Method of preparing encapsulated pigment dispersions with monomers which have a lower critical solution temperature

• US 8,859,644 B2
• Filed: 12/15/2011
• Issued: 10/14/2014
• Est. Priority Date: 12/15/2010
• Status: Active Grant

• Current Assignee: DuPont Electronics, Inc. (DuPont de Nemours, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Wolfe, Michael Stephen, Anton, Waifong Liew, Lee, Hee Hyun
• Primary Examiner(s): NGUYEN, VU ANH
• Application Number:
  US13/884,618
• Publication Number:
  US 20130225754A1
• Time in Patent Office: 1,034 Days
• Field of Search: 524/457, 524/458, 524/461, 523/206
• US Class Current: 523/206
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• 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: C01P 2006/22 Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
• CPC Class Codes: C08F 2/44 Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• CPC Class Codes: C08F 220/10 Esters
• CPC Class Codes: C08F 292/00 Macromolecular compounds obtained by polymerising monomers on to inorganic materials
• CPC Class Codes: C09B 67/0008 with organic coatings
• CPC Class Codes: C09B 67/0013 with polymeric coatings
• CPC Class Codes: C09B 67/009 polymeric dispersing agent
• CPC Class Codes: C09C 1/56 Treatment of carbon black ; Purification
• CPC Class Codes: C09C 3/10 Treatment with macromolecular organic compounds C09C3/006 takes precedence
• CPC Class Codes: C09D 11/322 Pigment inks
• CPC Class Codes: C09D 11/40 Ink-sets specially adapted for multi-colour inkjet printing
• CPC Class Codes: C09D 7/41 Organic pigments; Organic dyes
• CPC Class Codes: C09D 7/45 Anti-settling agents
• CPC Class Codes: C09D 7/62 modified by treatment with other compounds

Abstract

Processes for encapsulating pigment dispersions is described and are used in inkjet inks providing stability with regard to heat aging test conditions and solvent challenges. Prints from these inks have better durability than prints made from dispersions that are not encapsulated.

Claims

1. A method of making an aqueous encapsulated pigment dispersion, comprising the steps:

a) dispersing a pigment with a polymeric dispersant in an aqueous vehicle;

b) adding an encapsulation monomer mixture to the aqueous vehicle of step (a) at a first temperature;

wherein the encapsulation monomer mixture comprises 50 to 100 weight percent of a first monomer, 0 to 50 weight percent of a second monomer, and 0 to 25 weight percent of a third monomer,

wherein the first monomer is soluble in an aqueous solution below the first monomer'"'"'s Lower Critical Solution Temperature and sparingly soluble above Lower Critical Solution Temperature,

wherein the second monomer is a hydrophobic acrylate monomer and the third monomer is a hydrophilic acrylic monomer;

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

d) heating the mixture from step c) to a second temperature at least 20°

C. above the first temperature; and

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

2. The method of claim 1 wherein the weight ratio of encapsulation monomer mixture to pigment is from 0.1 to 10.

3. The method of claim 1 wherein the weight ratio of encapsulation monomer mixture to pigment is from 0.25 to 5.

4. The method of claim 1 wherein the first monomer has a Lower Critical Solution Temperature of between 5°

and 85°

C.

5. The method of claim 1 wherein the encapsulation monomer mixture further comprises a polymeric dispersant.

6. The method of claim 1 wherein the first monomer is selected from the group consisting of ethoxytriethylenegylcol methacrylate, 2-(2-ethoxyethoxy) ethyl acrylate;

ethylene glycol methyl ether methacrylate, and mixtures thereof.

7. The method of claim 1 where the second monomer is selected from the group consisting of benzyl methacrylate, butyl methacrylate, cyclohexyl 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, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-ethoxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and di- and tri-methacrylates and mixtures thereof.

8. The method of claim 1 wherein the third 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.

9. The method of claim 1 wherein the encapsulation monomer mixture further comprises vinyl monomer selected from the group consisting of styrene, alpha-methyl styrene, substituted styrenes, vinyl acetate, and vinyl butyrate and vinyl benzoate and mixtures thereof and wherein the vinyl monomer is at most 20 weight percent of the first monomer.

10. The method of claim 1 wherein the polymeric dispersant has a number average molecular weight of 2000 to 9500 daltons.

11. The method of claim 1 wherein the pigment with a polymeric dispersant used in step (a) is purified prior to addition of the encapsulation monomer mixture to the aqueous vehicle.

12. The method of claim 11 wherein the purified method is ultrafiltration.

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

14. The method of claim 1 wherein the polymeric dispersant used in step (a) is an ionically stabilized polymeric dispersant and comprises a polymeric ionic dispersant, in an aqueous vehicle, wherein:

(a) the polymeric ionic dispersant is physically adsorbed to the pigment,

(b) the polymeric ionic dispersant stably disperses the pigment in the aqueous vehicle,

(c) the average particle size of the dispersion is less than about 300 nm, and

(d) when the aqueous pigment dispersion is added to about 1.5 g of an aqueous sodium chloride solution of about 0.16 molar salt, in an amount of

(i) 0.04 grams for pigment dispersions of about 10 wt % or more solids (based upon the total weight of the dispersion),

(ii) 0.08 grams for pigment dispersions of about 5-10 wt % solids (based upon the total weight of the dispersion), and

(iii) 0.12 grams for pigment dispersions of about 5 wt % or less solids (based upon the total weight of the dispersion),

the pigment precipitates out of the aqueous salt solution when observed after storing for 24 hours at room temperature.

15. An aqueous pigmented ink jet ink comprising the aqueous encapsulated pigment of 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.

16. An ink set comprising at least one cyan ink, at least one magenta ink and at least one yellow ink, wherein at least one of the inks is an aqueous pigmented ink jet ink as set forth in claim 15.