Processes for the preparation of toners

• US 5,164,282 A
• Filed: 04/17/1989
• Issued: 11/17/1992
• Est. Priority Date: 04/17/1989
• Status: Expired due to Fees

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Mahabadi, Hadi K.
• Primary Examiner(s): McCamish, Marion E.
• Assistant Examiner(s): CROSSAN, STEPHEN
• Application Number:
  US07/339,539
• Time in Patent Office: 1,310 Days
• Field of Search: 430/137, 430/109, 524/849, 526/201
• US Class Current: 430/108.2
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: G03G 9/0806 whereby chemical synthesis of at least one of the toner components takes place
• CPC Class Codes: G03G 9/0812 Pretreatment of components
• CPC Class Codes: G03G 9/08793 Crosslinked polymers

Abstract

A process for the preparation of toner particles which comprises mixing at least one resin monomer with a polymerization initiator, a crosslinking component and a chain transfer component; effecting bulk polymerization until partial polymerization has been accomplished; mixing with the aforementioned partially polymerized product pigment or dye particles, thereby forming an organic phase; dispersing the organic phase in water containing a stabilizing component whereby there is obtained a suspension of toner particles in water; and polymerizing the toner suspension.

Claims

1. A process for the preparation of toner particles with an average diameter from about 5 to about 25 microns, which comprises mixing from about 1 to about 10 monomers with a polymerization initiator, a crosslinking component and a chain transfer component;

effecting bulk polymerization until from about 10 to about 40 weight percent of the monomer has polymerized;

mixing with the aforementioned partially polymerized product pigment or dye particles until an organic phase is formed;

dispersing the organic phase in water containing a stabilizing component selected from the group consisting of nonionic and ionic water soluble polymeric stabilizers, polyvinyl alcohol, gelatins, starches, gums, alginates, zein, and casein, which dispersion is accomplished with a high shear homogenizer, whereby there is obtained a suspension of toner particles in water; and

polymerizing the toner suspension, and wherein bulk and suspension polymerization are accomplished by heating to a temperature of from about 50°

to 100°

C.

2. A process in accordance with claim 1 wherein the pigment particles are cyan, magenta, yellow, red, blue, green, brown black, or mixtures thereof.

3. A process in accordance with claim 1 wherein the number and weight average molecular weight of the polymer prepared in the bulk polymerization step is from about 5,000 to about 50,000 and from about 10,000 to about 300,000, respectively.

4. A process in accordance with claim 1 wherein the molecular weight distribution of the toner polymer resin in the toner particles has one peak, or a plurality of peaks.

5. A process in accordance with claim 1 wherein the particle size and particle size distribution of the resulting toner is controlled by the mixing time, stabilizing concentration, and the viscosity of the organic phase during dispersion of the organic phase in water containing stabilizing component.

6. A process in accordance with claim 1 wherein the monomer or comonomers are selected from vinyl monomers.

7. A process in accordance with claim 1 wherein the monomer(s) are styrene derivatives thereof;

monocarboxylic acids and the derivatives thereof;

dicarboxylic acids with a double bond and the derivatives thereof;

vinyl esters;

vinyl ketones;

vinyl naphthalene;

unsaturated mono-olefins;

vinylidene halides; and

mixtures thereof.

8. A process in accordance with claim 1 wherein the monomer(s) are styrene, α

-methylstyrene, p-chlorostyrene, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methacrylic acids, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile or acrylamide;

maleic acid, monobutyl maleate, or dibutylmaleate;

vinyl chloride, vinyl acetate or vinyl benzoate;

vinyl methyl ketone and vinyl ether ketone; and

vinyl ethyl ether or vinyl isobutyl ether;

isobutylene;

vinylidene chloride;

N-vinyl pyrrole;

or mixtures thereof.

9. A process in accordance with claim 8 wherein the polymerization initiator is azoisobutyronitrile, azodimethylvaleronitrile, azobiscyclohexanitrile, 2-methylbutyronitrile, diazoamine-azobenzene, or mixtures thereof.

10. A process in accordance with claim 1 wherein the polymerization initiator is selected from the group consisting of azo, diazo compounds, and mixtures thereof.

11. A process in accordance with claim 1 wherein the crosslinking component is selected from the group consisting of compounds having two or more polymerizable double bonds;

and divinyl compounds.

12. A process in accordance with claim 1 wherein the crosslinking component is selected from the group consisting of ethylene glycol diacrylate, ethylene glycol dimethyacrylate, divinyl ether, divinyl sulfite, divinyl sulfone, divinylbenzene, and divinylnaphthalene.

13. A process in accordance with claim 1 wherein the chain transfer component is selected from a group consisting of mercaptans and halogenated hydrocarbons.

14. A process in accordance with claim 1 wherein the chain transfer agent is carbon tetrachloride, butylmercaptan, or laurylmercaptan.

15. A process in accordance with claim 1 wherein the stabilizing component is selected from a group consisting of methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, block copolymers, and barrier stabilizers.

16. A process in accordance with claim 1 wherein the stabilizer is tricalcium phosphate, talc or barium sulfate.

17. A process in accordance with claim 1 wherein the pigment is carbon black, magnetites, nigrosine dye, aniline blue 2,9-dimethyl-substituted quinacridone, an anthraquinone dye, a diazo dye, Cl Solvent Red 10, Lithol Scarlet, or Hostaperm Pink.

18. A process in accordance with claim 1 wherein the pigment is copper tetra-4 (octadecyl sulfonamido) phthalocyanine, X-copper phthalocyanine, Cl Pigment Blue, Anthrathrene Blue, Sudan Blue, diarylide yellow 3,3-dichlorobenzidene acetoacetanilides, a monazo pigment, Cl Solvent Yellow 16, a nitrophenyl amine sulfonamide, Cl Dispersed Yellow 33, 2,5-dimethoxy-4-sulfonanilide phenylazo-4'"'"'-chloro-2,5-dimethoxy acetoacetanilide, or Permanent Yellow FGL.

19. A process in accordance with claim 2 wherein the toner is blended with surface additives.

20. A process in accordance with claim 19 wherein the additives are comprised of colloidal silica.

21. A process in accordance with claim 1 wherein the toner contains a linear polymeric alcohol.

22. A process in accordance with claim 1 wherein there is added to the partially polymerized mixture a polyhydroxy compound.

23. A process for the preparation of toner particles with an average diameter of from about 5 to about 20 microns, which comprises mixing resin monomer, comonomers, or mixtures thereof and wherein from 1 to about 10 monomers are selected with a polymerization initiator, a crosslinking component and a chain transfer component;

effecting bulk polymerization until from about 10 to about 40 weight percent of the monomer, comonomers, or mixtures thereof have been polymerized;

mixing with the partially polymerized product pigments or dyes thereby forming an organic phase;

dispersing the organic phase in water containing a stabilizing component selected from the group consisting of nonionic and ionic water soluble polymeric stabilizers, polyvinyl alcohol, gelatins, starches, gums, alginates, zein, and casein, which dispersion is accomplished with a high shear homogenizer, thereby obtaining a suspension of toner particles in water;

polymerizing the toner suspension whereby there are formed toner particles; and

subsequently washing and drying the toner particles, and wherein bulk and suspension polymerization are accomplished by heating to a temperature of from about 50°

to 120°

C.

24. A process in accordance with claim 23 wherein the dried toner particles are blended with flow aid additives, and have incorporated therein charge enhancing additives.

25. A process in accordance with claim 24 wherein the resulting toner particles are of an average diameter of from about 5 to about 25 microns.

26. A process in accordance with claim 24 wherein the charge enhancing additive is an alkyl pyridinium halide, a quaternary ammonium sulfate, or a sulfonate.

27. A process in accordance with claim 26 wherein the charge additive is stearyl phenethyl dimethyl ammonium tosylate, distearyl dimethyl ammonium methyl sulfate, stearyl dimethyl hydrogen ammonium tosylate cetyl pyridinium chlorides, or cetyl pyridinium tetrafluoroborates.

28. A process in accordance with claim 23 wherein the suspension of toner particles in water is formed in a container and then transferred to a reactor.

29. A process in accordance with claim 23 wherein the dispersion of the organic phase in the water containing stabilizing component is accomplished with a high shear homogenizer.

30. A semisuspension polymerization process for obtaining toner particles with an average diameter of from about 5 to about 25 microns, and wherein from 1 to about 10 monomers are selected, which comprises mixing at least one resin monomer with a polymerization initiator, a crosslinking component and a chain transfer component;

effecting bulk polymerization until from about 10 to about 40 weight percent of the said monomer has been polymerized;

mixing with the aforementioned partially polymerized product pigment or dye particles, thereby forming an organic phase;

dispersing the organic phase in water containing a stabilizing component selected from the group consisting of nonionic and ionic water soluble polymeric stabilizers, polyvinyl alcohol, gelatins, starches, gums, alginates, zein, and casein, which dispersion is accomplished with a high shear homogenizer, whereby there is obtained a suspension of toner particles in water; and

polymerizing the toner suspension.

31. A process in accordance with claim 30 wherein there are obtained toner particles with an average diameter of from about 6 to about 18 microns.

32. A process for the preparation of toner particles with an average diameter of from about 5 to about 25 microns and wherein from 1 to about 10 monomers are selected by semisuspension polymerization which comprises mixing at least one resin monomer with a polymerization initiator, a crosslinking component and a chain transfer component;

effecting bulk polymerization until from about 10 to about 40 weight percent of the monomer has polymerized;

mixing with the aforementioned partially polymerized product pigments or dye particles until an organic phase is formed;

dispersing the organic phase in water containing a stabilizing component selected from the group consisting of nonionic and ionic water soluble polymeric stabilizers, polyvinyl alcohol, gelatins, starches, gums, alginates, zein, and casein, which dispersion is accomplished with a high shear homogenizer, whereby there is obtained a suspension of toner particles in water; and

polymerizing the toner suspension.

33. A process which comprises mixing a monomer or comonomer with a polymerization initiator, a crosslinking component, and a chain transfer component;

(2) effecting bulk polymerization by increasing the temperature of the aforementioned mixture from about 50°

C. to about 100°

C. until from about 10 to about 40 weight percent of monomer of comonomers have been polymerized;

(3) mixing with the aforementioned partially polymerized monomer product pigments and optional additive components with a high shear mixer thereby formulating a uniform organic phase;

(4) dispersing the organic phase into water containing a stabilizing component selected from the group consisting of nonionic and ionic water soluble polymeric stabilizers, polyvinyl alcohol, gelatins, starches, gums, alginates, zein, and casein, thereby forming a toner suspension;

(5) transferring the resulting toner suspension to a reactor and polymerizing by increasing the process temperature to about 55°

to about 120°

C. thereby completing the conversion of a monomer or comonomers to a polymer product;

(6) washing the resulting product;

(7) separating the polymer particle; and

(8) drying the toner particles obtained.

34. A process in accordance with claim 33 wherein the additives include charge enhancing components.

35. A process in accordance with claim 33 wherein the organic phase is dispersed into from about 2 to about 5 times its volume of water which contains from about 1 to about 5 weight percent of stabilizing component and wherein the dispersion is accomplished with a high sheer mixer.

36. A process in accordance with claim 33 wherein the washing of the product is accomplished with water and/or an alcohol.

37. A process in accordance with claim 33 wherein the polymer particles are separated by filtration.

38. A process in accordance with claim 33 wherein there are obtained toner particles with an average particle size of from about 5 to about 25 microns.

39. A process in accordance with claim 33 wherein there are obtained toner particles with an average particle size of from about 6 to about 18 microns.

40. A process in accordance with claim 33 wherein there is optionally blended with the resulting toner particles flow additives and/or charge enhancing additives.