Method of preparing encapsulated pigment dispersions which include polyurethane dispersions

• US 8,912,249 B2
• Filed: 12/15/2011
• Issued: 12/16/2014
• Est. Priority Date: 04/25/2011
• Status: Expired due to Fees

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Anton, Waifong Liew, Lee, Hee Hyun, Otley, Michael Joseph, Wolfe, Michael Stephen
• Primary Examiner(s): NGUYEN, VU ANH
• Application Number:
  US14/005,958
• Publication Number:
  US 20140011941A1
• Time in Patent Office: 1,097 Days
• Field of Search: 524/501, 523/206, 523/207, 523/210
• US Class Current: 523/160
• CPC Class Codes: C09B 67/0002 Grinding; Milling with solid grinding or milling assistants
• CPC Class Codes: C09B 67/0013 with polymeric coatings
• CPC Class Codes: C09B 67/0022 Wet grinding of pigments
• CPC Class Codes: C09B 67/009 polymeric dispersing agent
• CPC Class Codes: C09B 67/0091 Process features in the making of dispersions, e.g. ultrasonics
• CPC Class Codes: C09D 11/324 containing carbon black
• CPC Class Codes: C09D 11/326 characterised by the pigment dispersant
• CPC Class Codes: C09D 11/38 characterised by non-macromolecular additives other than solvents, pigments or dyes
• CPC Class Codes: C09D 11/40 Ink-sets specially adapted for multi-colour inkjet printing

Abstract

A process for encapsulating pigment dispersions is provided where a pigment is dispersed with a polymeric dispersant in an aqueous solvent system. An acrylate monomer and a polyurethane dispersion are added and the resultant mixture is polymerized. Optionally, the acrylate monomer/polyurethane mixture may be emulsified in water with an added surfactant or polymeric dispersant and up to 20% acrylic or other vinyl monomers based on the acrylate may be added to the acrylate monomer/polyurethane mixture before polymerization. Such encapsulated pigment dispersions may be used in inkjet inks and are stable to heat, aging test conditions, and solvent challenges. Prints from these inks have better durability.

Claims

1. A method of making an encapsulated pigment comprising steps of:

a) dispersing a pigment using a polymeric dispersant in an aqueous vehicle wherein the polymeric dispersant is selected from the group consisting of acrylic dispersant comprising acrylic and acrylate monomers and polyurethane dispersant and mixtures thereof and wherein the polymeric dispersant has a number average molecular weight of 2,000 to 9,500 daltons;

b) adding at least one encapsulation monomer and at least one aqueous polyurethane dispersion to the aqueous vehicle of step (a) to form a first dispersed pigment/encapsulation monomer/polyurethane dispersion/aqueous mixture and wherein the encapsulation monomer comprises acrylate monomers;

c) dispersing the encapsulation monomer/aqueous mixture using high shear mixing to form a second dispersed pigment/encapsulation monomer/aqueous polyurethane dispersion /aqueous mixture; and

d) polymerizing the encapsulation monomer by adding a polymerization initiator to the second dispersed pigment/encapsulation monomer/aqueous polyurethane dispersion/aqueous mixture.

2. The method of claim 1, wherein the encapsulation monomer and the aqueous polyurethane dispersion are mixed together prior to addition to the dispersed pigment in the aqueous vehicle.

3. The method of claim 1, wherein the weight ratio of said encapsulation monomer to said pigment is from 0.1 to 10.

4. The method of claim 1, wherein the aqueous polyurethane dispersion is from 10 to 75 weight percent polyurethane solids and weight ratio of the polyurethane solids to encapsulation monomer is from 0.1 to 10.

5. The method of claim 1, wherein the encapsulation monomer comprises at least one selected from the group consisting of benzyl methacrylate, butyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, methacrylonitrile, glycidyl methacrylate, p-tolyl methacrylate, sorbyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, phenyl acrylate, phenoxyethyl acrylate, glycidyl acrylate, p-tolyl acrylate, sorbyl acrylate, ethoxytriethyleneglycol methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-ethoxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and mixtures thereof.

6. The method of claim 1, wherein the encapsulation monomer further comprises an acrylic monomer that is at most 20 weight percent of the acrylate monomer.

7. The method of claim 6, wherein the acrylic monomer is selected from the group consisting of methacrylic acid, acrylic acid, maleic acid, maleic acid monoester, itaconic acid, itaconic acid monoester, crotonic acid, crotonic acid monoester, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, t-butylaminoethyl methacrylate, t-butylaminoethyl acrylate and mixtures thereof.

8. The method of claim 1, wherein the encapsulation monomer further comprises at least one vinyl monomer which is at most 20 weight percent of the acrylate monomer, said vinyl monomer is selected from the group consisting of styrene, alpha-methyl styrene, substituted styrenes, N-alkyl acrylamides, N-alkyl methacrylamides, vinyl acetate, vinyl butyrate, vinyl benzoate, and mixtures thereof.

9. The method of claim 1, wherein the polymeric dispersant is substituted with crosslinkable moieties where the crosslinkable moieties are selected from the group consisting of acetoacetoxy, acid, amine, epoxy, hydroxyl, blocked isocyanates and mixtures thereof.

10. The method of claim 9, wherein the polymeric dispersant substituted with crosslinkable moieties is reacted with a crosslinking agent where the crosslinking agent is chosen from acetoacetoxy, acid, amine, anhydride, epoxy, hydroxyl, isocyanates, blocked isocyanates and mixtures thereof.

11. The method of claim 1, where the polymeric dispersant is crosslinked after the pigment is dispersed and before the encapsulation monomer is added.

12. The method of claim 1, wherein the polyurethane in the aqueous polyurethane dispersion has a number average molecular weight of 2000 to 50,000 daltons.

13. The method of claim 1, wherein the polyurethane in the aqueous polyurethane dispersion has an acid number of 10 to 75 mg KOH/gram of the polyurethane solids of the polyurethane dispersion.

14. The method of claim 1, wherein the polyurethane of the aqueous polyurethane dispersion comprises a diol, a diol with an ionic substituent, and a diisocyanate,

wherein the molar amount of isocyanate from the diisocyanate exceeds the molar amount of the isocyanate-reactive groups of the diol and the diol with the ionic substituent.

15. The method of claim 1, wherein the pigment of step (a) is purified prior to adding the encapsulation monomer and the aqueous polyurethane dispersion.

16. The method of claim 15, wherein said pigment is purified by ultrafiltration.

17. The method of claim 1, wherein the polymeric dispersant is a structured polymeric dispersant selected from the group consisting of block polymer dispersant, branched polymer dispersant, graft star polymer dispersant, and mixtures thereof.

20. An aqueous pigmented inkjet ink comprising the aqueous encapsulated pigment as set forth in claim 1, having from about 0.1 to about 10 wt % pigment based on the total weight of the ink, a weight ratio of pigment to dispersant of from about 0.33 to about 400, a surface tension in the range of about 20 dyne/cm to about 70 dyne/cm at 25°

C., and a viscosity of lower than about 30 cP at 25°

C.

21. The method of claim 1, wherein the encapsulation monomer comprises a dimethacrylate and/or trimethacrylate.

18. A method of making an encapsulated pigment comprising the steps of:

a) dispersing a pigment using a first polymeric dispersant in an aqueous vehicle, wherein the first polymeric dispersant comprises acrylic and acrylate monomers and wherein the first polymeric dispersant has a number average molecular weight of 2000 to 9500 daltons;

b) preparing an aqueous emulsion comprising at least one encapsulation monomer, and least one aqueous polyurethane dispersion and a surfactant or a second polymeric dispersant, wherein the second polymeric dispersant comprises acrylic and acrylate monomers and wherein the encapsulation monomer comprises acrylate monomers;

c) adding the aqueous emulsion of step (b) to the aqueous vehicle of step (a) to form a first dispersed pigment/encapsulation monomer/aqueous polyurethane dispersion/aqueous mixture;

d) dispersing the encapsulation monomer/aqueous polyurethane dispersion/aqueous mixture using high shear mixing to form a second dispersed pigment/encapsulation monomer/aqueous mixture; and

e) polymerizing the encapsulation monomer by adding a polymerization initiator to the second dispersed pigment/encapsulation monomer/aqueous mixture.

19. The method of claim 18, wherein the encapsulation monomer comprises at least one selected from the group consisting of benzyl methacrylate, butyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, methacrylonitrile, glycidyl methacrylate, p-tolyl methacrylate, sorbyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, phenyl acrylate, phenoxyethyl acrylate, glycidyl acrylate, p-tolyl acrylate, sorbyl acrylate, ethoxy triethyleneglycol methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-ethoxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and mixtures thereof.

22. The method of claim 18, wherein the encapsulation monomer comprises a dimethacrylate and/or trimethacrylate.