Toner emulsion aggregation process

• US 5,418,108 A
• Filed: 06/25/1993
• Issued: 05/23/1995
• Est. Priority Date: 06/25/1993
• Status: Expired due to Term

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Patel, Raj D., Kmiecik-Lawrynowicz, Grazyna E.
• Primary Examiner(s): Rodee, Christopher D.
• Application Number:
  US08/082,741
• Time in Patent Office: 697 Days
• Field of Search: 430/137, 430/109, 528/936, 523/335
• US Class Current: 430/137.14
• CPC Class Codes: G03G 9/0804 whereby the components are brought together in a liquid dispersing medium
• CPC Class Codes: G03G 9/0815 Post-treatment
• CPC Class Codes: Y10S 528/936 Coagulating

Abstract

A process for the preparation of toner compositions with controlled particle size and selected morphology comprising

(i) preparing a pigment dispersion in water, which dispersion is comprised of pigment, ionic surfactant, and optionally a charge control agent;

(ii) shearing the pigment dispersion with a polymeric latex comprised of resin of submicron size, a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant and a nonionic surfactant thereby causing a flocculation or heterocoagulation of the formed particles of pigment, resin and charge control agent, and generating a uniform blend dispersion of solids of resin, pigment, and optional charge control agent in the water and surfactants;

(iii) (a) continuously stirring and heating the above sheared blend to form electrostatically bound toner size aggregates; or

(iii) (b) further shearing the above blend to form electrostatically bound well packed aggregates; or

(iii) (c) continuously shearing the above blend, while heating to form aggregated flake-like particles;

(iv) heating the above formed aggregated particles about above the Tg of the resin to provide coalesced particles of toner; and optionally

(v) separating said toner particles from water and surfactants; and

(vi) drying said toner particles.

Claims

1. A process for the preparation of toner compositions with controlled particle size and selected morphology consisting essentially of

(i) preparing a pigment dispersion in water, which dispersion is comprised of pigment, ionic surfactant, and optionally a charge control agent;

(ii) shearing the pigment dispersion with a polymeric latex comprised of resin of submicron size, a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant and a nonionic surfactant thereby causing the formation of a uniform blend dispersion of resin particles, pigment particles, and optional charge control agent particles in water and surfactants, and wherein said resin particles, pigment particles, and optional charge control agent particles are flocculated or heterocoagulated together in said dispersion;

(iii) (a) continuously stirring and heating the above sheared blend to form electrostatically bound toner size aggregates;

or

(iii) (b) further shearing the above blend to form electrostatically bound well packed aggregates;

or

(iii) (c) continuously shearing the above blend, while heating to form aggregated flake particles;

(iv) heating the above formed aggregated particles above about the Tg of the resin to provide coalesced particles of toner; and

optionally

(v) separating said toner particles from water and surfactants; and

(vi) drying said toner particles.

2. A process in accordance with claim 1 wherein the morphology of the toner particles is controlled to be from grape, cauliflower, raspberry, or potato up to substantially perfect spheres.

3. A process in accordance with claim 1 wherein the temperature above the resin Tg (step iv) primarily controls the morphology of the toner particles.

4. A process in accordance with claim 1 wherein the morphology of the toner particles is controlled by the shear rate in the range of from about 5,000 revolutions per minute to 15,000 revolutions per minute applied in the blending step (ii).

5. A process in accordance with claim 1 wherein the surfactant utilized in preparing the pigment dispersion is a cationic surfactant, and the counterionic surfactant present in the latex mixture is an anionic surfactant.

6. A process in accordance with claim 1 wherein the surfactant utilized in preparing the pigment dispersion is an anionic surfactant, and the counterionic surfactant present in the latex mixture is a cationic surfactant.

7. A process in accordance with claim 1 wherein the dispersion of pigment (i) is accomplished by homogenizing at from about 1,000 revolutions per minute to about 10,000 revolutions per minute at a temperature of from about 25°

C. to about 35°

C. for a duration of from about 1 minute to about 120 minutes.

8. A process in accordance with claim 1 wherein the dispersion of pigment (i) is accomplished by an ultrasonic probe at from about 300 watts to about 900 watts of energy, at from about 5 to about 50 megahertz of amplitude, at a temperature of from about 25°

C. to about 55°

C., and for a duration of from about 1 minute to about 120 minutes.

9. A process in accordance with claim 1 wherein the dispersion of pigment (i) is accomplished by microfluidization in a microfluidizer, or in nanojet for a duration of from about 1 minute to about 120 minutes.

10. A process in accordance with claim 1 wherein generating a uniform blend dispersion of resin particles, pigment particles, and optional charge control agent particles (ii) is accomplished by homogenizing at from about 1,000 revolutions per minute to about 10,000 revolutions per minute for a duration of from about 1 minute to about 120 minutes with a polytron or homogenizer.

11. A process in accordance with claim 1 wherein the heating of the blend of latex, pigment particles, surfactants and optional charge control agent particles in (iii a and c) is accomplished at temperatures of from about 20°

C. to about 5°

C. below the Tg of the resin for a duration of from about 0.5 hour to about 48 hours.

12. A process in accordance with claim 1 wherein the heating of the statically bound aggregate particles to form toner composition particles comprised of pigment particles, resin particles and optional charge control agent particles is accomplished at a temperature of from about 10°

C. above the Tg of the resin to about 95°

C. above Tg for a duration of from about 1 hour to about 8 hours, and wherein the resin of (ii) is of a submicron size of from about 0.05 to about 1 micron.

13. A process in accordance with claim 1 wherein the resin is selected from the group consisting of poly(styrene-butadiene), poly(paramethyl styrene-butadiene), poly(meta-methyl styrene-butadiene), poly(alpha-methylstyrene-butadiene), poly(methylmethacrylate-butadiene), poly(ethylmethacrylate-butadiene), poly(propylmethacrylate-butadiene), poly(butylmethacrylate-butadiene), poly(methylacrylate-butadiene), poly(ethylacrylate-butadiene), poly(propylacrylate-butadiene), poly(butylacrylate-butadiene), poly(styrene-isoprene), poly(paramethylstyrene-isoprene), poly(meta-methylstyrene-isoprene), poly(alpha-methylstyrene-isoprene), poly(methylmethacrylate-isoprene), poly(ethylmethacrylate-isoprene), poly(propylmethacrylate-isoprene), poly(butylmethacrylate-isoprene), poly(methylacrylate-isoprene), poly(ethylacrylate-isoprene), poly(propylacrylate-isoprene), and poly(butylacrylate-isoprene).

14. A process in accordance with claim 1 wherein the resin is selected from the group consisting of poly(styrene-butadiene-acrylic acid) poly(styrene-butadiene-methacrylic acid) poly(styrene-butylmethacrylate-acrylic acid), or poly(styrene-butylacrylate-acrylic acid), polyethylene-terephthalate, polypropylene-terephthalate, polybutylene-terephthalate, polypentylene-terephthalate, polyhexalene-terephthalate, polyheptadene-terephthalate, and polyoctalene-terephthalate.

15. A process in accordance with claim 1 wherein the nonionic surfactant is selected from the group consisting of polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly(ethyleneoxy) ethanol, polyvinyl alcohol, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, and carboxy methyl cellulose.

16. A process in accordance with claim 1 wherein the ionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium dodecylnaphthalene sulfate, sodium lauryl sulfate, sodium alkyl naphthalene sulfonate, and potassium alkyl sulfonate.

17. A process in accordance with claim 1 wherein the pigment is carbon black, cyan, yellow, magenta, red, blue, green, brown, or mixtures thereof.

18. A process in accordance with claim 1 wherein the pigment is present in the amount of from about 0.1 to about 10 percent by weight.

19. A process in accordance with claim 1 wherein the pigment particles are from about 0.01 to about 1 micron in volume average diameter;

the resin utilized in (ii) is from about 0.01 to about 3 microns in average volume diameter;

the coalesced particles formed in (iv) are from about 1 to about 20 microns in average volume diameter;

the toner composition isolated is from about 1 to about 20 microns in average volume diameter; and

the geometric size distribution thereof of said toner composition is from about 1.15 to about 1.35.

20. A process in accordance with claim 1 wherein the toner particles are washed with warm water, and the surfactants are removed from the toner surface, followed by drying.

21. A process in accordance with claim 1 wherein there is added to the surface of the obtained toner particles additives of metal salts, metal salts of fatty acids, silicas, metal oxides, or mixtures thereof in an amount of from about 0.1 to about 10 weight percent of the obtained toner particles.

22. A process in accordance with claim 1 wherein the morphology of the toner particles is controlled by the shear time in the range of from about 5 minutes to about 2 hours applied in the blending step (ii).

23. A process for the preparation of toner comprising

(i) preparing a pigment dispersion, which dispersion is comprised of pigment and an ionic surfactant;

(ii) shearing the pigment dispersion with a polymeric latex comprised of resin with a size of from about 0.05 to about 1 micron in average volume diameter, a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant, and a nonionic surfactant thereby causing the formation of a uniform dispersion of pigment particles and resin in said surfactants, and wherein pigment particles and resin contained in said dispersion and wherein said pigment particles and resin are flocculated or heterocoagulated together in said dispersion;

(iii) (a) stirring and heating the uniform dispersion of pigment particles and resin particles (ii) to form electrostatically bound toner size aggregates;

or

(iii) (b) shearing the above uniform dispersion of pigment particles and resin particles (ii) further from 2 to about 24 hours to form electrostatically bound densely packed aggregates;

or

(iii) (c) shearing the above uniform dispersion of pigment particles and resin particles (ii), while heating, to form electrostatically bound toner size aggregates in the form of flakes; and

(iv) heating the statically bound aggregated particles above about the glass transition temperature of the resin to provide coalesced particles of toner.

24. A process in accordance with claim 23 wherein the glass transition temperature of resin is in the range of about 50°

C. to about 80°

C., and heating is accomplished for a period of from about 30 minutes to about 10 hours.

25. A process in accordance with claim 23 wherein subsequent to (iv) the following is accomplished:

(v) separating said toner particles from water and surfactants by filtration; and

(vi) drying said toner particles.

26. A process in accordance with claim 23 wherein the formed toner particles have a volume average diameter of from about 1 to about 10 microns, and wherein the solids are comprised of resin and pigment in an amount of about 5 to about 25 percent, and which solids are contained in water and anionic/nonionic/cationic surfactants.