Toner emulsion aggregation processes

• US 5,370,963 A
• Filed: 06/25/1993
• Issued: 12/06/1994
• 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): GOODROW, JOHN L
• Application Number:
  US08/082,651
• Time in Patent Office: 529 Days
• Field of Search: 430/106, 430/110, 430/137
• 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

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 pigment, an ionic surfactant, and an optional charge control agent;

(ii) shearing at high speeds the pigment dispersion with a polymeric latex comprised of resin, a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant and a nonionic surfactant thereby forming a uniform homogeneous blend dispersion comprised of resin, pigment, and optional charge agent;

(iii) heating the above sheared homogeneous blend below about the glass transition temperature (Tg) of the resin while continuously stirring to form electrostatically bounded toner size aggregates with a narrow particle size distribution;

(iv) heating the statically bound aggregated particles above about the Tg of the resin particles to provide coalesced toner comprised of resin, pigment, and optional charge control agent, and subsequently optionally accomplishing (v) and (vi);

(v) separating said toner; and

(vi) drying said toner.

Claims

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

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

(ii) shearing at high speeds the pigment dispersion with a polymeric latex comprised of resin, a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant and a nonionic surfactant thereby forming a uniform homogeneous blend dispersion comprised of resin, pigment, and optional charge agent;

(iii) heating the above sheared homogeneous blend below about the glass transition temperature (Tg) of the resin while continuously stirring to form electrostatically bounded toner size aggregates with a narrow particle size distribution;

(iv) heating the statically bound aggregated particles above about the Tg of the resin particles to provide coalesced toner comprised of resin, pigment, and optional charge control agent, and subsequently optionally accomplishing (v) and (vi);

(v) separating said toner; and

(vi) drying said toner.

2. A process in accordance with claim 1 wherein the homogeneous dispersion of pigment and resin is dispersed in water containing surfactants, and enables a narrow particle size distribution or GSD of aggregates formed in (iii) of from about 1.16 to about 1.26.

3. A process in accordance with claim 1 wherein the homogeneous blend (ii) is achieved by shearing the dispersion of the latex, the pigment and surfactants in water at a speed of from about 3,000 to about 15,000 revolutions per minute.

4. A process in accordance with claim 1 wherein the shearing (ii) of the latex, pigment, and surfactants is achieved with a polytron or a homogenizer.

5. A process in accordance with claim 1 wherein the shearing (ii) of the latex, pigment, and oppositely charged surfactants is achieved by a continuous shearing device with a variable gap adjustment of from about 0.1 to about 3 millimeters.

6. A process in accordance with claim 1 wherein the shearing (ii) of the latex, pigment, and oppositely charged surfactant is achieved at a temperature of from 0°

to about 40°

C.

7. A process in accordance with claim 1 wherein the homogeneous blend of the latex, pigment, and surfactants is subjected to shearing for from about 2 minutes to about 120 minutes to obtain a narrow particle size distribution of aggregated particles.

8. A process in accordance with claim 1 wherein the time of shearing (ii) controls the homogeneity of the blend of latex particles, pigment, and surfactants.

9. 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.

10. 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.

11. A process in accordance with claim 1 wherein the pigment dispersion of (i) is accomplished by homogenizing at from about 1,000 to about 10,000 revolutions per minute and preferably between about 2,000 to about 5,000 revolutions per minute at a temperature of from about 20°

C. to about 35°

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

12. A process in accordance with claim 1 wherein the pigment 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.

13. 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.

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

15. A process in accordance with claim 1 wherein the heating of the blend in (iii) is accomplished at temperatures from about 20°

C. to about 5°

C. below the Tg of the resin for a duration of from about 0.5 to about 6 hours.

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

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

C. above the Tg of the resin for a duration of from about 1 hour to about 8 hours.

17. 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(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).

18. 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-butyl methacrylate-acrylic acid), poly(styrene-butyl acrylate-acrylic acid), polyethylene-terephthalate, polypropylene-terephthalate, polybutylene-terephthalate, polypentylene-terephthalate, polyhexalene-terephthalate, polyheptadene-terephthalate, poly(styrene-butadiene), and polyoctalene-terephthalate.

19. 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 octyphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, and dialkylphenoxy poly(ethyleneoxy)ethanol;

and which surfactant is selected in an amount of from 0 to about 5 percent by weight of the mixture.

20. A process in accordance with claim 1 wherein the anionic 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;

and which surfactant is selected in an effective concentration of from about 0.01 to about 10 percent and preferably from about 0.02 to about 5 percent by total weight of the aqueous mixture.

21. A process in accordance with claim 1 wherein the cationic surfactant is an alkylbenzalkonium chloride present in the effective concentration of from about 0.01 to about 10 percent and preferably from about 0.02 to about 2 percent by total weight of the mixture.

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

23. 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.

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

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

the statically bound aggregate particles formed in (iii) are from about 1 to about 10 microns in average volume diameter; and

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

25. A process in accordance with claim 1 wherein the toner isolated is from about 1 to about 20 microns in average volume diameter, and the geometric size distribution thereof is from about 1.15 to about 1.35.

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

27. A process in accordance with claim 1 wherein there is added to the surface of the isolated toner 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.

28. A process in accordance with claim 1 wherein the speed of shearing (ii) is in the range of from about 4,000 to about 15,000 revolutions per minute and preferably in the range of from about 6,000 to about 12,000 revolutions per minute, thereby controlling the homogeneity of the blend of the latex particles, pigment, and oppositely charged surfactant in water.

29. A process in accordance with claim 1 wherein in (iii) the Tg of the resin is in range of from about 40°

C. to about 85°

C. and preferably is in the range of from about 50°

C. to about 75°

C.

30. A process in accordance with claim 1 wherein stirring is accomplished continuously at from about 200 to about 1,000 and preferably between about 300 to about 700 revolutions per minute.

31. A process in accordance with claim 1 wherein the Tg of the resin is 54°

C.

32. A process in accordance with claim 1 wherein the statically bound aggregated particles are heated to a temperature of from about 5°

C. to about 50°

C. above the resin Tg, which resin Tg is from about 40°

C. to about 85°

C.

33. A process in accordance with claim 3 wherein said speed is from about 6,000 to about 12,000, and the particle size of the formed toner is from about 3 to about 7 microns in average volume diameter.

38. A process in accordance with claim 3 wherein said speed is from about 3,000 to about 15,000 revolutions per minute in (ii) and there is formed a uniform homogeneous dispersion of flocculated particles of resin and pigment;

and in (iii) electrostatically bounded toner size aggregates with a GSD of from about 1.16 to about 1.26 are formed; and

there results in (iv) a toner with a volume average diameter of from about 1 to about 10 microns.

39. A process in accordance with claim 1 wherein a freezing agent or stabilizing agent component anionic or nonionic surfactant is added to the formed aggregates of (iii).

40. A process in accordance with claim 1 wherein the shearing (ii) of the latex, pigment, and surfactants is achieved with a continuous on-line homogenizer comprising a 3 stage rotator stator.

34. 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;

(ii) shearing at high speeds of from about 3,000 to about 15,000 revolutions per minute the pigment dispersion with a polymeric latex comprised of resin of submicron size in the range of from about 0.5 to about 1 micron, a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant and a nonionic surfactant thereby resulting in a uniform homogeneous blend with particles of less than or equal to from about 0.5 to about 1 micron in average volume diameter, and which particles are comprised of resin and pigment;

(iii) heating the above sheared homogeneous blend below, from about 5°

C. to about 25°

C., the glass transition temperature (Tg) of the resin and wherein the Tg of the resin is in range of from about 40°

C. to about 85°

C. and preferably in the range of from about 50°

C. to about 75°

C., while continuously stirring at from about 200 to about 1,000 revolutions per minute and preferably from about 300 to about 700 revolutions per minute to form electrostatically bound toner size aggregates with a narrow particle size distribution; and

(iv) heating the statically bound aggregated particles at from about 5°

C. to about 50°

C. above the resin Tg to provide coalesced particles of a toner composition comprised of polymeric resin, pigment and, optionally a charge control agent.

35. A process in accordance with claim 34 wherein subsequent to (iv) the following steps are accomplished:

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

(vi) drying said toner.

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

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

(ii) shearing at high speeds of from about 3,000 to about 15,000 revolutions per minute the pigment dispersion with a latex blend comprised of resin, 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 and resin to form a uniform viscous dispersion of solids of resin and pigment, from about 5 to about 25 weight percent, in water, and anionic/nonionic/cationic surfactant system;

(iii) heating the above sheared blend at a temperature of from about 5°

to about 25°

C. below the Tg of the resin particles while continuously stirring to form electrostatically bound relatively stable, for Coulter Counter measurements, toner size aggregates with a narrow particle size distribution;

(iv) heating the statically bound aggregated particles at a temperature of from about 5°

to about 50°

C. above the Tg of the resin to provide a mechanically stable toner composition comprised of resin, and pigment; and

optionally

(v) separating said toner; and

(vi) drying said toner.

37. A process for the preparation of toner comprising:

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

(ii) shearing at high speeds the pigment dispersion with a latex blend comprised of resin, a nonionic surfactant, and a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant thereby forming a uniform homogeneous dispersion;

(iii) heating the above sheared blend below about, equal to, or slightly higher than the glass transition temperature (Tg) of the resin to form aggregates with a narrow particle size distribution; and

(iv) heating the statically bound aggregated particles above, or equal to the Tg of the resin.