Hollow titanium oxide particles for white inks

WO 2015/047306 A1
White pigment dispersions
Hewlett-Packard Development Company

We have discussed the issues regarding white ink jet inks many times in these pages when we have described the many different approaches employed to get over the unavoidable issue of good white pigments being generally heavy, and the pigment size being necessarily large in order to scatter the light. This leads to settling, and potentially complex ink systems.

Some of the more promising white ink jet ink inventions have involved neutral density hollow resin particles – using low refractive index “bubbles” rather than high refractive index dense pigment particles. Others have used a combination of the two. This patent poses the question that if titanium dioxide is the best white pigment, but is too dense, then why not lower its density to give a pigment incorporating the best of both worlds.

The patent suggests two approaches to achieving this, both of which grow the titanium dioxide particles around a template, to give hollow pigment particles with an overall density less than the bulk. The first approach uses a carboxylic acid functional polymer dispersion, such as poly(methyl vinyl ether-alt-maleic acid), in the presence of titanium (IV) oxysulfate. The patent suggests that the carboxylic acid groups of the dispersion strongly coordinate with the Ti4+ groups, resulting in a titanium rich shell. Calcination of this mixture at 550C results in the inventive low density pigment.

The second approach uses an amazing sequence of chemical reactions to form the hollow titanium dioxide particles. A mixture of titanium (IV) oxysulfate is dissolved into water, hydrogen peroxide and urea. The hydrogen peroxide decomposes to water and oxygen, and onto these bubbles adsorbs the titanium oxo species, which are reduced in situ by ammonia (from the hydrolysed urea) to give titanium hydroxide. The resultant sludge is calcined at high temperature to yield the hollow titanium dioxide particles with a claimed 35% reduction in density over standard titanium dioxide.

Inks were made from these lower density pigments and successfully jetted through HP thermal printheads. Pigment settling was claimed to be undetectable during the 45 day experiment.