Controlled release dual walled microcapsules
View Patent ↗A method of forming dual melamine/acrylic walled 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 use of select (meth)acrylate monomers and/or oligomers and/or select self-condensing melamine resins.
1. A method of making microcapsules whose shell wall comprises on one surface a melamine resin and on its other surface a (meth)acrylate polymer, said melamine resin derived from an aqueous phase composition and said (meth)acrylic polymer comprising the reaction product of 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 or (B) a combination of (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 derived from an oil phase composition, and an intermediate region comprising an interpenetrating network and/or copolymer of melamine resin and (meth)acrylate polymer, said method comprising:
(i) forming an oil-in-water or a water-in-oil emulsion of the melamine based aqueous phase and the (meth)acrylate ester oil phase,
(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.
2. The method of claim 1 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 subsequent to forming the emulsion but prior to initiating wall formation.
3. The method of claim 1 wherein the oil phase composition, prior to forming the emulsion, comprises oligomers and/or prepolymers of some or all of the (meth)acrylate polymer wall forming components of the oil phase composition.
4. The method of claim 1 wherein the (meth)acrylate polymer is derived from (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.
5. The method of claim 1 wherein the (meth)acrylate polymer is derived form (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.
6. The method of claim 1 wherein the (meth)acrylate polymer is derived from (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.
7. The method of claim 1 wherein the (meth)acrylate polymer is derived from (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.
8. The method of claim 1 wherein the aqueous phase composition comprises monomers, oligomers and/or prepolymers of the precursors or building blocks for a melamine-based polyurea, a melamine-formaldehyde resin, a melamine-aldehyde resin, dimethylol melamine urea, methylated dimethylol melamine urea, methylated melamine formaldehyde, methylated methylol melamine, end mixtures of melamine formaldehyde with urea formaldehyde.
9. The method of claim 8 wherein the method further comprises the step of oligomerizing and/or prepolymerizing the monomeric and/or oligomeric precursor components for the melamine resin.
10. The method of claim 9 wherein the water phase further comprises a polymeric emulsifier.
11. The method of claim 10 wherein the polymeric emulsifier is one which comes out of solution during the wall forming process and is incorporated into the shell wall.
12. 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 prepolymers and polymers of the wall forming materials and the second reaction step comprises subjecting the emulsion to second set of conditions which effectuates the formation of the shell wall.
13. 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 prepolymers and polymers 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.
14. The method of claim 13 wherein the third step effects the cross-linking of the (meth)acrylate polymer.
15. The method of claim 1 wherein initiation of wall formation from the oil phase and the aqueous phase is concurrent.
16. 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.
17. The method of claim 16 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.
18. The method of claim 16 wherein wall formation of the second wall forming composition is initiated after a seed capsule is formed of the first wall forming material.