Controlled release microcapsules
A method of forming microcapsules having improved physical properties and release control as well as the microcapsules formed by the process wherein the capsule wall is formed by the concurrent polymerization of monomers, oligomer and/or prepolymers on the inside of the capsule wall and different monomers, oligomers and/or prepolymers on the exterior of the capsule wall as it forms.
1. A method of making microcapsules whose shell wall comprises on one surface a first (meth)acrylate polymer and on its other surface a second (meth)acrylate polymer, said first (meth)acrylate polymer derived from an aqueous phase (meth)acrylate polymer wall forming composition and said second (meth)acrylic polymer derived from an oil phase first (meth)acrylate polymer wall forming composition, and an intermediate region comprising an interpenetrating network and/or copolymer of the two wall forming compositions, said method comprising:
(i) forming an oil-in-water or a water-in-oil emulsion of the two (meth)acrylate polymer wall forming compositions,
(ii) subjecting, the emulsion to conditions for concurrently, at last in part, polymerizing the wall forming materials of each of the oil phase and water phase, and
(iii) allowing the reaction to continue until the microcapsules of desired wall thickness are attained, wherein said process further comprises
(I) the step of oligomerizing and/or prepolymerizing some or all of the (meth)acrylate polymer wall forming components of the oil phase composition, the aqueous phase composition or both prior to forming the emulsion, (II) the step of oligomerizing and/or prepolymerizing some or all of the (meth)acrylate polymer wall forming components of the oil phase composition, the aqueous phase composition or both subsequent to forming the emulsion but prior to initiating wall formation, or (III) using oligomers and/or prepolymers of the wall forming components of the oil phase composition, the aqueous phase composition or both.
2. The method of claim 1 wherein oil phase (meth)acrylate polymer wall forming composition comprises either (A) a combination of (a) at least one oil soluble or dispersible amine (meth)acrylate, (b) at least one oil soluble or dispersible acidic (meth)acrylate or at least one oil soluble or dispersible simple acid or, both, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer, (B) a combination of (a) at least one oil soluble or dispersible acidic (meth)acrylate, (h) at least one oil soluble or dispersible simple base, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer, or (C) one or more oil soluble or dispersible mono-, di- or multi-functional (meth)acrylate monomers or oligomers.
3. The method of claim 2 wherein the method further comprises the step of oligomerizing and/or prepolymerizing some or all of the (meth)acrylate polymer wall forming components of the oil phase composition, the aqueous phase composition or both prior to forming the emulsion in step (i).
4. The method of claim 2 wherein the method further comprises the step of oligomerizing and/or prepolymerizing some or all of the (meth)acrylate polymer wall forming components of the oil phase composition, the aqueous phase composition or both subsequent to forming the emulsion in step (i) but prior to initiating wall formation in steps (ii).
5. The method of claim 2 wherein the process uses oligomers and/or prepolymers of the oil phase composition (A), (B) or (C), the aqueous phase composition or both.
6. The method of claim 2 wherein the oil phase wall forming composition comprises (A) (a) at least one oil soluble or dispersible amine (meth)acrylate, (b) at least one oil soluble or dispersible acidic (meth)acrylate, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer.
7. The method of claim 2 wherein the oil phase wall forming composition comprises (A) (a) at least one oil soluble or dispersible amine (meth)acrylate, (b) at least one oil soluble or dispersible simple acid, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer.
8. The method of claim 2 wherein the oil phase wall forming composition comprises (A) (a) at least one oil soluble or dispersible amine (meth)acrylate, (b) the combination of at least one oil soluble or dispersible acidic (meth)acrylate and at least one oil soluble or dispersible simple acid, and (c) at least one, oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer.
9. The method of claim 2 wherein the oil phase wall forming composition comprises (B) (a) at least one oil soluble or dispersible acidic (meth)acrylate, (b) at least one oil soluble or dispersible simple base, and (c) at least one oil soluble or dispersible multifunctional (meth)acrylate monomer or oligomer.
10. The method of claim 2 wherein the oil phase wall forming composition comprises (C) one or more oil soluble or dispersible mono-, di- or multi-functional (meth)acrylate monomers or oligomers.
11. The method of claim 1 wherein the aqueous phase wall forming composition comprises one or more polyethylene glycol di(meth)acrylates, ethoxylated mono- or multi-functional (meth)acrylates, or (meth)acrylate monomers and/or oligomers.
12. The method of claim 1 herein the water phase further comprises a polymeric emulsifier.
13. The method of claim 12 wherein the polymeric emulsifier is one which comes out of solution during the wall forming process and is incorporated into the shell wall.
14. The method of claim 1 wherein the wall formation is a two-step reaction process where the first reaction step comprises subjecting the emulsion to such conditions as will form oligomers and/or prepolymers of the wall forming materials and the second reaction step comprises subjecting the emulsion to a second set of conditions which effectuates the formation of the shell wall.
15. The method of claim 1 wherein the wall formation is a three-step reaction process where the first step comprising subjecting the emulsion to such conditions as will form oligomers and/or prepolymers of the wall forming materials, the second step comprises subjecting the emulsion to a second set of conditions which effectuates building of the shell wall and the third step comprises subjecting the emulsion to a third set of conditions, which may be merely an extension or continuation of the second set of conditions, to cross-link the polymer(s) of the shell wall.
16. The method of claim 15 wherein the third step effects the cross-linking of the oil phase derived (meth)acrylate polymer.
17. The method of claim 1 wherein initiation of wall formation from the oil phase and the aqueous phase is concurrent.
18. The method of claim 1 wherein initiation of the wall formation from one of the oil phase and the aqueous phase is staggered relative to the other.
19. The method of claim 18 wherein wall formation of the second wall forming composition is initiated after the shell wall is partially formed from the first wall forming material but before the shell wall is impermeable to the wall forming material of the second wall forming composition.
20. The method of claim 18 wherein wall formation of the second wall forming composition is initiated after a seed capsule is formed of the first wall forming material.