Toner aggregation and coalescence processes

• US 5,403,693 A
• Filed: 06/25/1993
• Issued: 04/04/1995
• 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., Hopper, Michael A.
• Primary Examiner(s): Rodee, Christopher D.
• Application Number:
  US08/083,157
• Time in Patent Office: 648 Days
• Field of Search: 430/137, 523/335, 523/346, 523/352, 528/936
• 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 9/0812 Pretreatment of components
• 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 comprising:

(i) preparing a pigment dispersion in water, which dispersion is comprised of a pigment, an ionic surfactant in amounts of from about 0.5 to about 10 percent by weight of water, and an optional charge control agent;

(ii) shearing the pigment dispersion with a latex mixture comprised of a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant, a nonionic surfactant, and resin particles, thereby causing a flocculation or heterocoagulation of the formed particles of pigment, resin, and charge control agent;

(iii) stirring the resulting sheared viscous mixture of (ii) at from about 300 to about 1,000 revolutions per minute to form electrostatically bound substantially stable toner size aggregates with a narrow particle size distribution;

(iv) reducing the stirring speed in (iii) to from about 100 to about 600 revolutions per minute, and subsequently adding further anionic or nonionic surfactant in the range of from about 0.1 to about 10 percent by weight of water to control, prevent, or minimize further growth or enlargement of the particles in the coalescence step (iii); and

(v) heating and coalescing from about 5 to about 50° C. above about the resin glass transition temperature, Tg, which resin Tg is from between about 45° C. to about 90° C. and preferably from between about 50° C. and about 80° C. the statically bound aggregated particles to form said toner composition comprised of resin, pigment and optional charge control agent.

Claims

1. A process for the preparation of toner compositions with a particle size of from about 1 to about 25 microns in average volume diameter consisting essentially of:

(i) preparing a pigment dispersion in water, which dispersion is comprised of a pigment, an ionic surfactant in amounts of from about 0.5 to about 10 percent by weight of water, and an optional charge control agent;

(ii) shearing the pigment dispersion with a latex mixture comprised of a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant, a nonionic surfactant, and resin particles, thereby causing a flocculation or heterocoagulation of pigment, resin particles, and optional charge control agent;

(iii) stirring the mixture of (ii) at from about 300 to about 1,000 revolutions per minute to form electrostatically bound substantially stable toner size aggregates with a narrow particle size distribution;

(iv) reducing the stirring speed in (iii) to from about 100 to about 600 revolutions per minute, and subsequently adding further ionic or nonionic surfactant in the range of from about 0.1 to about 10 percent by weight of water to prevent, or minimize further growth or enlargement of the toner size aggregates of (iii) in the coalescence step (v); and

(v) heating and coalescing from about 5 to about 50°

C. above about the resin glass transition temperature, Tg, which resin Tg is from between about 45°

C. to about 90°

C. the statically bound aggregated particles to form said toner composition comprised of resin particles, pigment and optional charge control agent.

2. A process in accordance with claim 1 wherein the surfactant utilized in preparing the pigment dispersion is a cationic surfactant in an amount of from about 0.01 weight percent to about 10 weight percent and the counterionic surfactant present in the latex mixture is an anionic surfactant present in an amount of from about 0.2 weight percent to about 5 weight percent;

and wherein the molar ratio of cationic surfactant introduced with the pigment dispersion to the anionic surfactant introduced with the latex can be varied from about 0.5 to about 5.

3. A process in accordance with claim 2 wherein the cationic surfactant is a quaternary ammonium salt.

4. A process in accordance with claim 2 wherein the artionic surfactant concentration is about 0.1 to about 5 weight percent of the latex mixture of resin, pigment, optional charge control agent, and the cationic surfactant concentration is about 0.1 to about 5 weight percent of the aqueous phase of resin, pigment, and optional charge control agent.

5. A process in accordance with claim 1 wherein to prevent or minimize further growth or enlargement of the toner size aggregates of (iii) in the coalescing step (v) said ionic surfactant of (iv) is added.

6. A process in accordance with claim 1 wherein the addition of further ionic surfactant (iv) stabilizes the toner size aggregates of (iii) and as a result fixes their particle size and particle size distribution, and wherein the particle size is in the range of from about 3 to about 10 microns in average volume diameter, and the particle size distribution is in the range of from about 1.16 to about 1.26.

7. A process in accordance with claim 1 wherein the ionic surfactant added acts to increase the electrostatic repulsions between the aggregates, thereby increasing their stability, and wherein the aggregates formed have a volume average diameter of from about 3 to about 10 microns and do not grow further in size.

8. A process in accordance with claim 1 wherein to prevent or minimize further growth or enlargement of the toner size aggregates of (iii) in the coalescing step (v) there is added from about 0.02 percent to 5 percent by weight of water of said nonionic surfactant after aggregation (iii), and the speed in (iv) is reduced to from about 200 to about 600 revolutions per minute.

9. A process in accordance with claim 8 wherein the addition of nonionic surfactant further stabilizes the aggregated particles by steric repulsion and as a result fixes their size and particle size distribution as achieved in (iii) of from about 3 to about 10 microns, and wherein the GSD thereof is from about 1.20 to about 1.26.

10. A process in accordance with claim 1 wherein the ionic surfactant utilized for minimizing, or preventing particle growth in the coalescence step is comprised of sodium dodecyl benzene sulfonates.

11. A process in accordance with claim 1 wherein the nonionic surfactant (iv) utilized for controlling particle growth in the coalescence (v) is an alkyl phenoxypoly(ethylenoxy) ethanol.

12. 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.

13. A process in accordance with claim 1 wherein the dispersion of (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., and for a duration of from about 1 minute to about 120 minutes.

14. A process in accordance with claim 1 wherein the dispersion of (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.

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

16. A process in accordance with claim 1 wherein homogenization is accomplished in (ii) by homogenizing at from about 1,000 revolutions per minute to about 10,000 revolutions per minute, and for a duration of from about 1 minute to about 120 minutes.

17. A process in accordance with claim 1 wherein the heating of the statically bound aggregate particles to form toner size composite particles comprised of pigment, resin, and optional charge control agent is accomplished at a temperature of from about 60°

C. to about 95°

C., and for a duration of from about 1 hour to about 8 hours.

18. 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(para-methyl styrene-isoprene), poly(meta-methyl styrene-isoprene), poly(alphamethylstyrene-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).

19. 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), poly(styrene-butylacrylate-acrylic acid), polyethylene-terephthalate, polypropylene-terephthalate, polybutylene-terephthalate, polypentylene-terephthalate, polyhexalene-terephthalate, polyheptadene-terephthalate, and polyoctalene-terephthalate.

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

21. A process in accordance with claim 1 wherein the ionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecylbenzene sulfate and sodium dodecylnaphthalene sulfate.

22. A process in accordance with claim 1 wherein the resin is from about 0.01 to about 3 microns in average volume diameter, the pigment particles are from about 0.01 to about 1 micron in volume average diameter, the toner 98 is from about 3 to about 15 microns in average volume diameter, and the geometric size distribution thereof is from about 1.16 to about 1.30.

23. A process in accordance with claim 1 wherein the statically bound aggregate particles formed in (iii) are from about 1 to about 15 microns in average volume diameter.

24. A process in accordance with claim 1 wherein the nonionic surfactant concentration is about 0.1 to about 5 weight percent of the latex mixture.

25. A process in accordance with claim 1 wherein there is added to the surface of the formed toner composition of (v) 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.

26. A process in accordance with claim 1 wherein diluting the flocculated mixture of (iii) is accomplished with water of from about 50 percent of solids to about 15 percent of solids, which solids are comprised of the resin latex and pigment particles.

27. A process in accordance with claim 1 wherein the formed toner composition of (v) is washed with warm water and the surfactants are removed from the formed toner composition of (v) surface, followed by drying.

28. A process in accordance with claim 1 wherein in (iv) said speed is reduced to from about 100 to about 200 revolutions per minute.

29. A process in accordance with claim 1 wherein said speed in (iv) is reduced to about 250 rpm from about 650 rpm in (iii).

30. A process for the preparation of toner compositions with a size of from about 1 to about 25 microns in average volume diameter comprising:

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

(ii) shearing the pigment dispersion with a latex mixture comprised of a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant, a nonionic surfactant, and resin, thereby causing a flocculation or heterocoagulation of the pigment and resin;

(iii) stirring the sheared mixture at about 300 to about 1,000 rpm to form electrostatically bound stable toner size aggregates with narrow particle size distribution, which aggregates are of a particle size in the range of about 3 to about 10 microns in average volume diameter, and wherein said narrow particle size distribution or GSD is from about 1.16 to about 1.26;

(iv) reducing the stirring speed to from about 200 to about 600 revolutions per minute and subsequently optionally adding additional ionic or nonionic surfactant in the range of from about 0.1 to 10 percent by weight, or water primarily to prevent further growth of the particles in the coalescence step (v); and

(v) heating and coalescing from about 5°

C. to about 50°

C. above the resin Tg, which resin Tg is between about 45°

C. and about 90°

C., the statically bound aggregated particles to form said toner composition comprised of polymeric resin and pigment.

31. A process in accordance with claim 30 wherein the size of the particles in (iv) is from about 3 to about 10 microns in average volume diameter, and the GSD is from about 1.16 to about 1.26.

34. A process in accordance with claim 30 wherein the ionic or nonionic surfactant is selected in an amount of about 0.1 to about 5 percent by weight.

32. A process for the preparation of toner consisting essentially of:

(i) preparing a pigment dispersion in water, which dispersion is comprised of a pigment, and an ionic surfactant in amounts of from about 0.5 percent to about 10 percent based on the amount of water;

(ii) shearing the pigment dispersion with a latex mixture comprised of a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant, a nonionic surfactant, and resin, thereby causing a flocculation or heterocoagulation of the pigment and resin;

(iii) further stirring of the resulting mixture to form electrostatically bound relatively stable toner size aggregates with a narrow particle size distribution;

(iv) adding further surfactant to minimize further growth, or freeze the particle .size in the coalescence step (v), which size is from about 3 to about 10 microns in average volume diameter with a GSD of from about 1.16 to about 1.26; and

(v) heating and coalescing, above the resin Tg the statically bound aggregated particles to form a toner composition comprised of resin and pigment.

33. A process for the preparation of toner compositions with a particle size of from about 3 to about 10 microns in average volume diameter consisting essentially of:

(i) preparing a pigment dispersion in water, which dispersion is comprised of a pigment, an ionic surfactant in amounts of from about 0.5 to about 10 percent by weight of water, and an optional charge control agent;

(ii) shearing the pigment dispersion with a latex mixture comprised of a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant, a nonionic surfactant, and resin particles, thereby causing a flocculation or heterocoagulation of pigment, resin particles, and optional charge control agent;

(iii) stirring the mixture of (ii) at from about 300 to about 1,000 revolutions per minute to form electrostatically bound substantially stable toner size aggregates with a narrow particle size distribution, and wherein said stable toner size aggregates have a particle size in the range of from 3 to 10 microns in average volume diameter, and wherein said narrow particle size distribution is from about 1.16 to about 1.26;

(iv) reducing the stirring speed in (iii) to from about 100 to about 600 revolutions per minute, and subsequently adding further ionic or nonionic surfactant in the range of from about 0.1 to about 10 percent by weight of water to prevent, or minimize further growth or enlargement of the toner size aggregates of (iii) in the coalescing step (v); and

(v) heating and coalescing at from about 5°

to about 50°

C. above about the resin glass transition temperature, which resin glass transition temperature is from between about 45°

C. to about 90°

C. the electrostatically bound aggregated particles to form said toner composition comprised of resin particles, pigment particles and optional charge control agent particles.