Electrostatic ink compositions

1. A liquid electrostatic ink composition comprising a liquid carrier having dispersed therein:

chargeable particles comprising a thermoplastic resin having acidic side groups; and

globular particles having a carbohydrate core and a shell surrounding the carbohydrate core, the carbohydrate core being a monosaccharide or a polysaccharide of a saccharide unit selected from the group consisting of ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, and galactose, and the shell being a hydrocarbon having a drop point, measured according to ASTM D3954-15, of at least 120° C., the globular particles having a D50 of from 2 μm to 7 μm and a D90 of 10 μm or less, the D50 and D90 being measured in the liquid carrier using laser diffraction and volume distribution, in accordance with ISO13220, wherein the hydrocarbon is polyethylene.

2. The liquid electrostatic ink composition according to claim 1 , wherein the polyethylene comprises high density polyethylene.

3. The liquid electrostatic ink composition according to claim 1 , wherein the polyethylene has a drop point of at least 125° C.

4. The liquid electrostatic ink composition according to claim 1 , wherein at least some of the globular particles have an aspect ratio of 1.5 or less.

5. The liquid electrostatic ink composition according to claim 1 , wherein the globular particles are present in an amount of from 3 wt % to 15 wt % of the solids of the liquid electrostatic ink composition.

6. The liquid electrostatic ink composition according to claim 1 , wherein the liquid electrostatic ink composition lacks halogenated compounds.

7. The liquid electrostatic ink composition according to claim 1 , wherein the thermoplastic resin having acidic side groups is a copolymer of an alkylene monomer and a monomer selected from acrylic acid and methacrylic acid.

8. A method of forming an electrostatic ink composition comprising:

grinding a thermoplastic resin having acidic side groups in a liquid carrier to provide a slurry comprising particles comprising the thermoplastic resin dispersed in the liquid carrier;

adding globular particles to the slurry, the globular particles having a carbohydrate core and a shell surrounding the carbohydrate core, the carbohydrate core being a monosaccharide or a polysaccharide of a saccharide unit selected from the group consisting of ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, and galactose, and the shell comprising a hydrocarbon having a drop point, measured according to ASTM D3954-15, of at least 120° C., and the globular particles having a D50 of from 2 μm to 7 μm and a D90 of 10 μm or less, the D50 and D90, when measured in the liquid carrier using laser diffraction and volume distribution, in accordance with ISO13220, wherein the hydrocarbon is polyethylene;

wherein the globular particles are mixed in the slurry without reducing the particle size of the globular particles.

9. The method according to claim 8 , wherein the globular particles are mixed in the slurry by stirring or shaking the slurry.

10. The method according to claim 8 , wherein a charge director is added to the slurry either before or after adding the globular particles to the slurry.

11. A substrate having printed thereon:

a layer formed from a thermoplastic resin having acidic side groups;

wherein globular particles protrude above the surface of the thermoplastic resin, the globular particles having a carbohydrate core and a shell surrounding the carbohydrate core, the carbohydrate core being a monosaccharide or a polysaccharide of a saccharide unit selected from the group consisting of ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, and galactose, and the shell comprising a hydrocarbon having a drop point, measured according to ASTM D3954-15, of at least 120° C., wherein the hydrocarbon is polyethylene.

12. The substrate according to claim 11 , wherein at least some of the globular particles have a diameter of from 2 μm to 10 μm.