Toner aggregation processes

• US 5,364,729 A
• Filed: 06/25/1993
• Issued: 11/15/1994
• 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): MARTIN, ROLAND E
• Application Number:
  US08/082,660
• Time in Patent Office: 508 Days
• Field of Search: 430/137, 523/322, 523/335, 523/339
• 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

Abstract

A process for the preparation of toner compositions comprising:

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

(ii) shearing said pigment dispersion with a latex or emulsion blend comprised of resin, a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant and a nonionic surfactant;

(iii) heating the above sheared blend below about the glass transition temperature (Tg) of the resin, to form electrostatically bound toner size aggregates with a narrow particle size distribution; and

(iv) heating said bound aggregates above about the Tg of the resin.

Claims

1. A process for the preparation of toner compositions comprising:

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

(ii) shearing said pigment dispersion with a latex or emulsion blend comprised of resin, a counterionic surfactant with a charge polarity of opposite sign to that of said ionic surfactant and a nonionic surfactant;

(iii) heating the above sheared blend below about the glass transition temperature (Tg) of the resin, to form electrostatically bound toner size aggregates with a narrow particle size distribution; and

(iv) heating said bound aggregates above about the Tg of the resin.

4. A process in accordance with claim 1 wherein the aggregation (iii) is a kinetically controlled process.

5. A process in accordance with claim 1 wherein the aggregation of smaller particles to form the toner size aggregates is about 10 times faster when the temperature is increased to from about room temperature to about 50°

C., and wherein said temperature is below the resin Tg.

6. A process in accordance with claim 1 wherein the particle size distribution of the aggregated particles is narrower, about 1.40 decreasing to about 1.16, when the temperature is increased from room temperature to 50°

C., and wherein said temperature is below the resin Tg.

7. A process in accordance with claim 1 wherein the number of fines of unaggregated submicron particles present is smaller, from more than about 20 percent to less than about 2 percent, when the temperature is increased from room temperature to 50°

C., and wherein said temperature is below the resin Tg.

8. A process in accordance with claim 1 wherein the temperature of the aggregation (iii) controls the speed at which particles submicron in size are collected to form toner size aggregates.

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 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.

12. 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.

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 I minute to about 120 minutes.

14. A process in accordance with claim 1 wherein the shearing or 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 I minute to about 120 minutes.

15. A process in accordance with claim 1 wherein the heating of the blend of latex, pigment, surfactants and optional charge control agent in (iii) 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 6 hours.

16. 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 10°

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

C. 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-methylstyrene-butadiene), poly(alpha-methylstyrene-butadiene), poly(methylmethacrylatebutadiene), poly(ethylmethacrylate-butadiene), poly(propylmethacrylatebutadiene), poly(butylmethacrylate-butadiene), poly(methylacrylatebutadiene), poly(ethylacrylate-butadiene), poly(propylacrylate-butadiene), poly(butylacrylate-butadiene), poly(styrene-isoprene), poly(para-methyl styrene-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).

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-butylmethacrylateacrylic acid), or poly(styrene-butylacrylate-acrylic acid), polyethyleneterephthalate, polypropylene-terephthalate, polybutylene-terephthalate, polypentylene-terephthalate, polyhexalene-terephthalate, polyheptadeneterephthalate, polystyrene-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 methyl cellulose, 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 dialkylphenoxy poly(ethyleneoxy)ethanol.

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 and sodium dodecylnaphthalene sulfate.

22. A process in accordance with claim 1 wherein the pigment is carbon black, magnetite, cyan, yellow, magenta, and mixtures thereof.

23. A process in accordance with claim 1 wherein the resin utilized in (ii) is from about 0.01 to about 3 microns in average volume diameter;

and the pigment particles are from about 0.01 to about 3 microns in volume average diameter.

24. A process in accordance with claim 1 wherein the toner particles isolated are from about 2 to about 15 microns in average volume diameter, and the geometric size distribution thereof is from about 1.15 to about 1.35.

25. A process in accordance with claim 1 wherein the aggregates formed in (iv) are about 1 to about 10 microns in average volume diameter.

26. A process in accordance with claim 1 wherein the nonionic surfactant concentration is from about 0.1 to about 5 weight percent;

the anionic surfactant concentration is about 0.1 to about 5 weight percent; and

the cationic surfactant concentration is about 0.1 to about 5 weight percent of the toner components of resin, pigment and charge agent.

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

28. 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.

29. A process in accordance with claim 1 wherein the toner particles isolated are from about 3 to 15 microns in average volume diameter, and the geometric size distribution thereof is from about 1.15 to about 1.30.

30. A process in accordance with claim 1 wherein the electrostatically bound aggregate particles formed in (iii) are from about 1 to about 10 microns in average volume diameter.

33. A toner obtained by the process of claim 1 and comprised of resin particles, pigment and charge control agent.

34. A developer composition comprised of the toner of claim 33 and carrier particles.

35. A process in accordance with claim 1 wherein said resin of (ii) is submicron in average volume diameter, the sheared blend of (iii) is continuously stirred, and subsequent to (iv) said toner is separated by filtration and subjected to drying.

38. A process in accordance with claim 1 wherein heating in (iii) is from about 5°

C. to about 25°

C. below the Tg.

39. A process in accordance with claim 1 wherein heating in (iii) is accomplished at a temperature of from about 29°

to about 59°

C.

40. A process in accordance with claim 1 wherein the resin Tg in (iii) is from about 50°

to about 80°

C.

41. A process in accordance with claim 1 wherein heating in (iv) is from about 5°

to about 50°

C. above the Tg.

42. A process in accordance with claim 1 wherein the resin Tg in (iv) is from about 50°

to about 80°

C.

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

C. and heating in (iv) is from about 59°

to about 104°

C.

44. A process in accordance with claim 1 wherein the resin Tg in (iii) is from about 52°

to about 65°

C.; and

the resin Tg in (iv) is from about 52°

to about 65°

C.

2. A process in accordance with claim I wherein the temperature below the resin Tg of (iii) controls the size of the aggregated particles in the range of from about 2.5 to about 10 microns in average volume diameter.

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

31. A process in accordance with claim 2 wherein the nonionic surfactant concentration is about 0.1 to about 5 weight percent of the toner components;

and wherein the anionic surfactant concentration is about 0.1 to about 5 weight percent of the toner components.

32. A process in accordance with claim 2 wherein the toner is washed with warm water and the surfactants are removed from the toner surface, followed by drying.

3. A process in accordance with claim I wherein the size of said aggregates can be increased to from about 2.5 to about 10 microns by increasing the temperature of heating in (iii) to from about room temperature to about 50°

C.

36. 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 of a diameter of from about 0.01 to about 1 micron, and an ionic surfactant;

(ii) shearing the pigment dispersion with a latex blend comprised of resin of submicron size of from about 0.01 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 causing a flocculation or heterocoagulation of the formed particles of pigment, and resin to form a uniform dispersion of solids in the water and surfactant;

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

to about 20°

C. below the Tg of the resin to form electrostatically bound 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 polymeric resin and pigment; and

optionally

(v) separating said toner particles; and

(vi) drying said toner particles.

45. A process in accordance with claim 36 wherein the heating in (iii) is equal to or slightly above the resin Tg.

46. A process in accordance with claim 36 wherein the heating in (iv) is equal to or slightly above the resin Tg.

37. A process for the preparation of toner compositions 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 blend 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 to form a uniform dispersion of solids in the water and surfactant;

(iii) heating the above sheared blend below about or about equal to the glass transition temperature (Tg) of the resin to form electrostatically bound toner size aggregates with a narrow particle size distribution;

(iv) heating the statically bound aggregated particles above about or about equal to the Tg of the resin particles to provide a toner composition comprised of resin;

followed by optionally

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

(vi) drying said toner particles.

47. A process in accordance with claim 37 wherein the heating in (iii) is equal to or slightly above the resin Tg.

48. A process in accordance with claim 37 wherein the heating in (iv) is equal to or slightly above the resin Tg.