Polymeric particles
Polymeric particles comprising a polymeric matrix that has been formed from a blend of monomers comprising a first monomer which is an ethylenically unsaturated ionic monomer and a second monomer which is an ethylenically unsaturated hydrophobic monomer which is capable of forming a homopolymer of glass transition temperature in excess of 50° C., wherein secondary particles are distributed throughout the matrix, in which the secondary particles comprise a hydrophobic polymer that has been formed from an ethylenically unsaturated hydrophobic monomer which is capable of forming a homopolymer of glass transition temperature in excess of 50° C. and optionally other monomers, which hydrophobic polymer is different from the polymeric matrix. Also claimed is a process for preparing particles. The particles have improved shatter resistance. Preferably the polymeric particles comprise an active ingredient, especially a colorant. Such particles combine improved shatter resistance with the ability to retain the active ingredient. The particles of the invention can be used in a variety of industrial applications, for instance in the manufacture of inks, paper and cosmetics.
1. Polymeric particles comprising a polymeric matrix, an active ingredient and secondary particles, which active ingredient and secondary particles are distributed throughout the matrix, which matrix polymer is a copolymer consisting of (meth)acrylic acid or salt units thereof and styrene units,
wherein
the secondary particles consist of a hydrophobic polymer consisting of methyl methacrylate units and 70 wt. % styrene units and,
the secondary particles have a core shell configuration in which the core comprises the hydrophobic polymer and the shell comprises the matrix polymer, and the polymeric matrix is crosslinked.
2. Polymeric particles according to claim 1 , in which the (meth)acrylic acid or salt thereof is a salt of a volatile counterion component.
3. Polymeric particles according to claim 2 in which the (meth)acrylic acid or salt thereof is an acid salt of a volatile counterion component, wherein the volatile counterion component is ammonia or a volatile amine.
4. Polymeric particles according to claim 2 in which the (meth)acrylic acid or salt thereof is an amine salt of a volatile counterion component, wherein the volatile counterion component is a volatile carboxylic acid.
5. Polymeric particles according to claim 1 , which comprise an active ingredient selected from the group consisting of UV absorbers, UV reflectors, flame retardants and active dye tracer materials.
6. Polymeric particles according to claim 1 , in which the (meth)acrylic acid or salt thereof is a free acid.
7. Polymeric particles according to claim 1 in which the polymeric particles have an average particle size of below 100 microns.
8. Polymeric particles according to claim 1 in which the (meth)acrylic acid or salt thereof is a salt of ammonium acrylate, and ammonium zirconium carbonate or zinc oxide is used as a cross-linking agent.
9. Polymeric particles according to claim 1 in which the secondary particles have an average particle size of below 750 nm.
10. Polymeric particles according to claim 9 in which the secondary particles have an average particle size in the range between 50 and 500 nm.
11. Polymeric particles according to claim 1 in which the matrix polymer is impermeable to the active ingredient.
12. A process of preparing polymeric particles comprising a polymeric matrix, an active ingredient and secondary particles which active ingredient and secondary particles are distributed throughout the matrix,
wherein the polymeric matrix is a copolymer consisting of (meth)acrylic acid or salt units thereof and styrene units,
in which the secondary particles consist of a hydrophobic polymer consisting of methyl methacrylate units and 70 wt. % styrene units, which process comprises the steps,
A) providing an aqueous phase of a polymeric salt formed from a copolymer consisting of (meth)acrylic acid or salt units thereof and styrene units and the active ingredient,
B) forming the secondary particles in the aqueous phase or combining the secondary particles with the aqueous phase,
C) forming a dispersion consisting essentially of the aqueous phase in a water immiscible liquid phase which comprises an amphipathic polymeric stabiliser to form an emulsion, and
D) subjecting the dispersion to dehydration wherein water is evaporated from the aqueous particles thereby forming solid particles comprising the secondary particles distributed throughout the matrix polymer,
wherein the secondary particles have a core shell configuration in which the core comprises the hydrophobic polymer and the shell comprises the matrix polymer and the polymeric matrix is crosslinked.
13. A process according to claim 12 , in which the (meth)acrylic acid or salt thereof is a salt of a volatile counterion component.
14. A process according to claim 13 in which the (meth)acrylic acid or salt thereof is a salt of a volatile counterion component, wherein the volatile counterion component is ammonia or a volatile amine.
15. A process according to claim 12 , in which the particles comprise an active ingredient selected from colourant.
16. A process according to claim 15 in which the colourant is a dye, pigment or lake.
17. A process according to claim 12 , in which the (meth)acrylic acid or salt thereof is a free acid.
18. A process according to claim 12 , in which a cross-linking agent is included in the aqueous phase and the matrix polymer becomes cross-linked during the dehydration step.
19. A process according to claim 18 in which the matrix polymer is impermeable to the active ingredient.
20. A process according to claim 18 in which the dehydration step involves vacuum distillation.
21. A process according to claim 12 in which the polymeric particles have an average particle size of below 100 microns.
22. A process according to claim 12 in which the polymeric matrix is a copolymer consisting of monomer units of styrene and ammonium acrylate, and ammonium zirconium carbonate or zinc oxide is used as a cross-linking agent.
23. A process according to claim 12 in which the secondary particles have an average particle size of below 750 nm.
24. A process according to claim 23 in which the secondary particles have an average particle size in the range between 50 and 500 nm.
25. A process according to claim 12 in which particles are formed as a micro emulsion within the aqueous phase by microemulsion polymerisation.
26. A process according to claim 12 in which the dehydration step involves spray drying.