Titania-Free Toner Additive Formulation With Cross-Linked Organic Polymeric Additive

A toner process comprising:

• contacting at least one resin;
• an optional wax;
• an optional colorant;
• and an optional aggregating agent;
• heating to form aggregated toner particles;
• optionally, adding a shell resin to the aggregated toner particles, and heating to a further elevated temperature to coalesce the particles;
• adding a surface additive comprising:
• at least one medium silica surface additive having an average primary particle diameter of 30 to 50 nanometers, the at least one medium silica provided at a surface area coverage of 40 to 100 percent of the parent toner particle surface area;
• at least one large cross-linked organic polymeric additive having an average primary particle diameter of 75 to 120 nanometers, the at least one large cross-linked organic polymeric additive provided at a surface area coverage of 5 to 29 percent of the parent toner particle surface area;
• at least one positive charging surface additive, wherein the at least one positive charging surface additive is:
• (a) a titanium dioxide surface additive having an average primary particle size of 15 to 40 nanometers, the titanium dioxide present in an amount of less than or equal to 1 part per hundred based on 100 parts of the parent toner particles;
• and wherein the parent toner particles further contain a small silica having an average primary particle diameter of 8 to 16 nanometers, the small silica present at a surface area coverage of 5 to 75 percent of the parent toner particle surface area;
• or
• (b) a non-titanium dioxide positive charging metal oxide surface additive, wherein the non-titanium dioxide positive charging metal oxide surface additive has an average primary particle size of 8 to 30 nanometers, and wherein the non-titanium dioxide positive charging metal oxide surface additive is present at a surface area coverage of 5 to 15 percent of the parent toner particle surface area;
• and wherein the parent toner particles further optionally contain a small silica having an average primary particle diameter of 8 to 16 nanometers, the small silica present at a surface area coverage of 0 to 75 percent of the parent toner particle surface area;
• and
• wherein a total surface area coverage of all of the surface additives combined is 100 to 140 percent of the parent toner particle surface area;
• and
• optionally, recovering the toner particles.