Process for the preparation of pigment dispersion, pigment dispersion obtained by the same, ink jet recording ink comprising the same, and recording method and recorded material using the same

• US 6,916,862 B2
• Filed: 04/10/2001
• Issued: 07/12/2005
• Est. Priority Date: 04/10/2000
• Status: Expired due to Fees

• Current Assignee: Seiko Epson Corporation (Seiko Group)
• Original Assignee: Seiko Epson Corporation (Seiko Group)
• Inventors: Ota, Hitoshi, Hara, Kazuhiko, Yatake, Masahiro, Komatsu, Hidehiko
• Primary Examiner(s): SHOSHO, CALLIE E
• Application Number:
  US09/832,171
• Publication Number:
  US 20020075369A1
• Time in Patent Office: 1,554 Days
• Field of Search: 523/160, 523/161, 523/200, 523/205, 524/495, 524/556, 524/577, 524/588, 524/555, 106/31.6, 106/31.89
• US Class Current: 523/200
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C09B 67/0002 Grinding; Milling with solid grinding or milling assistants
• CPC Class Codes: C09B 67/0017 Influencing the physical properties by treatment with an acid, H2SO4
• CPC Class Codes: C09B 67/0019 of phthalocyanines
• CPC Class Codes: C09B 67/0022 Wet grinding of pigments
• CPC Class Codes: C09B 67/0023 of phthalocyanines
• CPC Class Codes: C09B 67/0086 anionic dispersing agents
• CPC Class Codes: C09B 67/0089 non ionic dispersing agent, e.g. EO or PO addition products
• CPC Class Codes: C09C 1/565 comprising an oxidative treatment with oxygen, ozone or oxygenated compounds, e.g. when such treatment occurs in a region of the furnace next to the carbon black generating reaction zone
• CPC Class Codes: C09D 11/322 Pigment inks

Abstract

Provided is a process for the preparation of a pigment dispersion which comprises a pigment surface treatment step of introducing at least one hydrophilic dispersibility-providing group onto the surface of a pigment directly and/or with the interposition of a polyvalent group, and a dispersion step of dispersing a surface-treated pigment obtained at the surface treatment step in an aqueous medium, characterized in that the dispersion step involves the dispersion of the surface-treated pigment in admixture with a wetting agent and water and a resin for providing dispersibility and/or fixability is added during and/or after the dispersion step.

Claims

1. A process for the preparation of a pigment dispersion which comprises

a) a pigment surface treatment step of introducing at least one hydrophilic dispersibility-providing group onto the surface of a pigment directly and/or with the interposition of a polyvalent group to form a surface treated pigment that is self-dispersible in water and that comprises said at least one hydrophilic dispersibility-providing group in an amount of not lower than 10×

10<sup>−

6</sup> per gram of particulate pigment,

b) a dispersion step of dispersing a surface-treated pigment obtained at said surface treatment step in an aqueous medium, wherein said dispersion step involves the dispersion of said surface-treated pigment in admixture with a wetting agent and water, wherein the wetting agent is selected from the group consisting of glycol ethers, 1,2-(C₄-C₁₀ alkyl)diols, 1,3-(C₄-C₁₀ alkyl)diols, 1,5-(C₄-C₁₀ alkyl)diols, and 1,6-(C₄-C₁₀ alkyl)diols, and is present in amount that enhances a dispersion efficiency of particles of the surface-treated pigment in water, and

(c) adding a resin for providing dispersibility an or fixability during and/or after said dispersion step to form said pigment dispersion, wherein the pigment dispersion has a liquid component comprising polyvalent metal ions in a total amount of not more than 600 ppm, wherein the dispersion step results in a dispersion having a pigment concentration of from about 5 to 50% by weight.

2. The process for the preparation of a pigment dispersion claim 1, wherein the surface tension at 20°

C. of the mixture at said dispersion step is not higher than 40 mN/m.

3. The process for the preparation of pigment dispersion according to claim 1, wherein the wetting agent further comprises acetylene glycols and/or acetylene alcohols in an amount of from not lower than {fraction (1/50)} of to twice the amount of said pigment by weight.

4. The process for the preparation of a pigment dispersion according to claim 3, wherein said acetylene glycols and acetylene alcohols are compounds represented by the following general formulae (I) and (II), respectively:

wherein R¹, R², R¹ and R⁴ each independently represent an alkyl group; and

the sum of m₁ and n₁ is from 0 to 30; and

wherein R₅ and R₆ each independently represent an alkyl group; and

m₂ is from to 30.

5. The process for the preparation of a pigment dispersion according to claim 1, wherein said hydrophilic dispersibility-providing group to be introduced onto the surface of a pigment at said surface treatment step comprise at least one selected from the group consisting of functional groups represented by the following general formulae and salts thereof —

OM, —

COOM, —

CO—

, —

SO₃M, —

SO₂M, —

SO₂NH₂, —

RSO₂M, —

PO₃HM, —

PO₃M₂, —

SO₂NHCOR, —

NH₃, and —

NR₃ in which M represents a hydrogen atom, alkaline metal, ammonium or organic ammonium; and

R represents a C_1-12 alkyl group, a phenyl group which may have a substituent or a naphthyl group which may have a substituent.

6. The process for the preparation of a pigment dispersion according to claim 1, wherein said hydrophilic dispersibility-providing group to be introduced onto the surface of a pigment at said surface treatment step is a sulfur-containing dispersibility-providing group.

7. The process for the preparation of a pigment dispersion according to claim 1, wherein the amount of said resin to be added is from not lower than {fraction (1/10)} of to three times the amount of said pigment by weight.

8. The process for the preparation of a pigment dispersion according to claim 1, wherein said resin comprises an alkali-soluble resin and/or a vinyl polymer obtained by the copolymerization of (a) one or more selected from the group consisting of silicon macromer represented by the following general formula (III) and acrylamide or methacrylamide-based monomer (excluding said monomer having salt-producing groups), (b) a polymerizable unsaturated monomer having a salt producing group and (c) a monomer copolymerizable with

these monomers in the presence of a radical polymerization initiator:

X(Y)_vSi(R)_3-w(Z)_w 

 

(III)

wherein X represents a polymerizable unsaturated group;

Y represents a divalent connecting group;

R represents a hydrogen atom, a lower alkyl group, an aryl group or an a alkoxy group, with the proviso that a plurality of R'"'"'s may be the same or different;

Z represent a monovalent siloxane polymer moiety having a number-average molecular weight of at least about 500;

v represents 0 or 1; and

w represents an integer of from 1 to 3.

9. The process for the preparation of a pigment dispersion according to claim 8, wherein among said resins, the alkali-soluble resin is a styreneacryli c acid copolymer.

10. The process for the preparation of a pigment dispersion according to claim 1, wherein said resin exhibits a glass transition temperature of not lower than 50°

C.

11. The process for the preparation of a pigment dispersion according to claim 1, wherein said resin has a weight-average molecular weight of from 1,600 to 50,000.

12. The process for the preparation of a pigment dispersion according to claim 1, wherein said resin exhibits an acid value of from 10 to 250.

13. The process for the preparation of a pigment dispersion according to claim 1, wherein Si, Ca, Mg, Fe, Cr and Ni ions incorporated in the liquid component of the pigment dispersion are each not higher than 100 ppm.

14. The process for the preparation of a pigment dispersion according to claim 1, wherein said pigment for introducing a hydrophilic dispersibility-providing group at said surface treatment step comprises a carbon black pigment and/or an organic pigment.

15. The process for the preparation of a pigment dispersion according to claim 1, wherein said pigment for introducing a hydrophilic dispersibility-providing group at said surface treatment step comprises one or more pigments selected from the group consisting of C.I. pigment red, C.I. pigment yellow, C.I. pigment violet, C.I. pigment blue, C.I. pigment orange, C.I. pigment green, and C.I. pigment brown.

16. The process for the preparation of a pigment dispersion according to claim 1, wherein said pigment for introducing a hydrophilic dispersibility-providing group at said surface treatment step comprises one or more pigments selected from the group consisting of phthalocyanine pigment, quinacridone pigment, condensed azo pigment, isoindolinone pigment, quinophthalone pigment, anthraquinone pigment, benzimidazolone pigment, and perylene pigment.

17. The process for the preparation of a pigment dispersion according to claim 1, wherein said surface treatment step involves the of a polymer material onto the surface of a pigment directly and/or with the interposition of a polyvalent group.

18. A pigment dispersion prepared by the process for the preparation of a pigment dispersion described in claim 1.

19. An ink jet recording ink at least comprising the pigment dispersion described in claim 18.

20. An ink jet recording method which comprises energizing the ink described in claim 19 so that it is ejected from a recording head and attached to a recording medium.

21. The ink jet recording method according to claim 20, wherein said energy is a dynamic energy.

22. The ink jet recording method according to claim 20, wherein said energy is a heat energy.

23. A recorded material obtained by the method described in claim 20.

24. The process according to claim 1, wherein the wetting agent is present in an amount of from 0.1 to 30% by weight based on the weigh of the pigment dispersion in the dispersion step.

25. A process for the preparation of a recording liquid comprising the steps of (i) providing a pigment dispersion prepared by the process of claim 1;

and

(ii) subsequent to the preparation of said pigment dispersion, mixing the pigment dispersion with at least a solvent to form the recording liquid.

26. The process as claimed in claim 25, wherein step (ii) comprises mixing the pigment dispersion with at least the solvent, a surfactant and water to form the recording liquid.

27. The process as claimed in claim 26, wherein the recording liquid has a solid component comprising the surface treated pigment and resin and a liquid component comprising the wetting agent, solvent, surfactant, polyvalent metal ions and water, the solid component of the recording liquid being present in an amount by weight that is less than an amount by weight of the wetting agent, solvent, surfactant and polyvalent metal ions present in the liquid component of the recording liquid.

28. The process as claimed in claim 27, wherein the pigment dispersion has (i) a liquid component comprising the wetting agent, water and polyvalent metal ions and (ii) a solid component comprising the surface treated pigment the resin, said solid component being present in the pigment dispersion in an amount by weight that is greater than a total amount by weight of the wetting agent and polyvalent metal ions present in the liquid component.

29. The process according to claim 28, wherein the pigment dispersion consists essentially of the surface treated pigment, the resin, the wetting agent, the polyvalent metal ions and water.

30. The process according to claim 28, wherein the pigment dispersion consists essentially of the surface treated pigment, the resin, the wetting agent, a neutralizing agent, the polyvalent metal ions and water.

31. The process according to claim 1, the resin is added during said dispersion step.

32. A process for the preparation of a pigment dispersion which comprises:

(a) a pigment surface treatment step of introducing at least one hydrophilic dispersibility-providing group onto the surface of a pigment directly and/or with the interposition of a polyvalent group to form a surface treated pigment that is self-dispersible in water and that comprises said at least one hydrophilic dispersibility-providing group in an amount of not lower than 10×

10<sup>−

6</sup> equivalent per gram of particulate pigment,

(b) a dispersion step of dispersing a surface treated pigment obtained at said surface treatment step in an aqueous medium, wherein said dispersion step involves the dispersion of said surface-treated pigment in admixture with a wetting agent and water wherein the wetting agent is selected from the group consisting of acetylene glycols, acetylene alcohols, glycol ethers and alkylene glycols and is present in an amount that enhances a dispersion efficiency of particles of the surface-treated pigment in water, and

(c) adding a resin for providing dispersibility and/or fixability during and/or after said dispersion step to form said pigment dispersion, wherein the pigment dispersion has a liquid component comprising polyvalent metal ions in a total amount of not more than 600 ppm,

wherein the dispersion step results in a dispersion having a pigment concentration of from about 5 to 50% by weight; and

wherein said resin comprises a vinyl polymer obtained by the copolymerization of (a) one or more selected from the group consisting of silicon macromer represented by the following general formula (III) and acrylamide or methacrylamide-based monomer (excluding said monomer having salt-producing groups),

(b) a polymerizable unsaturated monomer having a salt producing group and (c) a monomer copolymerizable with these monomers in the presence of a radical polymerization initiator;

X(Y)_vSi(R)_3-w(Z)_W 

 

(III)

wherein X represents a polymerizable unsaturated group;

Y represents a divalent connecting group;

R represents a hydrogen atom, a lower alkyl group, an aryl group or an alkoxy group, with the proviso that a plurality of R'"'"'s may be the same or different;

Z represents a monovalent siloxane polymer moiety having a number-average molecular weight of at least about 500;

v represents 0 or 1; and

w represents an integer of from 1 to 3.

33. The process for the preparation of a pigment dispersion according to claim 32, wherein the surface tension at 20°

C. of the mixture at said dispersion step is not higher than 40 mN/m.

34. The process for the preparation of a pigment dispersion according to claim 32, wherein the wetting agent comprises acetylene glycols and/or acetylene alcohols in an amount of from not lower than {fraction (1/50)} of to twice the amount of said pigment by weight.

35. The process for the preparation of a pigment dispersion according to claim 34, wherein said acetylene glycols and acetylene alcohols are compound represented by the following general formulae (I) and (II), respectively:

wherein R¹, R²,

R³ and R⁴ each independently represents an alkyl group; and

the sum of m₁ and n₁ is from 0 to 30; and

wherein R⁵ and R⁶ each independently represents an alkyl group; and

m₂ is from 0 to 30.

36. The process for the preparation of a pigment dispersion according to claim 32, wherein said hydrophilic dispersibility-providing group to be introduced onto the surface of a pigment at said surface treatment step comprise at least one selected from the group consisting of functional groups represented by the following general formulae and salts thereof —

OM, —

COOM, —

CO—

, —

SO₃M, —

SO₂M, —

SO₂NH₂, —

RSO₂M, —

PO₃HM, —

PO₃M₂, —

SO₂NHCOR, —

NH₃, and —

NR₃ in which M represents a hydrogen atom, alkaline metal, ammonium or organic ammonium; and

R represents a C_1-12 alkyl group, a phenyl group which may have a substituent or a naphthyl group which may have a substituent.

37. The process for the preparation of a pigment dispersion according to claim 32, wherein said hydrophilic dispersibility-providing group surface of a pigment at said surface treatment step is a sulfur-containing dispersibility providing group.

38. The process for the preparation of a pigment dispersion according to claim 32, wherein the amount of said resin to be added is from not lower than {fraction (1/10)} of to three times the amount of said pigment by weight.

39. The process for the preparation of a pigment dispersion according to claim 32, wherein said resin exhibits a glass transition temperature of not lower than 50°

C.

40. The process for the preparation of a pigment dispersion according to claim 32, said resin has a weight-average molecular weight of from 1,600 to 50,000.

41. The process for the preparation of a pigment dispersion to claim 32, wherein said resin exhibits an acid value of from 10 to 250.

42. The process for the preparation of a pigment dispersion according to claim 32, wherein Si, Ca, Mg, Fe, Cr and Ni ions incorporated in the liquid component of the pigment dispersion and are not higher than 100 ppm.

43. The process for the preparation of a pigment dispersion according to claim 32, wherein said pigment for introducing a hydrophilic dispersibility-providing group at said surface treatment step comprises a carbon black pigment and/or an organic pigment.

44. The process for the preparation of a pigment dispersion according to claim 32, wherein said pigment for introducing a hydrophilic dispersibility-providing group at said surface treatment step comprises one or more pigments selected from the group consisting of C.I. pigment red, C.I. pigment yellow, C.I. pigment violet, C.I. pigment blue, C.I. pigment orange, C.I. pigment green, and C.I. pigment brown.

45. The process for the preparation of a pigment dispersion according to claim 32, wherein said pigment for introducing a hydrophilic dispersibility-providing group at said surface treatment step comprises one or more pigments selected from the group consisting of phthalocyanine pigment, quinacridone pigment, condensed azo pigment, isoindolinone pigment, quinophthalone pigment, anthraquinone pigment, benzimidazolone pigment, and perylene pigment.

46. The process for the preparation of a pigment dispersion according to claim 32, wherein said surface treatment step involves the introduction of a polymer material onto the surface of a pigment directly and/or with the interposition of a polyvalent group.

47. A pigment dispersion prepared by the process for the preparation pigment dispersion according to claim 32.

48. An ink jet recording ink at least comprising the pigment dispersion according to claim 47.

49. An ink jet recording method which comprises energizing the ink according to claim 48 so that it is ejected from a recording lead and attached to a recording medium.

50. The ink jet recording method according to claim 49, wherein said energy is a dynamic energy.

51. The ink jet recording method according to claim 49, wherein said energy is a heat energy.

52. A recorded material obtained by the method described in claim 49.

53. The process according to claim 32, wherein the wetting agent is present in an amount of from 0.1 to 30% by weight based on the weight of the pigment dispersion in the dispersion step.

54. A process for the preparation of a recording liquid comprising the steps of:

(i) providing a pigment dispersion prepared by the process of claim 32; and

(ii) subsequent to the preparation of said pigment dispersion, mixing the pigment dispersion with at least a solvent to form the recording liquid.

55. The process as claimed in claim 54, wherein step (ii) comprising mixing the pigment dispersion with at least the solvent, a surfactant and water to form the recording liquid.

56. The process as claimed in claim 55, wherein the recording liquid has a solid component comprising the surface treated pigment and resin and a liquid component comprising the wetting agent, solvent, surfactant, polyvalent metal ions and water, the solid component of the recording liquid being present in an amount by weight that is less than an amount by weight of the wetting agent, solvent surfactant and polyvalent metal ions present in the liquid.

57. The process as claimed in claim 56, wherein the pigment dispersion has (i) a liquid component comprising the wetting agent, water and polyvalent metal ions and (ii) a solid component comprising the surface treated pigment and the resin, said solid component being present in the pigment dispersion in an amount by weight that is greater than a total amount by weight of the wetting agent and polyvalent metal ions present in the liquid component.

58. The process according to claim 57, wherein the pigment dispersion consists essentially of the surface treated pigment, the resin, the wetting agent, the polyvalent metal ions and water.

59. The process according to claim 57, wherein the pigment dispersion consists essentially of the surface treated pigment, the resin, the wetting agent, neutralizing agent, the polyvalent metal ions and water.

60. The process according to claim 32, wherein the resin is added during said dispersion step.

61. A process for the preparation of a recording liquid comprising the steps of:

(i) providing a pigment dispersion prepared by a process comprising

a) a pigment surface treatment step of introducing at least one hydrophilic dispersibility-providing group onto the surface of a pigment directly and/or with the interposition of a polyvalent group to form a surface treated pigment that is self dispersible in water and that comprises said at least one hydrophilic dispersibility-providing group in an amount of not lower than 10×

10<sup>−

6</sup> equivalent per gram of particulate pigment,

b) a dispersion step of dispersing a surface-treated pigment obtained at said surface treatment step in an aqueous medium, wherein said dispersion step involves the dispersion of said surface-treated pigment in admixture with a wetting agent and water wherein the wetting agent is selected from the group consisting of acetylene glycols, acetylene alcohols, glycol ethers and alkylene glycols and is present in an amount that enhances a dispersion efficiency of particles of the surface-treated pigment in water, and

(c) adding a resin for providing dispersibility an or fixability during and/or after said dispersion step to form said pigment dispersion, wherein the pigment dispersion has a liquid component comprising polyvalent metal ions in a total amount of not more than 600 ppm, wherein the dispersion step results in a dispersion having pigment concentration of from about 5 to 50% by weight; and

(ii) subsequent to the preparation of said pigment dispersion, mixing the pigment dispersion with at least a solvent to form the recording liquid, wherein step (ii) comprises mixing the pigment dispersion with at least the solvent, a surfactant and water to form the recording liquid, and wherein the recording liquid has a solid component comprising the surface treated pigment and resin and a liquid component comprising the wetting agent, solvent, surfactant, polyvalent metal ions and water, the solid component of the recording liquid being present in an amount by weight that is less than an amount by weight of the wetting agent, solvent, surfactant and polyvalent metal ions present in the liquid component of the recording liquid.