Process of making toner compositions

• US 5,344,738 A
• Filed: 06/25/1993
• Issued: 09/06/1994
• 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): MARTIN, ROLAND E
• Application Number:
  US08/083,146
• Time in Patent Office: 438 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 9/09741 cationic
• CPC Class Codes: G03G 9/0975 anionic
• CPC Class Codes: G03G 9/09758 comprising a heterocyclic ring

Abstract

A process for the preparation of toner compositions with a volume median particle size of from about 1 to about 25 microns, which process comprises:

(i) preparing by emulsion polymerization an anionic charged polymeric latex of submicron particle size, and comprised of resin particles and anionic surfactant;

(ii) preparing a dispersion in water, which dispersion is comprised of optional pigment, an effective amount of cationic flocculant surfactant, and optionally a charge control agent;

(iii) shearing the dispersion (ii) with the polymeric latex thereby causing a flocculation or heterocoagulation of the formed particles of optional pigment, resin and charge control agent to form a high viscosity gel in which solid particles are uniformly dispersed;

(iv) stirring the above gel comprised of latex particles, and oppositely charged dispersion particles for an effective period of time to form electrostatically bound relatively stable toner size aggregates with narrow particle size distribution; and

(v) heating the electrostatically bound aggregated particles at a temperature above the resin glass transition temperature (Tg) thereby providing the toner composition comprised of resin, optional pigment and optional charge control agent.

Claims

1. A process for the preparation of toner compositions with a volume median particle size of from about 1 to about 25 microns, which process comprises:

(i) preparing by emulsion polymerization an anionic charged polymeric latex of submicron particle size, and comprised of resin particles and anionic surfactant;

(ii) preparing a dispersion in water, which dispersion is comprised of pigment, an effective amount of cationic flocculant surfactant, and optionally a charge control agent;

(iii) shearing the dispersion (ii) with said polymeric latex thereby causing a flocculation or heterocoagulation of pigment, resin and charge control agent to form a high viscosity gel in which particles of pigment, resin and optional charge control agent are uniformly dispersed;

(iv) stirring the above gel for an effective period of time to form electrostatically bound relatively stable toner size aggregates with narrow particle size distribution; and

(v) heating the electrostatically bound relative stable toner size aggregates at a temperature above the resin glass transition temperature (Tg) thereby providing said toner compositions comprised of resin, pigment and optional charge control agent.

2. A process in accordance with claim 1 wherein the amount of cationic surfactant, or flocculant added is from about 0.01 to about 10 weight percent, thereby enabling a toner size of from about 3 to about 20 microns.

3. A process in accordance with claim 1 wherein the size of the toner after aggregation and coalescence is controlled by the molar ratio of 0.1:

1 to 5;

1 and preferably 0.5;

1 to 2;

1 of the cationic flocculant surfactant, and the counterionic anionic surfactant present in the latex.

4. A process in accordance with claim 1 wherein the size of the toner after aggregation and coalescence can be increased from 2 to 20 microns by increasing from 0.5:

1 to 4;

1 the molar ratio of the flocculant, or cationic surfactant added to cause said flocculation.

5. A process in accordance with claim 1 wherein the minimum molar ratio of flocculant, or cationic surfactant for enabling flocculation of particles into toner and the anionic surfactant present in the latex is about 0.5:

1, and thereby enabling aggregation of the particles in (iv).

6. A process in accordance with claim 1 wherein there is selected a minimum 1:

1 ratio of flocculant, or cationic surfactant and anionic surfactant present in the latex to thereby achieve narrow, from about 1.16 to about 1.26, particle size distribution.

7. A process in accordance with claim 1 wherein the flocculant, or cationic surfactant added partially reduces the charge of the anionic latex from about -120 to -70 millivolts to about -60 to 0 millivolts.

8. A process in accordance with claim 1 wherein the size from about 2 to about 20 microns of the aggregated/coalesced particles is controlled by the net charge, in the range of -60 millivolts to 0 millivolts, on the particles after addition of counterionic surfactant.

9. A process in accordance with claim 1 wherein the size of the electrostatically bound relatively stable toner size aggregates is from about 3 to about 20 microns average volume diameter or volume median diameter, and is controlled by the size of the latex particles which are from about 30 to about 500 nanometers in average volume diameter.

10. A process in accordance with claim 1 wherein by increasing said polymeric latex size from 30 to 500 nanometers the size of the electrostatically bound relatively stable toner size aggregates are increased to from about 3 to about 20 microns.

11. A process in accordance with claim 1 wherein the surfactant utilized in preparing the pigment dispersion is a cationic surfactant, and the anionic surfactant present in the latex mixture provides a negatively charged latex.

12. A process in accordance with claim 1 wherein a transparent toner is obtained.

13. A process in accordance with claim 1 wherein the surfactant used as a flocculant, or cationic surfactant enables a positively charged dispersion (ii).

14. A process in accordance with claim 13 wherein the dispersion of pigment in the cationic surfactant 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.

15. A process in accordance with claim 1 wherein the dispersion of pigment in the cationic surfactant 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.

16. 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.

17. A process in accordance with claim 1 wherein the cationic surfactant added as a flocculant causes a gel viscosity increase of from about 2 to about 8 centipoise to from about 500 to about 1,000 centipoise.

18. A process in accordance with claim 13 wherein the cationic surfactant added controls the viscosity in the range of from about 10 centipoise to about 5,000 centipoise of the resulting blend.

19. A process in accordance with claim 1 wherein the cationic surfactant is caprylamine(1-octylamine), caprylamine(1-decylamine), laurylamine(1-dodecylamine), myristylamine(1-tetradecylamine), palmitylamine(cetylamine or 1-hexadecylamine), stearylamine(1-octadecylamine), oleylamine(1-octadecenylamine), arachidylamine(1-eicosylamine), behenylamine(1-docosylamine);

secondary fatty amines such as, for example, dilaurylamine(di-n-dodecylamine);

lauryldimethylamine(n-dodecyldimethylamine);

dioctadecylamine, ditetradecylamine, trioctadecylamine, primary fatty amine acetates, or secondary fatty amine acetates; and

the cationic surfactant is a quaternary ammonium compound, benzalkonium chlorides, or benzalkonium bromides.

20. A process in accordance with claim 1 wherein the cationic surfactant is laurylpyridinium chloride, laurylpyridinium bromide, laurylpyridinium bisulfate, laurylpyridinium-5-chloro-2mercaptobenzothiazole, laurylpicolinium-p-tolueno sulfonate, tetradecylpyridinium bromide, cetyl pyridinium chloride, cetyl pyridinium bromide, 4-alkylmercaptopyridine, laurylisoquinilinium bromide, laurylisoquinilinium saccharinate, alkylisoquinilinium bromide, substituted imidazolinium compounds octyldimethylbenzyl ammonium chloride, dodecyldimethylbenzyl ammonium chloride, octadecyldimethylbenzyl ammonium chloride, or cetyltrimethyl ammonium bromide.

21. A process in accordance with claim 1 wherein the cationic surfactant is poly(vinylpyridine), poly(vinylmethylpyridinium bromide), poly(vinylpyridine) dodecyl bromide, polysulfonium compounds, poly(triethyl hexadecylphosphonium bromide) or poly(trimethyldodecyl phosphonium bromide).

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

23. A process in accordance with claim 1 wherein the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium dodecyl naphthalene sulfate, sodium lauryl sulfate, sodium alkyl naphthalene sulfonate, potassium alkyl sulfonate;

and which surfactant is selected in an effective concentration of from 0.01 to 10 percent and preferably from 0.02 to 3 percent by total weight of aqueous mixture.

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

25. 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);

and which resin is present in said toner in the amount of from about 50 to about 97 percent by the total weight of all toner components.

26. 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.

27. A process in accordance with claim 1 wherein polymer latex of (i) contains a nonionic surfactant selected from the group consisting of polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, and dialkylphenoxy poly(ethyleneoxy)ethanol, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyvinyl alcohol, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, and which surfactant is selected in an amount of from 0 percent to about 10 percent by weight and preferably from about 0.02 to about 2 percent by weight of the aqueous mixture comprised of anionic surfactant, nonionic surfactant, and water.

28. A process in accordance with claim 1 wherein the pigment is carbon black, cyan, magenta or yellow present in an amount of from about 0.1 to about 10 weight percent.

29. A process in accordance with claim 1 wherein there is added to the toner obtained surface additives of metal salts, metal salts of fatty acids, silicas, or mixtures thereof.

31. A process in accordance with claim 1 wherein in (iii) the charge polarity of opposite sign is from about -70 to about -120 millivolts.

32. A process in accordance with claim 3 wherein the toner after aggregation and coalescence is controlled by the molar ratio of 0.1:

1 to 5;

1 and preferably 0.5;

1 to 2;

1 of the cationic flocculant surfactant and the counterionic surfactant present in the latex.

33. A process in accordance with claim 1 wherein in (v) the Tg of the resin is in the range of from about 50°

C. to about 80°

C. and preferably is in the range of from about 52°

C. to about 65°

C.

34. A process in accordance with claim 1 wherein the amount of cationic flocculant to the anionic surfactant present in the latex is in a molar ratio of from about 0.1:

1 to about 5;

1.

35. A process in accordance with claim 34 wherein said molar ratio is from about 0.5:

1 to about 2;

1.

30. A process for the preparation of a toner, which process comprises:

(i) preparing by emulsion polymerization of styrene, butylacrylate and acrylic acid in the concentration of from about 20 percent to about 50 percent with an ammonium persulfate as an initiator in a concentration of from 0.5 percent to 5 percent and dodecanethiol as a chain transfer agent in the concentration of from about 0.5 percent to 5 percent and in a mixture of 1 to 3 percent solution of nonoionic surfactant and 1 to 3 percent solution of anionic surfactant, an anionic polymeric latex of a submicron particle size of from about 0.1 to about 3 microns of 20 to 50 percent of solids of poly(styrene-butylacrylate-acrylic acid) in a water anionic/nonionic surfactant and with an effective charge mobility or zeta potential of from about -70 to about -120 millivolts;

(ii) preparing by sonication, homogenization or microfluidization a pigment dispersion, which dispersion is comprised of a pigment, a controlled amount of from about 0.01 to about 10 weight percent of cationic surfactant, and an optional charge control agent;

(iii) shearing by a high shear blender or homogenizer at 5,000 to 15,000 rpm the pigment dispersion (ii) with a polymeric latex (i) comprised of resin, a counterionic surfactant with a negative charge of -70 to -120 millivolts, and which is an opposite polarity to that of the pigment dispersion which was prepared with the cationic 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 comprised of a polymeric latex of poly(styrene-co-butylacrylate-co-acrylic acid), pigment, and optional charge controlling agent;

(iv) stirring at from about 200 to 500 revolutions per minute for from about 1 to about 24 hours the above sheared blend of latex particles and oppositely charged pigment particle, to form electrostatically bound relatively stable, to withstand Coulter Counter measurements, toner size aggregates with a narrow particle size distribution, or GSD of from about 1.16 to about 1.26 as determined on the Coulter Counter;

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

C. to about 50°

C. above the Tg of the resin in the range of from about 50°

C. to about 80°

C. and preferably in the range of from about 52°

C. to about 65°

C. to provide a toner comprised of said resin, pigment and optionally a charge control agent; and

optionally

(vi) separating said toner by filtration; and

(vii) drying said toner.

36. A process for the preparation of toner with particle sizes of from about 1 to about 25 microns in average volume diameter, which process comprises:

(i) preparing by emulsion polymerization an anionic charged polymeric latex of a submicron particle size, which size is from about 30 nanometers to about 700 nanometers, and with an effective charge mobility or zeta potential of from about -70 to about -120 millivolts, and which latex is comprised of resin and anionic surfactant;

(ii) preparing a pigment dispersion, which dispersion is comprised of pigment, a controlled effective amount of from about 1 to about 10 weight percent of cationic surfactant, and optionally a charge control agent;

(iii) shearing the pigment dispersion (ii) with said polymeric latex (i), thereby causing a flocculation or heterocoagulation of the formed particles of pigment, resin and optional charge control agent to form a uniform dispersion of solids comprised of resin, pigment, and optional charge control agent;

(iv) stirring at from about 200 to about 500 revolutions per minute for from about 1 to about 24 hours the above sheared blend of latex particles and oppositely charged pigment particles to form electrostatically bound relatively stable, as determined by Coulter Counter measurements, toner size aggregates with a narrow particle size distribution, or GSD, of from about 1.16 to about 1.26;

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

C. to about 50°

C. above the Tg of the resin at temperatures of 60°

C. to 95°

C. to provide a toner composition comprised of resin, pigment and optionally a charge control agent; and

optionally

(vi) separating the toner particles; and

(vii) drying said toner particles.

37. A process in accordance with claim 36 wherein in (iii) the solids are comprised of from about 85 to about 97 percent of resin, about 3 to about 15 percent of pigment, and about 0 to about 5 percent of charge control agent.