Process for producing encapsulated toner

• US 4,904,562 A
• Filed: 09/23/1987
• Issued: 02/27/1990
• Est. Priority Date: 09/25/1986
• Status: Expired due to Term

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Yamazaki, Masuo, Akashi, Yasutaka, Yusa, Hiroshi, Kohtaki, Takaaki
• Primary Examiner(s): Goodrow, John L.
• Application Number:
  US07/100,359
• Time in Patent Office: 888 Days
• Field of Search: 430/137, 430/138, 430/106.6, 428/403
• US Class Current: 430/138
• CPC Class Codes: B01J 13/08 Simple coacervation, i.e. addition of highly hydrophilic material combined with spraying B01J13/043; combined with mechanical division B01J13/04
• CPC Class Codes: G03G 9/09392 Preparation thereof
• CPC Class Codes: Y10T 428/2991 Coated

Abstract

An encapsulated toner for electrophotography is produced through a process, comprising: preparing a solution of a shell material resin set to an acidic (or basic) pH region; dispersing solid core particles in the solution to form a dispersion; changing the pH of the dispersion to a pH region, which is preferably a basic (or acidic) pH region, where the shell material resin is precipitated from the dispersion; and coating the solid core particles with the precipitated shell material resin. The shell material is preferably a proton-attracting basic (or dissociative acidic) vinyl-type copolymer and is dissolved in a pH-adjusted aqueous medium comprising water and a polar solvent, such as a lower alcohol. Thus, an encapsulated toner with excellent triboelectric chargeability and environmental characteristic is prepared without coalescence of capsules or formation of free shells.

Claims

1. A process for producing an encapsulated toner, comprising:

preparing a solution of a shell material resin set to an acidic pH region or a basic pH region wherein the shell material resin comprises a vinyl copolymer having a number-average molecular weight of 5,000 to 40,000, said shell material resin being dissolved in an aqueous medium containing an organic solvent having a solubility parameter of at least 11.0,

dispersing solid core particles in the solution to form a dispersion,

changing the pH of the dispersion to a pH region where the shell material resin is precipitated from the dispersion, and

coating the core particles with the precipitated shell material resin.

2. A process according to claim 1, wherein the solution of the shell material resin is set to an acidic pH region, the solid core particles are dispersed in the solution, and the pH of the dispersion is changed to a basic pH region to precipitate the shell material resin.

3. A process according to claim 2, wherein the core particles have a pressure fixability.

4. A process according to claim 1, wherein said organic solvent is a lower alcohol.

5. A process according to claim 4, wherein said organic solvent is a lower alcohol having 1-5 carbon atoms.

6. A process according to claim 2, wherein said shell material resin comprises a resin formed from a monomer (A) providing a film-formability (A), a monomer (B1) providing a proton-attracting function (B1) of forming a proton-added product under the action of an acidifying agent in an aqueous medium, and a monomer (C) providing mainly a solubility-promoting function (C) of providing the proton-added product with a solubility in the aqueous medium.

7. A process according to claim 6, wherein said monomer (A) is styrene (St);

said monomer (B1) is N,N-dimethylaminoethyl methacrylate (DM) or N,N-diethylaminoethyl methacrylate (DE); and

said monomer (C) is a monomer selected from the group consisting of methyl methacrylate (MMA), 2-ethylhexyl methacrylate (2EHA), n-butyl methacrylate (BMA), butadiene (BD), isoprene (IP) and acrylonitrile (AN).

8. A process according to claim 6, wherein said shell material resin is a vinyl copolymer selected from the group consisting of St-MMA-DM copolymer St-MAA-DE copolymer, St-2EHA-DM copolymer, St-MMA-2EHA-DM copolymer, St-MMA-MBA-DM copolymer, St-MMA-BD-DM copolymer, St-MMA-IP-DM copolymer and St-AN-MMA-DM copolymer.

9. A process according to claim 1, wherein said shell material resin has a number-average molecular weight of 10,000 to 30,000.

10. A process according to claim 1, wherein said shell material resin has a ratio of weight-average molecular weight/number-average molecular weight in the range of 1.5-4.5, and a glass transition temperature of 40°

C. or higher.

11. A process according to claim 10, wherein said shell material resin has a glass transition temperature of 60°

-120°

C.

12. A process according to claim 6, wherein said shell material resin is a vinyl copolymer formed from 30-90 mol % of the monomer (A), 5-65 mol % of the monomer (B1), and 5-30 mol % of the monomer (C).

13. A process according to claim 1, wherein said shell material resin is contained in a proportion of 0.5-20 wt. parts per 100 wt. parts of the aqueous medium.

14. A process according to claim 13, wherein said shell material resin is contained in a proportion of 1.0-10 wt. parts per 100 wt. parts of the aqueous medium.

15. A process according to claim 2, wherein said solution of the shell material resin is set to a pH value of 5±

1.5.

16. A process according to claim 15, wherein said shell material resin is dissolved in the aqueous medium with the aid of an acidifying agent to provide said solution of the shell material resin.

17. A process according to claim 1, wherein the precipitation of the shell material resin is effected at a temperature of -10°

to +30°

C.

18. A process according to claim 1, wherein the precipitation of the shell material resin is effected at a temperature of -10°

to +5°

C.

19. A process according to claim 2, wherein the pH of the dispersion is changed by adding a basifying agent to the dispersion.

20. A process according to claim 19, wherein said basifying agent is added to the dispersion at a rate H (ml/min) satisfying the following condition:

space="preserve" listing-type="equation">(H/F×

G)=0.005 to 20,

wherein F denotes the concentration of the shell material resin in the aqueous medium (g/l), and G denotes the amount of the aqueous medium (l).

21. A process according to claim 19, wherein said basifying agent is a basic substance selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia gas, ethylenediamine, diethylene triamine, triethylene-diamine and aqueous solutions of these.

22. A process according to claim 21, wherein the basifying agent is ammonia water.

23. A process according to claim 1, wherein the solid core particles are dispersed in the solution in a proportion of 10-50 wt. parts per 100 parts of the aqueous medium constituting the solution.

24. A process according to claim 3, wherein said solid core particles comprise at least two of the following resins or waxes (a)-(c);

(a) a resin or wax with a hardness-imparting function having a Vickers hardness of 2-8 kg/mm² as measured under a weight of 10 g applied for 15 sec;

(b) a resin or wax with a releasability-imparting function having a critical surface tension of 15-40 dyne/cm at 20°

C.; and

(c) a resin or wax with a fixability-imparting function having a compression modulus of 0.1-50 kg/mm².

25. A process according to claim 24, wherein said solid core particles comprise a binder resin obtained by heating said at least two of the resins or waxes (a)-(c) in the presence of a radical generating agent.

26. A process according to claim 1, wherein said solid core particles comprise 15-180 wt. parts of a magnetic substance per 100 wt. parts of the resinous component therein.

27. A process according to claim 26, wherein said solid core particles comprise 50-150 wt. parts of the magnetic substance per 100 wt. parts of the resinous component therein.

28. A process according to claim 1, wherein said solid core particles comprise 0.1-20 wt. parts of a colorant per 100 wt. parts of the resin component therein.

29. A process according to claim 2, wherein said solid core particles are coated with a 0.01-2.0 μ

m-thick shell having a triboelectric chargeability.

30. A process according to claim 1, wherein the solution of the shell material resin is set to a basic pH region, the solid core particles are dispersed in the solution, and the pH of the dispersion is changed to an acidic pH region to precipitate the shell material resin.

31. A process according to claim 30, wherein the core particles have a pressure-fixability.

32. A process according to claim 30, wherein said shell material resin is dissolved in an aqueous medium comprising water and an organic solvent having a solubility parameter of 11.0 or higher.

33. A process according to claim 32, wherein said organic solvent is a lower alcohol.

34. A process according to claim 33, wherein said organic solvent is a lower alcohol having 1-5 carbon atoms.

35. A process according to claim 30, wherein said shell material resin comprises a resin formed from a monomer (A) providing a film-formability (A), a monomer (B2) providing a dissociative function (B2) of forming a dissociated product under the action of a basifying agent in an aqueous medium, and a monomer (C) providing mainly a solubility-promoting function (C) of providing the dissociated product with a solubility in the aqueous medium.

36. A process according to claim 35, wherein the monmer (B2) also has a function of the monomer (C).

37. A process according to claim 36, wherein the monomer (B2) is a maleic acid mono-alkyl ester or methacrylic acid.

38. A process according to claim 35, wherein said shell material resin has a number-average molecular weight of 5,000 to 40,000.

39. A process according to claim 35, wherein said shell material resin has a number-average molecular weight of 10,000 to 30,000.

40. A process according to claim 35, wherein said shell material resin has a ratio of weight-average molecular weight/number-average molecular weight in the range of 1.5-4.5, and a glass transition temperature of 40°

C. or higher.

41. A process according to claim 40, wherein said shell material resin has a glass transition temperature of 60°

-120°

C.

42. A process according to claim 32, wherein said shell material resin is contained in a proportion of 0.5-20 wt. parts per 100 wt. parts of the aqueous medium.

43. A process according to claim 42, wherein said shell material resin is contained in a proportion of 1.0-10 wt. parts per 100 wt. parts of the aqueous medium.

44. A process according to claim 30, wherein said solution of the shell material resin is set to a pH value of 8-10.

45. A process according to claim 44, wherein said shell material resin is dissolved in the aqueous medium with the aid of a basifying agent to provide said solution of the shell material resin.

46. A process according to claim 30, wherein the precipitation of the shell material resin is effected at a temperature of -10°

to +30°

C.

47. A process according to claim 46, wherein the precipitation of the shell material resin is effected at a temperature of -10°

to +5°

C.

48. A process according to claim 30, wherein the pH of the dispersion is changed by adding an acidifying agent to the dispersion.

49. A process according to claim 48, wherein said acidifying agent is added to the dispersion at a rate H (ml/min) satisfying the following condition:

space="preserve" listing-type="equation">(H/F×

G)=0.005 to 20,

wherein F denotes the concentration of the shell material resin in the aqueous medium (g/l), and G denotes the amount of the aqueous medium (l).

50. A process according to claim 48, wherein said acidifying agent is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid and succinic acid.

51. A process according to claim 50, wherein said acidifying agent is acetic acid.

52. A process according to claim 30, wherein the solid core particles are dispersed in the solution in a proportion of 10-50 wt. parts per 100 parts of the aqueous medium constituting the solution.

53. A process according to claim 31, wherein said solid core particles comprise at least two of the following resins or waxes (a)-(c):

(a) a resin or wax with a hardness-imparting function having a Vickers hardness of 2-8 kg/mm² as measured under a weight of 10 g applied for 15 sec;

(b) a resin or was with a releasability-imparting function having a critical surface tension of 15-40 dyen/cm at 20°

C.; and

(c) a resin or wax with a fixability-imparting function having a compression modulus of 0.1-50 kg/mm².

54. A process according to claim 53, wherein said solid core particles comprise a binder resin obtained by heating said at least two of the resins or waxes (a)-(c) in the presence of a radical generating agent.

55. A process according to claim 53, wherein said solid core particles comprise 15-180 wt. parts of a magnetic substance per 100 wt. parts of the resinous component therein.

56. A process according to claim 55, wherein said solid core particles comprise 50-150 wt. parts of the magnetic substance per 100 wt. parts of the resinous component therein.

57. A process according to claim 53, wherein said solid core particles comprise 0.1-20 wt. parts of a colorant per 100 wt. parts of the resin component therein.

58. A process according to claim 30, wherein said solid core particles are coated with a 0.01-2.0 μ

m-thick shell having a triboelectric chargeability.