Granted Patent B2

US 12,365,853 · App. 17/437,870 · Granted Jul 22, 2025

Inventors: Andreas Herrmann (Satigny, CH); Damien Berthier (Satigny, CH); Serge Lamboley (Satigny, CH); Kitty Van Gruijthuijsen (Satigny, CH); Nicolas Paret (Satigny, CH)

Assignee: FIRMENICH SA

C11D3/505B01J13/16C11D3/2041C11D3/2065

Abstract

Claims (39)

1. A process for a preparation of a core-shell microcapsule slurry comprising the following steps:

a) adding at least one polyfunctional monomer in a hydrophobic material to form an oil phase;

b) preparing a dispersing phase, wherein the dispersing phase is not miscible with the oil phase;

c) adding the oil phase into the dispersing phase to form a two-phase dispersion;

d) optionally, adding a reactant to the dispersion obtained in step c); and

e) performing a curing step to form core-shell microcapsules in the form of a slurry,

wherein a stabilizer is added in step a) and/or step b),

wherein at least one cleavable multi-alcohol is added in step a) and/or in step b) and/or in step c) and/or in step d),

wherein the cleavable multi-alcohol has the following formula (I)

wherein each R 1 is independently H or CH 2 OH and wherein p and q are integers varying between 1 and 3,

wherein X is a C 2 to C 30 hydrocarbon group, optionally comprising one to ten heteroatoms, selected from the group consisting of O, S and N to form ether, ester, carboxylic acid, aldehyde, ketone, alcohol, thiol, disulfide, thioether, thioester, carbamate, amide, oxime, imine, amine or nitrile functional groups;

wherein the cleavable multi-alcohol is not trimethylol propane; and

wherein the core-shell microcapsules comprise a reaction product between the polyfunctional monomer and the cleavable multi-alcohol.

2. The process according to claim 1 , wherein X is a compound selected from the group consisting of disulfides, oxazolidines, imines, 1,4-addition products, carbonates and aryl ketone derivatives.

3. The process according to claim 1 , wherein X is selected from the group consisting of

with L being a O or a S atom or a NH group, M being a S atom or a NR 6 group, Y being a CH 2 , a CH 2 —CH 2 or a phenyl group, Z being a O(CH 2 ) x O or a (CH 2 ) x group with x being an integer varying between 1 and 4, and A being a COOCH 2 (CR 2 R 2 ) i , CHR 2 OCH 2 (CR 2 R 2 ); or (CR 2 R 2 )(CHR 2 ) x group,

with each R 2 being independently a H, CH 3 , CH 2 CH 3 , CH 2 OH or CH 2 CH 2 OH group and each R 3 being independently a CH 3 or CH 2 CH 3 group,

with R 4 being either H or CH 3 or, if Y is not phenyl group, then two R 4 taken together may represent a CH 2 or a CH 2 —CH 2 group,

with R 5 being either H or CH 3 ,

with R 6 being either H, a C 1 -C 6 alkyl group or a CH 2 —CH 2 —(CH 2 ) j —OH group, if t=1 two R 6 taken together might form a CH 2 —CH 2 —(CH 2 ) i group,

with h being an integer varying between 1 and 6, each i being individually of each other 0 or 1, each j being individually of each other an integer varying between 0 and 2, and

with k and l being integers varying between 0 and 2, and m and n being 1 or 2, with the proviso that k+l+m+n=4,

with t, u and u′ being 0 or 1, v and w being 1 or 2, and with the proviso that u+v+w=3 (if t=0) or u+u′+v+w=4 (if t=1), and

wherein the hatched and the bold lines are either linked to a hydrogen atom or indicate the bond between said X and the (CHR 1 OH) p (hatched line) or (CHR 1 OH) q (bold line) groups of the multi-alcohol of formula (I), with the proviso that at least one hatched and at least one bold line of X are linked to a CHR 1 OH group.

4. The process according to claim 1 , wherein the cleavable multi-alcohol is a compound selected from the group consisting of:

disulfides selected from the group consisting of 2,2′-disulfanediylbis(ethan-1-ol), 2,2′-disulfanediylbis(propane-1,3-diol), 3-(2,3-dihydroxypropyldisulfanyl)propane-1,2-diol, 2,2′-(disulfanediylbis(methylene))bis(2-methylpropane-1,3-diol), 2,2′-(disulfanediylbis(methylene))bis(2-ethylpropane-1,3-diol), bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl) 3,3′-disulfanediyldipropionate, and tetrakis(2-hydroxyethyl) 2,2′-disulfanediyldisuccinate,

oxazolidines selected from the group consisting of (3-(2-hydroxyethyl)oxazolidine-2,2-diyl)dimethanol, oxazolidine-2,2,4-triyltrimethanol, 2,2′-(ethane-1,2-diylbis(2-methyloxazolidine-2,3-diyl))bis(ethan-1-ol), (ethane-1,2-diylbis(2-methyloxazolidine-2,4,4-triyl))tetramethanol, 2,2′-(1,4-phenylenebis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2′-(furan-2,5-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2′-(cyclohexane-1,4-diylbis(oxazolidine-2,3-diyl))bis(ethan-1-ol), 2,2′-(1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ] tetradecane-4,12-diyl)bis(ethan-1-ol), (1,4-phenylenebis(oxazolidine-2,4,4-triyl))tetramethanol, (1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,3,11,11-tetrayl)tetramethanol, (1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, (3,11-diethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, (1,4-phenylenebis(4-ethyloxazolidine-2,4-diyl))dimethanol, (3,11-diethyl-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-3,11-diyl)dimethanol, and 2,2′-(3,11-bis(hydroxymethyl)-1,9-dioxa-4,12-diazadispiro[4.2.4 8 .2 5 ]tetradecane-4, 12-diyl)bis(ethan-1-ol),

imines and Schiff bases selected from the group consisting of 2,2′-((1,4-phenylenebis(methanylylidene))bis(azanylylidene))bis(propane-1,3-diol), and 2,2′-((furan-2,5-diylbis(methanylylidene))bis(azanylylidene))bis(propane-1,3-diol),

1,4-Addition products selected from the group consisting of 2-hydroxyethyl 3-((2-hydroxyethyl)thio)propanoate, 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl 3-((3-hydroxy-2-(hydroxymethyl)-2-methylpropyl)thio)-2-methylpropanoate, 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl(S)-3-((2,3-dihydroxypropyl)thio) propanoate, 2-ethyl-2-(((3-((2-hydroxyethyl)thio)propanoyl)oxy)methyl) propane-1,3-diyl bis(3-((2-hydroxyethyl)thio) propanoate), 4-hydroxybutyl 3-((1,3-dihydroxypropan-2-yl)amino)propanoate, bis(2-hydroxyethyl) 3,3′-(butylazanediyl)dipropionate, bis(2-hydroxyethyl) 3,3′-((4-hydroxybutyl)azanediyl)dipropionate, bis(2-hydroxyethyl) 3,3′-(piperazine-1,4-diyl)dipropionate, tetrakis(2-hydroxyethyl) 3,3′,3″,3′-(propane-1,3-diylbis(azanetriyl))tetrapropionate, and bis(3-((2-hydroxyethyl)thio)propyl) 2-((2-hydroxyethyl)thio)succinate,

carbonates selected from the group consisting of bis(2,3-dihydroxypropyl) carbonate, bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl) carbonate, and benzene-1,3,5-triyl tris(3-((2-hydroxyethyl)thio) propyl)tricarbonate,

aryl ketone derivatives selected from the group consisting of bis(2-hydroxyethyl) 2,2′-(methylenebis(4,1-phenylene))bis(2-oxoacetate), bis(2,2-bis(hydroxymethyl)butyl) 2,2′-(methylenebis(4,1-phenylene))bis(2-oxoacetate), bis(2-hydroxyethyl) 2,2′-(ethane-1,2-diylbis(4,1-phenylene))bis(2-oxoacetate), bis(3-hydroxy-2-(hydroxymethyl)-2-methylpropyl) 2,2′-(1,4-phenylene)bis(2-oxoacetate), and 1,1′-(1,4-phenylene)bis(5-hydroxypentan-1-one), and

mixtures thereof.

5. The process according to claim 1 , wherein the polyfunctional monomer is selected from the group consisting of at least one polyisocyanate, polyanhydride, poly acyl chloride, polyepoxide, polyacrylate monomers, polymethacrylate and polyalkoxysilane, and mixtures thereof.

6. The process according to claim 1 , wherein the reactant is selected from the group consisting of nitrogen nucleophile, sulfur nucleophile, enol carbon nucleophile, oxygen nucleophile, phosphor nucleophile and mixtures thereof.

7. The process according to claim 6 , wherein the reactant is selected from the group consisting of xylylene diamine, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, L-lysine, L-Lysine ethyl ester, O,O′-bis(2-aminopropyl)polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol, ethylene diamine, 1,3-diamino-2-hydroxypropane, diethylene triamine, spermine, spermidine, cystamine, cystine, cystine dialkyl ester, aminoguanidine bicarbonate, N,N′-diethylethylenediamine, polyamidoamine (PAMAM), chitosan, 3-aminopropyltriethoxysilane, L-arginine, 1,3-diaminopropane, N-ethylguanidine sulfate, 1,6-diaminohexane, guanidine salts, N,N,N′,N′-tetrakis(3-aminopropyl)-1,4-butanediamine, guanazole, 2-amino-1,3-propanediol, ethanolamine tris(2-aminoethyl) mine, tris(3-aminopropyl)amine, tris[2-(methylamino)ethyl]amine, 1-(2-Aminoethyl) piperazine, triethylenetetramine, triethanolamine, phthalic acid dipotassium salt, succinic acid disodium salt, dithiothreitol and mixtures thereof.

8. The process according to claim 1 , wherein the stabilizer is selected from the group consisting of gum Arabic, modified starch, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, anionic polysaccharides, acrylamide copolymer, inorganic particles, proteins and mixtures thereof.

9. The process according to claim 1 , wherein the hydrophobic material is a perfume.

10. The process according to claim 1 , wherein p and q are either 1 or 2.

11. The process according to claim 3 , with L being a O atom and M being a S atom.

Assignments (1)

Priority Claims (1)

Continuity (2)

References Cited (11)