Biodegradable polyurea/polyurethane microcapsules

1 . Process for preparing a biodegradable polyurea/polyurethane microcapsule comprising the following steps in this order:

(a) carrying out a first polymerisation and/or cross-linking step comprising:

(a1) providing an internal non-aqueous phase comprising at least one polyisocyanate having two or more isocyanate groups and at least one lipophilic active substance to be encapsulated;

(a2) providing an external aqueous phase comprising at least one protective colloid and optionally an emulsifier, and adjusting the pH of the external aqueous phase to a pH of from 1 to 5;

(a3) mixing the internal non-aqueous phase and the external aqueous phase to obtain an oil-in-water emulsion or dispersion; and

(a4) adding at least one first amino acid or amino acid hydrochloride and a catalyst and adjusting the pH of the resulting emulsion or dispersion to a pH of 4 to 8;

(b) carrying out a second polymerisation and/or cross-linking step by adding at least one hydroxyl group donor;

(c) carrying out a third polymerisation and/or crosslinking step by adding at least one second amino acid and adjusting the pH of the emulsion or dispersion to a pH of 4 to 8, to obtain a microcapsule dispersion;

(d) optionally adding a further catalyst and adjusting the pH of the resulting microcapsule dispersion to a pH of 4 to 7;

(e) curing the microcapsule dispersion obtained from step (c) or (d) at a temperature of at least 60° C. for a period of at least 60 minutes;

(f) adding at least one release agent and incorporating the release agent into the shell of the microcapsule;

(g) post-curing the microcapsules obtained in step (f);

and optionally:

(h) separating the microcapsules from the microcapsule dispersion and, if necessary, drying the microcapsules or adjusting the viscosity of the slurry comprising the microcapsules by adding a thickening agent.

2 . Process according to claim 1 , wherein the at least one polyisocyanate having two or more isocyanate groups is selected from the group consisting of aliphatic, cycloaliphatic, hydroaromatic, aromatic and heterocyclic polyisocyanates, their substitution products, and mixtures of the aforementioned compounds.

3 . Process according to claim 1 , wherein the at least one lipophilic active substance to be encapsulated is selected from the group consisting of fragrance compounds, flavourings, cooling agents, TRPV1 and TRPV3 modulators, substances which cause a pungent taste or a warmth or heat sensation on the skin or mucous membranes or a tingling sensation in the mouth or throat, active substances with a pungent or acrid or astringent effect, pesticides, biocides, insecticides, repellents, food additives, cosmetic active ingredients, pharmaceutical active ingredients, dyes, dye precursors, fluorescent dyes, agrochemicals, optical brighteners, solvents, waxes, silicone oils, lubricants, print coatings for paper, and mixtures of two or more of the above-mentioned active ingredients;

wherein the substances which cause a pungent taste or a warmth or heat sensation on the skin or mucous membranes are selected from the group consisting of paprika powder, chilli pepper powder, extracts of paprika, extracts of pepper, extracts of chilli pepper, extracts of ginger roots, extracts of grains of paradise, extracts of para cress, extracts of Japanese pepper, extracts of Kaempferia galanga, extracts of Alpinia galanga, extracts of water pepper, capsaicinoids; gingerols; shogaols; gingerdiones; paradoles; dehydrogingerdiones; piperine; piperine derivatives; ethyl 2-(4-hydroxy-3-methoxy-phenyl)acetate and 3-phenylpropyl 2-(4-hydroxy-3-methoxy-phenyl)acetate and mixtures thereof;

wherein the substances which cause a tingling sensation in the mouth or throat are selected from the group consisting of 2E,4E-decadienoic acid-N-isobutylamide; 2E,4Z-decadienoic acid-N-isobutylamide; 2Z,4Z-decadienoic acid-N-isobutylamide; 2Z,4E-decadienoic acid-N-isobutylamide; 2E,4E-decadienoic acid-N-([2S]-2-methylbutyl)amide; 2E,4E-decadienoic acid-N-([2S]-2-methylbutyl)amide; 2E,4E-decadienoic acid-N-([2R]-2-methylbutylamide); 2E,4Z-decadienoic acid-N-(2-methylbutyl)amide; 2E,4E-decadienoic acid-N-piperide; 2E-decenoic acid-N-isobutylamide; 3E-decenoic acid-N-isobutylamide; 3E-nonenoic acid-N-isobutylamide; 2E,6Z,8E-decatrienoic acid-N-isobutylamide; 2E,6Z,8E-decatrienoic acid-N-([2S]-2-methylbutyl)amide; 2E,6Z,8E-decatrienoic acid-N-([2R]-2-methylbutyl)amide; 2E-decen-4-ynoic acid-N-isobutylamide; 2Z-decen-4-ynoic acid-N-isobutylamide; 2E,6Z,8E, 10E-dodecatetraenoic acid-N-(2-methylpropyl)amide; 2E,6Z,8E, 10E-dodecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,6E,8E, 10E-dodecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8Z,10E,12E-tetradecapentaenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8E,10E,12E-tetradecapentaenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8Z,10E,12E-tetradecapentaenoic acid-N-(2-methyl-2-propenyl)amide; 2E,4E,8Z, 10E, 12E-tetradecapentaenoic acid-N-(2-methylpropyl)amide; 2E,4E,8Z, 11Z-tetradecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8Z, 11E-tetradecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8Z-tetradecatrienoic acid-N-(2-hydroxy-2-methylpropyl)amide and 2E,4E-tetradecadienoic acid-N-(2-hydroxy-2-methylpropyl)amide and mixtures thereof;

wherein the active substances with a pungent or acrid effect are selected from the group consisting of aromatic isothiocyanates, allyl isothiocyanate, cyclopropyl isothiocyanate, butyl isothiocyanate, 3-methylthiopropyl isothiocyanate and mixtures thereof, and

wherein the active substances with astringent effect are selected from the group consisting of: catechins, their oligomers and their C- and O-glycosides; dihydroflavonoids and their C- and O-glycosides, flavonols and their C- and O-glycosides, and mixtures thereof.

4 . Process according to claim 1 , wherein the at least one lipophilic active ingredient to be encapsulated is selected from the group consisting of fragrance compounds and flavourings having aldehyde, carboxylic acid or ester functionality.

5 . Process according to claim 1 , wherein the protective colloid is selected from the group consisting of

diols;

polyols;

polyvinylpyrrolidone, maleic acid vinyl copolymers, sodium lignosulphonates, maleic anhydride/styrene copolymers, ethylene/maleic anhydride copolymers, copolymers of ethylene oxide, propylene oxide and acid esters of polyethoxylated sorbitol, sodium dodecyl sulphate;

animal and vegetable polymers;

and mixtures of the aforementioned compounds.

6 . Process according to claim 1 , wherein the protective colloid is used in combination with starch.

7 . Process according to claim 1 , wherein the at least one first amino acid or amino acid hydrochloride is selected from the group consisting of arginine, histidine, lysine, tryptophan, ornithine, arginine hydrochloride, histidine hydrochloride, lysine hydrochloride, tryptophan hydrochloride, ornithine hydrochloride, and mixtures thereof.

8 . Process according to claim 1 , wherein the catalyst added in step (a4) is selected from the group consisting of diazobicyclo[2.2.2]octane (DABCO), bismuth catalyst, tin catalyst, and mixtures of the aforementioned catalysts; and the optionally further catalyst is selected from the group consisting of para-toluenesulfonic acid, sulfuric acid, germanium oxide and enzymatic catalysts.

9 . Process according to claim 1 , wherein the hydroxyl group donor is a polyol having two or more hydroxyl functional groups.

10 . Process according to claim 1 , wherein the at least one second amino acid is selected from the group consisting of arginine, histidine, aspartic acid, lysine, glycine, alanine, proline, cysteine, glutamine, leucine, serine, tryptophan, valine, threonine, ornithine, and mixtures thereof.

11 . Process according to claim 1 , wherein the at least one release agent is selected from the group consisting of

long-chain, aliphatic, linear or branched, saturated or unsaturated carboxylic acids with 12 to 30 C atoms;

long-chain, aliphatic, linear or branched, saturated or unsaturated primary alcohols with 12 to 30 C atoms;

esters of long-chain, aliphatic saturated carboxylic acids having 12 to 30 C atoms with long-chain, aliphatic primary alcohols having 12 to 30 C atoms;

and mixtures of the aforementioned release agents.

12 . Biodegradable polyurea/polyurethane microcapsule comprising:

(i) a core comprising at least one hydrophobic agent; and

(ii) a capsule shell comprising:

a reaction product of a polymerisation and/or cross-linking of at least one polyisocyanate having two or more isocyanate groups, in the presence of a protective colloid with at least one first amino acid or amino acid hydrochloride, a second polymerisation and/or cross-linking with at least one hydroxyl group donor, and a third polymerisation and/or cross-linking with at least one second amino acid;

at least one release agent; and

a further polyester-based cross-linking matrix or further polyester-based cross-linking units from the reaction of protective colloid, hydroxyl group donor and release agent,

wherein the protective colloid is selected from the group consisting of diols, polyols, polyvinylpyrrolidone, maleic acid vinyl copolymers, sodium lignosulphonates, maleic anhydride/styrene copolymers, ethylene/maleic anhydride copolymers, copolymers of ethylene oxide, propylene oxide and acid esters of polyethoxylated sorbitol, sodium dodecyl sulphate, animal and vegetable polymers, and mixtures of the aforementioned compounds;

the hydroxyl group donor is a polyol having two or more hydroxyl functional groups, and the release agent is selected from the group consisting of long-chain, aliphatic, linear of branched, saturated or unsaturated carboxylic acids with 12 to 30° C. atoms, long-chain, aliphatic, linear or branched, saturated or unsaturated primary alcohols with 12 to 30 C atoms, esters of long-chain, aliphatic saturated carboxylic acids having 12 to 30 C atoms with long-chain, aliphatic primary alcohols having 12 to 30° C. atoms and mixtures of the aforementioned release agents.

13 . Biodegradable polyurea/polyurethane microcapsule according to claim 12 , wherein the capsule shell comprises:

(a) a first crosslinking matrix or first crosslinking units from a polymerisation and/or crosslinking of at least one polyisocyanate having two or more polyisocyanate groups with at least one protective colloid and at least one first amino acid;

(b) a second crosslinking matrix or second crosslinking units from a crosslinking of at least one polyisocyanate having two or more polyisocyanate groups with at least one hydroxyl group donor;

(c) a third crosslinking matrix or third crosslinking units from a crosslinking of at least one polyisocyanate having two or more polyisocyanate groups with at least one second amino acid; and

(d) at least one release agent; and

(e) a further polyester-based cross-linking matrix or further polyester-based cross-linking units.

14 . Biodegradable polyurea/polyurethane microcapsule according to claim 12 , which has a biodegradability according to OECD 301 F after 28 days of ≥20% and/or has a free hydrophobic active ingredient content of ≤0.3 wt.-%.

15 . A method of manufacturing a product comprising incorporating the biodegradable polyurea/polyurethane microcapsule according to claim 12 into the product, wherein the product is a household product, textile care product, detergent, fabric softener, cleaning agent, scent booster, scent lotion, scent enhancer in liquid or solid form, cosmetic, personal care product, perfume composition, agricultural product, pharmaceutical product or print coating for paper.

16 . A household product, textile care product, detergent, fabric softener, cleaning agent, scent booster, scent lotion, scent enhancer, cosmetic, personal care product, perfume composition, agricultural product, pharmaceutical product or print coating for paper comprising the biodegradable polyurea/polyurethane microcapsule according to claim 12 .

17 . Process according to claim 2 , wherein the at least one lipophilic active substance to be encapsulated is selected from the group consisting of fragrance compounds, flavourings, cooling agents, TRPV1 and TRPV3 modulators, substances which cause a pungent taste or a warmth or heat sensation on the skin or mucous membranes or a tingling sensation in the mouth or throat, active substances with a pungent or acrid or astringent effect, pesticides, biocides, insecticides, repellents, food additives, cosmetic active ingredients, pharmaceutical active ingredients, dyes, dye precursors, fluorescent dyes, agrochemicals, optical brighteners, solvents, waxes, silicone oils, lubricants, print coatings for paper, and mixtures of two or more of the above-mentioned active ingredients;

wherein the substances which cause a pungent taste or a warmth or heat sensation on the skin or mucous membranes are selected from the group consisting of: paprika powder, chilli pepper powder, extracts of paprika, extracts of pepper, extracts of chilli pepper, extracts of ginger roots, extracts of grains of paradise, extracts of para cress, extracts of Japanese pepper, extracts of Kaempferia galanga, extracts of Alpinia galanga, extracts of water pepper, capsaicinoids; gingerols; shogaols; gingerdiones; paradoles; dehydrogingerdiones; piperine; piperine derivatives; ethyl 2-(4-hydroxy-3-methoxy-phenyl)acetate and 3-phenylpropyl 2-(4-hydroxy-3-methoxy-phenyl) acetate and mixtures thereof;

wherein the substances which cause a tingling sensation in the mouth or throat are selected from the group consisting of 2E,4E-decadienoic acid-N-isobutylamide; 2E,4Z-decadienoic acid-N-isobutylamide; 2Z,4Z-decadienoic acid-N-isobutylamide; 2Z,4E-decadienoic acid-N-isobutylamide; 2E,4E-decadienoic acid-N-([2S]-2-methylbutyl)amide; 2E,4E-decadienoic acid-N-([2S]-2-methylbutyl)amide; 2E,4E-decadienoic acid-N-([2R]-2-methylbutylamide); 2E,4Z-decadienoic acid-N-(2-methylbutyl)amide; 2E,4E-decadienoic acid-N-piperide; 2E-decenoic acid-N-isobutylamide; 3E-decenoic acid-N-isobutylamide; 3E-nonenoic acid-N-isobutylamide; 2E,6Z,8E-decatrienoic acid-N-isobutylamide; 2E,6Z,8E-decatrienoic acid-N-([2S]-2-methylbutyl)amide; 2E,6Z,8E-decatrienoic acid-N-([2R]-2-methylbutyl)amide; 2E-decen-4-ynoic acid-N-isobutylamide; 2Z-decen-4-ynoic acid-N-isobutylamide; 2E,6Z,8E, 10E-dodecatetraenoic acid-N-(2-methylpropyl)amide; 2E,6Z,8E, 10E-dodecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,6E,8E, 10E-dodecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8Z,10E,12E-tetradecapentaenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8E,10E,12E-tetradecapentaenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8Z,10E,12E-tetradecapentaenoic acid-N-(2-methyl-2-propenyl)amide; 2E,4E,8Z,10E, 12E-tetradecapentaenoic acid-N-(2-methylpropyl)amide; 2E,4E,8Z,11Z-tetradecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8Z,11E-tetradecatetraenoic acid-N-(2-hydroxy-2-methylpropyl)amide; 2E,4E,8Z-tetradecatrienoic acid-N-(2-hydroxy-2-methylpropyl)amide and 2E,4E-tetradecadienoic acid-N-(2-hydroxy-2-methylpropyl)amide and mixtures thereof;

wherein the active substances with a pungent or acrid effect are selected from the group consisting of aromatic isothiocyanates, allyl isothiocyanate, cyclopropyl isothiocyanate, butyl isothiocyanate, 3-methylthiopropyl isothiocyanate and mixtures thereof; and

wherein the active substances with astringent effect are selected from the group consisting of: catechins, their oligomers and their C- and O-glycosides; dihydroflavonoids and their C- and O-glycosides, flavonols and their C- and O-glycosides, and mixtures thereof.

18 . Process according to claim 2 , wherein the at least one lipophilic active ingredient to be encapsulated is selected from the group consisting of fragrance compounds and flavourings having aldehyde, carboxylic acid or ester functionality.

19 . Process according to claim 5 , wherein the protective colloid is used in combination with starch.

20 . Process according to claim 5 , wherein the at least one first amino acid or amino acid hydrochloride is selected from the group consisting of arginine, histidine, lysine, tryptophan, ornithine, arginine hydrochloride, histidine hydrochloride, lysine hydrochloride, tryptophan hydrochloride, ornithine hydrochloride, and mixtures thereof.