodiement (2a) the process comprising the steps:

a) providing a premix (1Mb) comprising at least one protective colloid in an aqueous solution, b) providing a premix (lib) comprising at least one component A), which is defined above and at least one hydrophobic component, and optionally the hydrophobic medium,

c) mixing premix (1Mb) and premix (lib) until an dispersion (III) is formed,

d) adding an aqueous solution (IV) containing at least one component B1 ), which is defined above, to the emulsion formed in step c),

e) forming a dispersion of microcapsules by heating the mixture obtained in step d) to a temperature of at least 30°C until microcapsules are formed.

Preferrably the hydrophobic component (Cb) is soluble in the hydrophobic medium. Hydrophilic medium is to be understood as meaning either water or those aqueous solutions which, apart from water, comprise up to 20% by weight of a water-miscible organic solvent, such as Cr to C4-alkanols, in particular methanol, ethanol, isopropanol or a cyclic ether, such as tetrahydrofuran. Suitable hydrophilic media are also ethylene glycol, glycerol, polyethylene glycols and butylene glycol, and their mixtures. Preferred hydrophilic media are water and mixtures of these solvents with water.

Typically hydrophobic medium comprises (preferably consists of) the oil body.

A "stable dispersion" in the sense of the present invention denotes a dispersion of

microcapsules which, upon visible inspection, shows no sign of phase separation, such as creaming, settling, precipitation or coagulation when stored for a period of two weeks at a temperature of 50°C.

The term "aqueous solution" in the sense of the invention denotes water and mixtures of water with at least one at least partly water-miscible organic solvent. Suitable organic solvents are e.g. Ci-C4-alkanols. The Ci-C4-alkanols are preferably selected from among methanol, ethanol, n- propanol, isopropanol and n-butanol. Mixtures of at least one Ci-C4-alkanol with water preferably comprise from 0.1 to 99.9% by weight, particularly preferably from 0.2 to 50% by weight, in particular from 0.3 to 10% by weight of at least one Ci-C4-alkanol, based on the total weight of the mixture. In a special embodiment the aqueous solution consists of water.

In one preferred embodiment, the process is carried out as follows:

a) providing a premix (1Mb) comprising at least one protective colloid in an aqueous solution and adjusting the pH in a range of from 5 to 12,

b) providing a further premix (lib) comprising at least one hydrophobic component and

component A),

c) mixing premix (1Mb) and premix (lib) until an dispersion is formed and adjusting the pH of the resulting dispersion in a range of from 5 to 10,

d) adding an aqueous solution (IV) containing at least one polyfunctional amine B1 ) to the dispersion formed in step c),

e) forming a dispersion of microcapsules by heating the mixture obtained in step d) to a

temperature of at least 30°C until microcapsules are formed.

Step a)

Premix (1Mb) provided in step a) contains an aqueous solvent. Suitable solvents are water and mixtures of water with at least one water-miscible organic solvent. Suitable water-miscible organic solvent are mentioned above. Preferably, the solvent is essentially water.

The aqueous solution provided in step a) of embodiment (2a), such as in premix (1Mb), or in step b) of embodiment (2), usually comprises at least one protective colloid, such as an hydrophilic protective colloid.

During the reaction between the component (A) and component (B), a protective colloid, preferably a hydrophilic protective colloid, may be present. Protective colloids are usually polymer systems which, in suspensions or dispersions, prevent a clumping together

(agglomeration, coagulation, flocculation) of the emulsified, suspended or dispersed

components. During solvation, protective colloids bind large amounts of water and in aqueous solutions produce high viscosities depending on the concentration. Within the context of the process described herein, the protective colloid may also have emulsifying properties. The aqueous protective colloid solution is likewise preferably prepared with stirring.

Preferably, the protective colloid (e.g. the hydrophilic protective colloid) is selected from polyvinylpyrrolidones, polyvinyl alcohols, maleic-vinyl copolymers, sodium lignosulfonates, maleic anhydride/styrene copolymers, ethylene/maleic anhydride copolymers, copolymers of ethylene oxide, propylene oxide and ethylenediamine, fatty acid esters of polyethoxylated sorbitol, sodium dodecylsulfate and mixtures thereof. More preferably, the protective colloid is selected from polyvinylpyrrolidones, polyvinyl alcohols and mixtures thereof.

Polyvinylpyrrolidones are particularly preferred.

The polyvinylpyrrolidones preferably have a K value (determined at 25°C in a 1 % by weight aqueous or ethanolic solution) of at least 10, particularly preferably of at least 20, more preferably of at least 80. Determination of the K value is described in H. Fikentscher

"Systematik der Cellulosen auf Grund ihrer Viskositat in Losung", Cellulose-Chemie 13 (1932), 58-64 and 71 -74, and Encyclopedia of Chemical Technology, Vol. 21 , 2 ^nd edition, 427-428 (1970).

Suitable commercially available polyvinylpyrrolidones are the Kollidon trademarks from BASF SE. Preferred polyvinylpyrrolidones useful in the practice of the present invention are available in three grades: Kollidon.RTM. 25 (BASF Corporation), Kollidon.RTM. 90 (BASF Corporation), and Kollidon.RTM. Cl-M (BASF Corporation). Kollidon.RTM. 25 has a weight average molecular weight of 28000-34000. Kollidon.RTM. 90 has a molecular weight average of 1000000- 1500000. Further commercially available polyvinylpyrrolidones are Kollidon 12 which has a weight average molecular weight of 2000-3000, Kollidon 17 which has a weight average molecular weight of 7000-1 1000 and Kollidon 30 which has a weight average molecular weight of 44000-54000.

Particular protective colloids include polyvinyl alcohol copolymers having a degree of hydrolysis in the range of 85 to 99.9%. As used herein, the term "polyvinyl alcohol copolymer" means a polymer of vinyl alcohol/vinyl acetate with comonomers. It is known that polyvinyl alcohol is produced by hydrolysis (deacetylation) of polyvinylacetate, whereby ester groups of polyvinyl acetate are hydrolysed into hydroxyl groups, thus forming polyvinyl alcohol. The degree of hydrolysis reflects the percentage of groups that are converted by hydrolysis. The term

"polyvinyl alcohol", qualified by a degree of hydrolysis, means therefore, a vinyl polymer containing both ester and hydroxyl groups. In a particular embodiment of the invention, copolymers of polyvinyl alcohol with a degree of hydrolysis in the range of 85 to 99.9%, more particularly 85 to 95% may be used as protective colloids. The degree of hydrolysis can be determined by techniques well known in the art, for example, according to DIN 53401. The polyvinyl alcohol copolymers contain addition comonomers, that is, comonomers that are polymerized with a vinyl ester in a first step, followed by hydrolysis of the ester groups to form the copolymer of polyvinyl alcohol in a second step. Copolymers may be formed by radical polymerization of vinyl acetate and comonomers in a manner known per se. Polyvinyl alcohol copolymers may contain unsaturated hydrocarbons as comonomers. These hydrocarbons may be modified with charged or non-charged functional groups. Particular comonomers include, but are not limited to: unsaturated hydrocarbons with 2 or 3 carbon atoms and no functional groups, thylene; unsaturated hydrocarbons having 2 to 6 carbon atoms and non-charged functional groups, such as hydroxyl groups, e.g. buten-1 ,4-diol; unsaturated hydrocarbons having anionic groups, such as carboxyl, and/or sulphonic acid groups; unsaturated hydrocarbons having cationic groups, such as quaternary ammonium groups.

Particular copolymers of polyvinyl alcohol include those having a degree of hydrolysis of 85 to 99.9%, and more particularly 85 to 95%; and which contain: 0.1 to 30 mol% of comonomers containing anionic groups as mentioned above; or

0.1 to 30 mol% of comonomers containing cationic groups as mentioned above; or 0.1 to 30 mol% of comonomers with unsaturated hydrocarbons having 2 to 6 carbon atoms and non-charged functional groups, especially two hydroxyl groups,

wherein mol% is based on the vinyl acetate/comonomer polymerization mixture.

Suitable copolymers of polyvinyl alcohol and comonomers having 1 ,2 diol structures are described in EP 2 426 172 and EP 2 648 21 1 which are herein incorporated by reference.

Particularly preferred polyvinyl alcohols are the Mowiol types available from Kuraray

The protective colloid can be, but does not have to be, a constituent of the capsule shell. The protective colloid may be, but does not have to be, a constituent of the capsule shell with amounts from 0.1 to at most 15% by weight, but preferably in the range from 1 to 5% by weight and in particular from 1.5 to 3% by weight, based on the weight of the capsules, being possible here.

Combinations of two or more different protective colloids may also be employed in the present invention. In a further preferred embodiment, the protective colloid comprises or consists of at least one polyvinylpyrrolidone.

Premix (lb) or premix (lib) or premix (1Mb) may also contain at least one emulsifier. Emulsifiers include non-ionic, cationic, anionic and zwitterionic surfactants. Suitable non-ionic surfactants are selected from the group consisting of products of the addition of 2 to 30 mol ethylene oxide and/or 0 to 5 mol propylene oxide onto linear Ce-22 fatty alcohols, onto C12-22 fatty acids, onto alkyl phenols containing 8 to 15 carbon atoms in the alkyl group and onto alkylamines containing 8 to 22 carbon atoms in the alkyl group; alkyl oligoglycosides containing 8 to 22 carbon atoms in the alkyl group and ethoxylated analogs thereof; addition products of 1 to 15 mol ethylene oxide onto castor oil and/or hydrogenated castor oil; addition products of 15 to 60 mol ethylene oxide onto castor oil and/or hydrogenated castor oil; partial esters of glycerol and/or sorbitan with unsaturated, linear or saturated branched fatty acids containing 12 to 22 carbon atoms and/or hydroxycarboxylic acids containing 3 to 18 carbon atoms and addition products thereof onto 1 to 30 mol ethylene oxide; partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5,000),

trimethylolpropane, pentaerythritol, sugar alcohols (for example sorbitol), alkyl glucosides (for example methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (for example cellulose) with saturated and/or unsaturated, linear or branched fatty acids containing 12 to 22 carbon atoms and/or hydroxycarboxylic acids containing 3 to 18 carbon atoms and addition products thereof onto 1 to 30 mol ethylene oxide; mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol and/or mixed esters of fatty acids containing 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol, mono-, di- and trialkyl phosphates and mono-, di- and/or tri-PEG-alkyl phosphates and salts thereof, wool wax alcohols, polysiloxane/polyalkyl/polyether copolymers and corresponding derivatives, block copolymers, for example Polyethyleneglycol-30 Dipolyhydroxystearate; polymer emulsifiers, for example Pemulen types (TR-1 , TR-2) of Goodrich; polyalkylene glycols and glycerol carbonate and ethylene oxide addition products.

Step b

Premix (lib) provided in step b) comprises at least one component (A) and at least one lipophilic component.

Premix (lib) is generally in liquid form. Preferably, premix (lib) contains no or only a minor amount of solid components. In the sense of the invention a minor amount means that the amount of solid components is at the most 5% by weight, preferably at the most 1 % by weight, more preferably at the most 0.1 % by weight, based on the total weight of premix (lib). In particular, premix (lib) contains no solid components.

Premix (lib) optionally contains at least one organic solvent. An organic solvent is particularly used if the mixture of the employed component (A) and the employed lipophilic components is not liquid under the conditions of process step b).

In a further preferred embodiment of the present invention, the hydrophobic component is used as the solvent for premix (lib). Preferably, premix (lib) contains no extraneous solvents apart from the hydrophobic component.

Step c)

In step c) the premix (1Mb) and premix (lib) are mixed until an dispersion (III) is formed. In order to form an dispersion (III) in the present process, the premix (1Mb) and premix (lib) are emulsified by processes known to the person skilled in the art, e.g. by introducing energy into the mixture through stirring using a suitable stirrer until the mixture emulsifies.

A preferred embodiment is a process, wherein a target range for the volume average diameter of the droplets of the hydrophobic

(discontinuous phase) of the resulting dispersion (III) is predefined,

the actual volume average diameter of the droplets of the hydrophobic phase in the mixture of premix (1Mb) and premix (lib) is determined,

the speed of the stirrer and/or the time of stirring of the mixture are adjusted until the target value volume average diameter of the droplets of the hydrophobic phase of the resulting dispersion (III) is reached in order to obtain the predefined target volume average diameter of the droplets of the hydrophobic phase.

Suitable devices for controlling the volume average diameter of the droplets of discontinuous phase of the resulting dispersion are known to those skilled in the art. Such devises are based, for example, on light scattering measurements. Suitable light scattering measurements are known to those skilled in the art and are commercially available from, for example , Malvern Instruments, e.g. Malvern autosizer.

The rate of stirring of the mixture of premix (1Mb) and premix (lib) in step c) is adjusted to influence the size of droplets of hydrophobic phase in the aqueous phase. After a period of vigorous stirring, an emulsion is obtained, in which the premix (lib) is dispersed as tiny droplets in the aqueous solution of premix (1Mb). The mixture of premix (1Mb) and premix (lib) is stirred vigorously. Preferred stirrer are MIG stirrer, propellers stirrer, paraviscs stirrer, INTERMIG stirrer and isojet stirrer. The pH is preferably adjusted using aqueous bases, preference being given to using sodium hydroxide solution (e.g. 5% strength by weight). Preferably the pH of emulsion (III) is adjusted from 3 to 12, in particular between 4 to 10, and more particular in the range from 5 to 10.

Step d)

The aqueous solution (IV) comprises at least one component (B). Preferably, the aqueous solution (IV) comprises at least one polyfunctional amine. Suitable amines are mentioned below. In a preferred embodiment, the aqueous solution comprises a polylysine.

Step e)

The polyaddition reaction in step e) is generally performed at a temperature of at least 30°C, preferably 50°C, more preferably in a range of from 65°C to 90°C and in particular 75°C to 90°C, in order to ensure sufficiently rapid reaction progress. Here, it may be preferred to increase the temperature in stages (e.g. in each case by 10°C) until then, following completion of the reaction, the dispersion is cooled down to room temperature (21 °C).

The reaction time typically depends on the reaction amount and temperature used. The period of time for the polyaddition reaction is ranging from a few minutes to several hours. Usually, microcapsule formation is established between ca. 60 minutes to 6 h or up to 8 h at the temperatures defined above. A further aspect of the invention relates to the processes according to the invention, wherein the obtained microcapsule dispersion described in embodimenet (1 ), embodiement (2) or embodiement (2a), as described above, may be dryed to provide microcapsules in solid form, preferably in form of a powder.

In another embodiment, the process according to the invention comprising an additional drying step) subjecting the microcapsules or microcapsule dispersion obtaind by the process described above in embodiemts (1 ), (2) and (2a) to a drying. The microcapsules or the microcapsule dispersion may be dried using techniques known in the art. For example, the solid capsules can be isolated by filtration and dryed. Drying of the isolated capsules may be performed by heating, e.g. in an oven or by contact with a heated gas stream. Preferably, drying of the dispersion is carried out by spray drying or fluid-bed drying.

Spray drying techniques and apparatus are well known in the art. A spray-drying process pushes suspended capsules through a nozzle and into a drying chamber. The capsules may be entrained in a fluid (such as air) that moves inside of a drying chamber. The fluid (which may be heated, for example at a temperature of 150 and 120°C, more preferably between 170°C and 200°C, and still more preferably between 175°C and 185°C) causes the liquid to evaporate, leaving behind the dried capsules which can then be collected from the process equipment and further processed. It is conventional to mix spray dried capsules with flow aids to produce a flowable powder that are not susceptible to caking. Flow aids include silicas or silicates, such as precipitated, fumed or colloidal silicas; starches; calcium carbonate; sodium sulphate; modified cellulose; zeolites; or other inorganic particulates known in the art. It is quite common, given the high temperatures and impaction forces encountered during a spray drying procedure, for core shell capsules to lose some of their core material. Furthermore, it may not be possible to work at sufficiently high temperatures for a sufficiently long period of time to drive off all moisture from the dispersion, without compromising the thermal stability of the capsules. Accordingly, the capsules emerging from a spray-drying process, as herein described, may contain small amounts of surface oil as well as residual moisture.

If the microcapsules or microcapsule dispersion of the present invention, irrespectively of its core material, are intended to be stored in the form of a dispersion, the pH of the dispersion is adjusted to a level of about 5 to 10. This may be achieved with the addition to an alkaline dispersion of a suitable acid, such as citric acid or formic acid.

In a further embodiment, the microocapsule or microcapsules or dispersion of the

microcapsules, irrespectively of its core material, may contain non-encapsulated, i.e. free hydrophobic components, external of the capsules in the aqueous dispersion. It is likewise possible for the ingredients of the core to migrate from the core of the

microcapsules (i.e. the hydrophobic component and/or further materials present in the core) into the shell. In a further embodiement of the invention, the microcapsule or microcapsules or dispersion of the microcapsules irrespectively of its core material, comprises at least one preservative in order to prevent microbial contamination of the microcapsules. The preservative may be contained in the aqueous suspending medium of the dispersion. Suitable preservatives include quaternary compounds, biguanide compounds, ethylhexylglycerin, caprylyl glycol, phenezhyl alcohol, propandiol, undecyl alcohol, tocopherol and mixtures thereof. Non-limiting examples of quaternary compounds include benzalkonium chlorides and/or substituted benzalkonium chlorides, di(C6-Ci4)alkyl di short chain (Ci- ₄ alkyl and/or hydroxyalkl) quaternary, N-(3- chloroallyl) hexaminium chlorides, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, diester quaternary ammonium compounds and mixtures thereof.

Preferred commercially available benzalkonium chlorides are sold by Lonza under the trademark Barquat(R), Maquat(R) trademarks from Mason, Variquat(R) trademarks from Witco/Sherex and Hyamine(R) trademarks from Lonza. Preferred commercially available di(C6- Ci ₄ )alkyl di short chain (Ci- ₄ alkyl and/or hydroxyalkl) quaternary are sold by Lonza under the trademark Bardac(R). Preferred commercially available N-(3-chloroallyl) hexaminium chlorides are sold by Dow under the trademark Dowicide(R) and Dowicil(R). Preferred commercially available benzethonium chlorides are sold by Rohm & Haas under the trademark Hyamine(R). Preferred commercially available methylbenzethonium chlorides are sold by Rohm & Haas under the trademark Hyamine(R) 10 ^* . Preferred commercially available cetylpyridinium chlorides are sold by Merrell Labs under the trademark Cepacol chloride. Examples of preferred dialkyl quaternary compounds are di(Cs- Ci2)dialkyl dimethyl ammonium chlorides. Preferred commercially available dialkyl quaternary and dioctyldimethylammonium chlorides are sold by Lonza under the trademark Bardac(R) 22 and (Bardac(R) 2050). The quaternary compounds useful as cationic preservatives and/or antimicrobial agents herein are preferably selected from the group consisting of dialkyldimethylammonium chlorides, alkyldimethylbenzylammonium chlorides, dialkylmethylbenzylammonium chlorides, and mixtures thereof. Other preferred cationic antimicrobial actives useful herein include diisobutylphenoxyethoxyethyl

dimethylbenzylammonium chloride and (methyl)diisobutylphenoxyethoxyethyl

dimethylbenzylammonium chloride (i.e. methylbenzethonium chloride). Preferred commercially available quaternary compounds are sold by Rohm & Haas under the trademark Hyamine(R) 1622. Preferred commercially available preservatives are sold by Schulke under the trademark Sensiva PA20, Sensiva PA40, Sensiva SC10, Sensiva SC50.

The microcapsule composition, microapsules and dispersion of microcapsules as defined above can be used in a large number of different applications, depending on the type of lipophilic component.

A preferred embodiment of the invention is the use of the microcapsule or of microcapsules dispersion irrespectively of its core, material according to the invention for a personal care composition or a composition used for industrial or institutional or hospital disinfection, a material protection composition or a pharmaceutical composition or a plant protection composition or home care products. A preferred embodiment of the invention is the use of the microcapsules or of microcapsules dispersion irrespectively of its core material according to the invention for a cosmetic

composition, a hygiene composition, a composition for industrial or institutional or hospital cleaning or disinfection, laundry detergents, fabric softeners, dishwashing liquids, household cleaners or industrial cleaners, oil recovery, adhesives, coatings, or constructions agro formulations.

Preference is given to using the microcapsules for the finishing of all kind of nonwovens, like wipes (for example wet wipes or dry wipes for cosmetic or cleaning purposes), but also for finishing papers (including wallpapers, toilet paper or papers for books and newsletters), for finishing diapers or sanitary napkins and similar hygienic products or textiles, e.g. in order to finish the papers or textiles with a dye or an insecticide, or in cosmetic compositions, e.g. for producing sunscreen compositions which comprise the UV filter in the form of the

microcapsules. Another use pertains to finishing diapers or sanitary napkins and similar hygienic products. Furthermore the microcapsules may be used in massage oils or cremes or personal lubricants, and suppositories, e.g. to provide this products with antiinflammatory actives. A preferred embodiment of the invention is the use of the microcapsules or of microcapsules dispersion according to the invention in finishing of textiles, papers or nonwovens.

A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in a pharmaceutical composition. Suitable pharmaceutical active substances and prodrugs include benzodiazepines, antihypertensives, vitamins, cytostatics, in particular taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antimycotics, fungicides, chemotherapeutics, urologies, thrombocyte aggregation inhibitors, sulfonamides, spasmolytics, hormones, immunoglobulins, sera, thyroid therapeutic agents, psychopharmacological agents, antiparkinsonians and other antihyperkinetic agents, ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, narcotics, antilipemics, hepatic therapeutic agents, coronary agents, cardiacs,

immunotherapeutics, regulatory peptides and their inhibitors, hypnotics, sedatives,

gynecological agents, antigouts, fibrinolytic agents, enzyme preparations and transport proteins, enzyme inhibitors, emetics, circulation-promoting agents, diuretics, diagnostics, corticoids, cholinergics, bile duct therapeutics, antiasthmatics, broncholytics, beta-receptor blockers, calcium antagonists, ACE inhibitors, antiarteriosclerotics, antiinflammatories, anticoagulants, antihypotensives, antihypoglycemics, antihypertonics, antifibrinolytics, antiepileptics,

antiemetics, antidotes, antidiabetics, antiarrhythmics, antianemics, antiallergics, anthelmintics, analgesics, analeptics, aldosterone antagonists and slimming agents. Examples of suitable pharmaceutical active substances are in particular the active substances mentioned in paragraphs 0105 to 0131 of US 2003/0157170. The formulation base of pharmaceutical compositions preferably comprises at least one pharmaceutically acceptable auxiliary. Pharmaceutically acceptable auxiliaries are auxiliaries which are known for use in the field of pharmaceuticals, food technology and related fields, in particular those listed in the relevant pharmacopeias (e.g., DAB, Ph. Eur., BP, NF), and other auxiliaries, the properties of which do not preclude a physiological application.

A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in a cosmetic composition. Suitable cosmetically active substances and cosmetic auxiliaries are described in Karl-Heinz Schrader, Grundlagen und Rezepturen der Kosmetika [Fundamentals and formulations of cosmetics], 2nd edition, Verlag Hiithig, Heidelberg, which is hereby incorporated by reference.

Suitable cosmetic auxiliaries are described, for example, in Fiedler, H.P., Lexikon der Hilfsstoffe fur Pharmazie, Kosmetik und angrenzende Gebiete [Encyclopedia of Auxiliaries for

Pharmaceuticals, Cosmetics and Related Fields], 4th edition, Aulendorf: ECV-Editio-Kantor- Verlag, 1996. Suitable cosmetic auxiliaries can be lubricants, wetting agents, emulsifying and suspending agents, preservatives, antioxidants, antiirritatives, chelating agents, emulsion stabilizers, film-forming agents, gel formers, odor-masking agents, resins, hydrocolloids, solvents, solubility promoters, neutralizing agents, permeation accelerators, pigments, quaternary ammonium compounds, refatting and superfatting agents, ointment, cream or oil base substances, silicone derivatives, stabilizers, sterilants, propellants, drying agents, opacifiers, thickeners, waxes, softeners or white oils.

A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in a hygiene composition. A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in a compostion for industrial or institutional or hospital cleaning disinfection. A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in a laundry detergents. A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in a fabric softners. A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above- described process in a dishwashing liquids. A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in a household cleaners. A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in a industrial cleaners. A further aspect of the present invention is the use of a microcapsule disperion as described above or obtained by the above-described process in oil recovery. A further aspect of the present invention is the use of a microcapsule disperion as described above or obtained by the above-described process in a adhesive. A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in coatings. A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in or as construction additives composition. Suitable construction additives are selected from plasticizers, superplasticizers, shrinkage reducing agents, corrosion inhibitors, defoaming agents, retardants, accelerators, seeding agents, concrete levelling agents, hydrophobization agents, accelerators for cementitious systems and mixtures thereof. Suitable hydrophobization and shrinkage reducing agents are silicon oil, reactive siloxanes, calcium soaps e.g. calcium stearate; hemiterpene alcohol e.g. isoprenol and fluore-based organo-compounds.

A further aspect of the present invention is the use of a microcapsule dispersion as described above or obtained by the above-described process in agro formulations. When used in agro formulations the hydrophobic component usually comprises a pesticide.

The microcapsules comprising a hydrophobic component selected from pesticides may optionally comprise auxiliaries which are customary in agrochemical formulations. The auxiliaries used depend on the particular application form and active substance, respectively. Examples for suitable auxiliaries are dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations). Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, further dispersants, emulsifiers, wetters, further adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents,

McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

The present invention furthermore relates to a method of controlling phytopathogenic fungi and/or undesired plant growth and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the microcapsules or the microcapsule dispersion, where the hydrophobic component comprises a pesticide, are allowed to act on the respective pests, their environment or the crop plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.

Examples of suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or gooseberries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tangerines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avocados, cinnamon or camphor; energy crops and industrial feedstock crops, for example maize, soybeans, wheat, oilseed rape, sugar cane or oil palm; maize; tobacco; nuts; coffee; tea; bananas; wine (dessert grapes and grapes for vinification); hops; grass, for example turf; sweetleaf (Stevia rebaudania); rubber plants and forest plants, for example flowers, shrubs, deciduous trees and coniferous trees, and propagation material, for example seeds, and harvested produce of these plants.

The term crop plants also includes those plants which have been modified by breeding, mutagenesis or recombinant methods, including the biotechnological agricultural products which are on the market or in the process of being developed. Genetically modified plants are plants whose genetic material has been modified in a manner which does not occur under natural conditions by hybridizing, mutations or natural recombination (i.e. recombination of the genetic material). Here, one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant's properties. Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of glycosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues. The user applies the microcapsule or the microcapsule dispersion usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, very preferably 50 to 200 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

EXAMPLES

The following examples are intented to further illustrate the present invention without limiting its scope in any way.

Determination of the Isocyanate Content was made as follows: Samples were taken from the reaction mixture. Approximately 0.5 g were weighted on an analytical balance. 100 ml. NMP and 25 ml. dibutylamine were added. The mixture was titrated with 0.1 M hydrochloric acid using a solvent pH-electrode and a Metrohm titration system.

Determination of the Water Content and the Hydroxyl Groups was performed with Karl-Fischer method according to DIN 51777 and DIN 53240. Mowiol® 15-97 was a powdered partially hydrolyzed polyvinyl alcohol, viscosity 15 mPas (4 % aqueous solution at 20 °C), degree of hydrolysis about 81 .5 mol%.

Culminal® MPHC 100 was a methylhydroxypropylcellulose with a viscosity of 90-125 mPas at 2% in water. Pergascript Red I 6B was a dye with CAS no. 50292-95-0.

Solvesso® 200 ND was an aromatic hydrocarbon fluid, destination range from 235-290 °C, naphthalene content about 0.9 %.

Poly-L-lysine was used as 50% in water with M _w ~ 2000 Da (20% a-polylysine and 80% ε- polylysine).

Polyester-Polyol A was a reaction product of trimethylolpropan (TMP) and ε-caprolacton, a clear liquid with hydroxy value of 564 mg KOH/g, acid value below 1 mg KOH/g, mean molecular weight 300 g/mol, and a viscosity of about 170 mPas (60 °C). Synthesis of NCO-functionalized oligoester (Product A)

A mixture of 57.4 g Polyester-Polyol A, 120 g methylethylketone and 128,4 g Isophorone- diisocyanate (IPDI) was heated to 100°C and gently stirred. The NCO-content was regularly measured to ensure the conversion rate. NCO content before reaction was about 15.86%. NCO content at the end of the reaction was about 8.64%, indicating for a conversion rate of about 91 %. 247g of the resulting product A was mixed with 150g of Solvesso® 200 ND. The mixture was then heated up to 60°C in a rotary evaporator, under 40 mbar pressure, in order to gently evaporate the methylethylketone from the mixture. The resulting Product A in Solvesso 200 ND had a solid content of 48.9%, and a NCO content of about 6.66%.

Example 1 : Microcapsules with tetraethylene pentamine (B1 )

The microcapsules were prepared by the following operation mode: Prepare the reactor charge by mixing all components together, and slowly add the Feed 1 into the reactor. The dye

Pergascript Red I 6B was dissolved in the Solvesso® 200 ND. Disperse the mixture using a disperser running with 6000 rpm for 15 minutes. Equip the reactor with an anchor stirring blade, and slowly add the Feed 2 into the reactor mixture over a time-period of 60 minutes. Afterwards heat-up the reaction mixture to 80°C within 60 minutes, and further stir at 80°C for additionally 120 minutes. Cool down the mix to room temperature.

Example 2 (comparative): Microcapsules with isophorone diisocyanate (C) and polylysine (B1 ) Quantity [g] Concentration [%]

Mowiol 15-79 50.0 10

Charge Water 185.3 100

Culminal MHPC 100 100.0 5

Solvesso 200 ND 199.6 100

Feed 1 Isophorone diisocyanate 13.1 100

Pergascript Red I 6B 0.4 100

Polylysine (B1 ) 73.8 50

Feed 2

Water 26.2 100

Feed 3 Sodium hydroxide 4.4 25

The microcapsules were prepared by the following operation mode: Prepare the reactor charge by mixing all components together, and slowly add the Feed 1 into the reactor. Disperse the mixture using a disperser running with 6000 rpm for 15 minutes. Slowly add the Feed 3 into the reactor. Equip the reactor with an anchor stirring blade, and slowly add the Feed 2 into the reactor mixture over a time-period of 60 minutes. Afterwards heat-up the reaction mixture to 80°C within 60 minutes, and further stir at 80°C for additionally 120 minutes. Cool down the mix to room temperature.

Example 3: Microcapsules with polylysine (B1 )

The microcapsules were prepared by the following operation mode: Prepare the reactor charge by mixing all components together, and slowly add the Feed 1 into the reactor. Disperse the mixture using a disperser running with 6000 rpm for 15 minutes. Slowly add the Feed 3 into the reactor. Equip the reactor with an anchor stirring blade, and slowly add the Feed 2 into the reactor mixture over a time-period of 60 minutes. Afterwards heat-up the reaction mixture to 80°C within 60 minutes, and further stir at 80°C for additionally 120 minutes. Cool down the mix to room temperature. Example 4: Microcapsules with (B1 ) polylysine

The microcapsules were prepared by the following operation mode: Prepare the reactor charge by mixing all components together, and slowly add the Feed 1 into the reactor. Disperse the mixture using a disperser running with 6000 rpm for 15 minutes. Slowly add the Feed 3 into the reactor. Equip the reactor with an anchor stirring blade, and slowly add the Feed 2 into the reactor mixture over a time-period of 60 minutes. Afterwards heat-up the reaction mixture to 80°C within 60 minutes, and further stir at 80°C for additionally 120 minutes. Cool down the mix to room temperature.

Example 5: Analytic results of the capsule suspensions

The capsule size was determined by Dynamic Light Scattering. Measurements were performed using a Malvern Particle Sizer 3600E type, and following a standard procedure described in the literature. D(0.5) is the median diameter of the volume of distribution. It is expressed in microns, and it indicates that 50% of the sample has a size smaller than that value, whereas 50% have a larger size. D(0.1 ) indicates that 10% of the sample has a size smaller than that value, whereas 90% have a larger size. D(0.9) indicates that 90% of the sample has a size smaller than that value, whereas 10% have a larger size.

The Total Solid Content (TSC) and the Evaporation Rate (ER) were determined as follows: The amount of total solid was determined by drying a given amount mo of the capsule dispersion in the drying oven at 105°C for 2 hours. After drying the new sample weight mi was determined and solid content was calculated as follow: SC% = [1- [(mo - m-i) / mo]] x 100. The evaporation rate was obtained by further drying the same sample at 13 °C for 1 additional hour, giving rise to anew sample weight rri2. The evaporation rate was calculated as follow: ER% = [(mi - 012) / m-i]] x 100. The results are summarized in the following Table. SCthe ^a > SCexp ER ^C > D(0.1 ) D(0.5) D(0.9)

Example 1 40.0% 37.0% 10.2% 3.27

Example 2 ^d > 40.0% 39.6% 3.5% 3.10

Example 3 40.0% 39.5% 2.4% 3.42

Example 4 39.1 % 38.6% - 3.25

a) SCthe corresponds to the theoretical solid content

b) SCex corresponds to the solid content experimentally measured

c) ER corresponds to the evaporation rate

d) comparative

The results demonstrated that the inventive microcapsules had similar particle size and evaporation rate as microcapsules based on the hardly biodegradable isocyanate isophorone diisocyanate used in Example 2. For comparison, the poly(ester-urethane) containing at least 2 isocyanate groups (component A) of the present invention has several ester bonds which allow for a good biodegradability of this microcapsule type at a similar particle size and evaporation rate.

Example 6: Capsule mechanical stability

Test method: A thin layer chromatography aluminium sheet coated with silica gel was cut into a piece of 10 cm * 20 cm. The 200 μηη casting blade was placed on the sheet and filled with the capsule dispersion. The casting blade then was pulled over the aluminium sheet resulting into a dispersion layer with an approximate thickness of 200 μηη. Afterwards the sheet was dried at room temperature. The round tip of a magnetic stir bar was used to put mechanical stress on the microcapsule layer without damaging the silica surface.

Samples of the Examples 1 to 4 were tested. No coloration due to the encapsulated Pergascript Red I 6B was observed before the mechanical trigger in all the samples. The dye could be released due to the mechanical stress and showing a fine line.

The results demonstrated that the inventive microcapsules had similar mechanical stability as microcapsules based on the hardly biodegradable isocyanate isophorone diisocyanate used in Example 2. For comparison, the poly(ester-urethane) containing at least 2 isocyanate groups (component A) of the present invention has several ester bonds which allow for a good biodegradability of this microcapsule type at a similar mechanical stability.

Example 7: Pesticidal microcapsules with tetraethylene pentamine (B1 )

Quantity [g] Concentration [%]

Mowiol 15-79 50.0 10

Charge

Water 203.2 100 Quantity [g] Concentration [%]

Culminal MHPC 100 100.0 5

Solvesso 200 ND 201.8 100

Feed 1 Product A 44.6 100

Pesticide 0.5 100

Tetraethylene pentamine (B1 ) 3.2 100

Feed 2

Water 46.8 100

The microcapsules are prepared by the operation mode as described in Example 1. Instead of the dye water-insoluble pesticides are used:

Example 7A): pyraclostrobin (water solubility 1.9 mg/l at 20 °C)

Example 7B): acetochlor (water solubility 0.2 g/l at 20 °C)

Example 7C): fipronil (water solubility 4 mg/l at 20 °C)

The particle size and evaporation rate are determined as in Example 5 and the results are similar to those of Example 1 in the Table of Example 5. The mechanical stability is determined as in Example 6 and the results are similar to those of Example 1.

Example 8: Pesticidal microcapsules with polylysine (B1 )

The microcapsules are prepared by the operation mode as described in Example 3. Instead of the dye water-insoluble pesticides are used:

Example 8A): pyraclostrobin (water solubility 1.9 mg/l at 20 °C)

Example 8B): acetochlor (water solubility 0.2 g/l at 20 °C)

Example 8C): fipronil (water solubility 4 mg/l at 20 °C).

The particle size and evaporation rate are determined as in Example 5 and the results are similar to those of Example 3 in the Table of Example 5. The mechanical stability is determined as in Example 6 and the results are similar to those of Example 3.