Water-in-oil capsule manufacture process and microcapsules produced by such process
View Patent ↗A novel method of forming water in oil microcapsules is disclosed. According to the invention microcapsules are obtained by steps comprising dispersing an oil soluble amine modified polyfunctional polyvinyl monomer and an oil soluble bi- or polyfunctional vinyl monomer along with a thermal or UV free radical initiator (optionally included in one or both of the oil or water phases) and an organic acid into an internal phase oil; heating or UV exposing for a time (and temperature) sufficient to oligomerize the amine modified polyfunctional polyvinyl monomer and oil soluble bi- or polyfunctional vinyl monomer forming a pre-polymer. Thereafter the process involves adding to the oil phase oil a water phase comprising a dispersion in water of an anionic emulsifier (and optionally initiator), and adding an emulsifying agent. Emulsifying the water phase into the oil phase (W/O) is controlled through the quantity of water employed. The emulsion is then UV exposed or heated for a time (and temperature) sufficient to decompose the free radical initiators in the oil and/or water phases; thereby forming microcapsule wall material at the interface of the water and oil phases.
1. A process for preparing microcapsules encapsulating a water phase, the process comprising:
dispersing an oil soluble amine modified ethoxylated trimethylol propane triacrylate and an oil soluble diethylene glycol dimethacrylate along with free radical initiator and an organic acid into an oil phase which is a nonsolvent for the water phase; the organic acid selected from the group consisting of monoalkyl maleate, alkyl benzene sulfonic acid, and alkyldiphenoxide sulfonic acid;
a first heating step comprising, heating for time and temperature sufficient to oligomerize the amine modified ethoxylated trimethylol propane triacrylate and a diethylene glycol dimethacrylate forming a pre-polymer;
adding to the oil phase a water phase comprising a dispersion in water of a polyacrylic or polymethacrylic acid, a core material, and an emulsifying agent;
emulsifying the water phase into the oil-phase forming droplets of the water phase dispersed in the oil phase;
a second heating step comprising, heating for a time and temperature sufficient to decompose at least a portion of the free radical initiator in the oil phase;
thereby forming microcapsule wall material at the interface of the water and oil phases the microcapsules encapsulating the water phase droplets; and a third heating step comprising heating to at least 90° C. for at least three hours to polymerize the wall material.
2. The process according to claim 1 wherein a free radical initiator is selected from an azo or peroxy initiator.
3. The process according to claim 1 wherein the oligomerization is accomplished by heating, in the first heating step, to at least 55° C. for at least one hour to form the prepolymer.
4. The process according to claim 1 wherein the emulsifying agent is selected from polyacrylic acid, polymethacrylic acid, alkyl succinamate, alkylarylsulfonic acid salt or alkyl sulfate salt.
5. The process according to claim 1 wherein a second initiator is added in addition to the water phase and wherein the initiator in the oil phase decomposes at a first temperature and the initiator in the water phase decomposes at a second temperature.
6. The process according to claim 5 wherein the initiators in the oil phase and the water phase are the same or different.
7. A process for preparing microcapsules encapsulating a water phase, the microcapsules obtained by steps consisting of:
providing an oil phase and a water phase containing a free radical initiator in at least one of said phases,
dispersing an oil soluble amine modified polyfunctional polyvinyl monomer or oligomer and an oil soluble bi- or polyfunctional vinyl monomer or oligomer and an organic acid into the oil phase; the organic acid selected from the group consisting of monoalkyl maleate, alkyl benzene sulfonic acid, and alkyldiphenoxide sulfonic acid;
adding to the internal phase oil the water phase which further comprises a dispersion in water of an anionic emulsifier, and emulsifying the water phase into the oil phase forming droplets of the water phase in the oil phase;
a first heating step comprising, heating for a time and temperature sufficient to decompose the free radical initiator in at least the oil or water phase, and sufficient to oligomerize or further oligomerize the amine modified polyfunctional polyvinyl monomer or oligomer and oil soluble bi- or polyfunctional vinyl monomer or oligomer forming a pre-polymer and thereby forming microcapsule wall material at the interface of the water and oil phases;
and a second heating step comprising heating to a temperature equal to or greater than the first heating step temperature for a time sufficient to polymerize the wall material.
8. The process according to claim 7 wherein a free radical initiator is selected from an azo or peroxy initiator.
9. The process according to claim 7 wherein the oligomerization is accomplished by heating, in the first heating step, to at least 55° C. for at least one hour to form the prepolymer.
10. The process according to claim 7 wherein the amine modified polyvinyl monomer is selected from amine modified ethoxylated trimethylol propane triacrylate, diacrylate amine, dimethacrylate amine, amine modified polyetheracrylate, and amine modified polyethermethacrylate.
11. The process according to claim 7 wherein the bi- or polyfunctional vinyl monomer or oligomer is selected from a polyacrylate, a polymethacrylate, a dimethacrylate, a diacrylate, a triacrylate, diethylene glycol dimethacrylate, pentaerythritoltriacrylate, trimethylol propane triacrylate, urethane diacrylate, urethane dimethacrylate, ethoxylated aliphatic difunctional urethane acrylate, and ethoxylated aliphatic difunctional urethane methacrylate.
12. The process according to claim 7 wherein the emulsifier is selected from polymethacrylic acid, acrylic acid butyl acrylate copolymer, alkyl succinamates, alkylaryl sulfonic acid salts or alkyl sulfate salts.
13. The process according to claim 7 wherein the second heating step comprises heating to at least 90° C. for at least three hours.
14. The process according to claim 7 wherein initiator is added to both the oil and water phases.
15. The process according to claim 14 wherein the initiator in the oil phase decomposes at a first temperature and the initiator in the water phase decomposes at a second temperature.
16. The process according to claim 14 wherein the initiators in the oil and water phases are the same or different.