Self-dispersed pigments and methods for making and using the same

• US 7,964,033 B2
• Filed: 08/22/2008
• Issued: 06/21/2011
• Est. Priority Date: 08/23/2007
• Status: Active Grant

• Current Assignee: Sensient Colors, LLC (Sensient Technologies Corporation)
• Original Assignee: Sensient Colors, LLC (Sensient Technologies Corporation)
• Inventors: Ulrich, Mark, Kane, John P., Shing, Vincent, Bogomolny, Michael, Ouellette, Daniel A., Sujeeth, Puthalath K.
• Primary Examiner(s): Green; Anthony J
• Application Number:
  US12/197,087
• Publication Number:
  US 20090050014A1
• Time in Patent Office: 1,033 Days
• Field of Search: 106/410, 106/412, 106/413, 106/476, 106/493, 106/494, 106/495, 106/496, 106/497, 106/498, 106/499
• US Class Current: 106/493
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2002/85 by XPS, EDX or EDAX data
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/22 Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C01P 2006/60 Optical properties, e.g. expressed in CIELAB-values
• CPC Class Codes: C09B 68/24 Azo-coupling
• CPC Class Codes: C09B 68/41 Polymers attached to the pigment surface C09B68/444, C09B68/446 take precedence
• CPC Class Codes: C09B 68/443 Carboxylic acid derivatives, e.g. carboxylic acid amides, carboxylic acid esters or CN groups
• CPC Class Codes: C09B 68/446 Amines or polyamines, e.g. aminopropyl, 1,3,4,-triamino-pentyl or polyethylene imine
• CPC Class Codes: C09B 68/46775 Triazine C09B68/427 takes precedence
• CPC Class Codes: C09C 1/56 Treatment of carbon black ; Purification
• CPC Class Codes: C09C 3/08 Treatment with low-molecular-weight non-polymer organic compounds C09C3/006, C09C3/048 take precedence
• 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 17/003 containing an organic pigment process features in the making of dye stuff preparations C09B67/00

Abstract

A method of modifying a pigment that includes reacting a reactive compound having an X-[Y]_n reactive group with a secondary compound N-S-ZM to form a substituted reactive intermediate [Y]_a-X-(N-S-ZM)_b. A pigment is reacted with the substituted reactive intermediate [Y]_a-X-(N-S-ZM)_b to attach the substituted reactive intermediate to the surface of the pigment to form a surface modified pigment. X may be a sulfonyl, phosphoryl, or 1,3,5-triazinyl group, Y may be a halogen leaving group, N may be a basic nucleophilic group, S may be an organic group, and ZM may be an ionizable end group. Also, n is an integer between 1 and 3, b is an integer between 1 and 3, and a=n−b. When n is equal to or greater than b, and if b is 2 or 3, each N-S-ZM can be the same or different.

Claims

1. A method of modifying a pigment, the method comprising:

reacting a reactive compound having an X-[Y]_n reactive group with a secondary compound N-S-ZM to form a substituted reactive intermediate [Y]_a-X-(N-S-ZM)_b; and

reacting a pigment with the substituted reactive intermediate [Y]_a-X-(N-S-ZM)_b to attach the substituted reactive intermediate to the surface of the pigment to form a surface modified pigment;

wherein X is a sulfonyl, phosphoryl, or 1,3,5-triazinyl group;

Y is a halogen leaving group;

N is a nucleophilic group;

S is an organic group;

ZM is an ionizable end group;

n is an integer between 1 and 3;

b is an integer between 1 and 3; and

a =n−

b;

wherein n is equal to or greater than b; and

wherein if b is 2 or 3, each N-S-ZM can be the same or different.

2. The method of claim 1, wherein b is 2 or 3, and each N-S-ZM is different.

3. The method of claim 1, wherein the pigment is in powder or wet cake form and is milled with a grind aid prior to the reaction with the substituted intermediate.

4. The method of claim 1, wherein Y comprises at least one of fluorine, chlorine, bromine, or iodine.

5. The method of claim 1, wherein N comprises at least one of an amine, an imine, a pyridine, or a thiol group.

6. The method of claim 1, wherein S comprises at least one of substituted or unsubstituted alkyls, aryls and polymer chains having a molecular weight range from about 300 to about 8000.

7. The method of claim 1, wherein Z comprises at least one of a carboxyl, sulfonyl, phenolic, or phosphoryl group and M comprises at least one of a proton or cation in salt form.

8. The method of claim 1, wherein the secondary compound N-S-ZM comprises at least one of a polymer, an amine, an amino acid, an alcohol, a thiol, and a combination thereof.

9. The method of claim 8, wherein the secondary compound N-S-ZM comprises at least one of amino benzoic acids, amino benzene sulfonic acids, amino phenols, amino sulfonic acids, polyethoxylated amino acids, sodium sulfanilate, sulfanilic acid, sodium p-aminobenzoate, p-aminophenol, ethyl 4-aminobenzoate, taurine, oleic acid (amino), tetramethylammonium 4-aminobenzoate, sodium 4-aminophenolate, sodium aminooleate, organic polymeric substrates, and combinations thereof.

10. The method of claim 9, wherein the organic polymeric substrates comprises at least one of linear alkyl and branched ethoxy and propoxy chain polymers with a molecular weight of about 300 to about 3000, linear polyethoxy polymeric amines, linear propoxy polymeric amines, styrene acrylic copolymers, polyethyleneimines, and combinations thereof.

11. The method of claim 1, wherein Z comprises at least one of ammonium, trimethylammonium, or tributylammonium and M comprises at least one of a halide or a negatively charged ion.

12. The method of claim 11, wherein the secondary compound N-S-ZM comprises at least one of a diamino aromatic, a polyethyleneimine, a polyguanidine, a quaternary ammonium compound, or a combination thereof.

13. The method of claim 1, wherein the pigment comprises at least one of carbon black, pigment red 122, pigment violet 19, pigment violet 23, pigment red 202, pigment red 188, pigment yellow 155, pigment yellow 97, pigment green 7, pigment blue 15:

3, pigment blue 15;

4, and pigment yellow 74, and combinations thereof.

14. The method of claim 1, further comprising milling the pigment to less than about 100 nm before, during, or after reacting the pigment with the substituted reactive intermediate.

15. The method of claim 1, wherein the substituted reactive intermediate [Y]_a -X-(N-S-ZM)_b is associated with charge-balancing counterions, further comprising at least partially substituting the counterions with at least one of alkali metals, alkaline earth metals, NR₁R₂R₃H⁺, and combinations thereof, wherein R₁, R₂, and R₃ are independently H or substituted or unsubstituted C₁-C₅ alkyl groups.

16. The method of claim 15, wherein the counterions are at least partially substituted with at least one of K+, Li+, NH₄+, monoethanolammonium, tetraethylammonium, triethanolammonium, tetramethylammonim, tetrabutylammonium, and combinations thereof.

17. The method of claim 1, wherein the surface modified pigment comprises about 0.01 to about 1.0 mMoles of S and about 0.01 to about 2.0 mMoles of active hydrogen per gram of pigment.

18. The method of claim 1, wherein the surface modified pigment comprises about 0.06 to about 0.7 mMoles of S and about 0.07 to about 1.6 mMoles of active hydrogen per gram of pigment.

19. The method of claim 1, wherein the surface modified pigment comprises pigment blue 15 comprising about 0.168 to about 0.430 mMoles of S and about 0.07 to about 0.313 mMoles of active hydrogen per gram of pigment.

20. The method of claim 1, wherein the surface modified pigment comprises pigment red 122 comprising about 0.062 to about 0.187 mMoles of S and about 0.077 to about 0.394 mMoles of active hydrogen per gram of pigment.

21. The method of claim 1, wherein the surface modified pigment comprises pigment yellow 74 comprising about 0.131 to about 0.178 mMoles of S and about 0.192 to about 0.290 mMoles of active hydrogen per gram of pigment.

22. The method of claim 1, wherein the surface modified pigment comprises carbon black comprising about 0.103 to about 0.702 mMoles of S and about 0.203 to about 1.579 mMoles of active hydrogen per gram of pigment.

23. The method of claim 1, wherein the surface modified pigment comprises sodium in the amount of about 100 to about 6500 ppm and potassium in the amount of about 30 to about 1200 ppm.

24. The method of claim 1, wherein the surface modified pigment comprises sulfur in the amount of about 50 ppm to about 2600 ppm.

25. The method of claim 1, wherein the surface modified pigment is a surface modified carbon black comprising carbon black having attached thereto:

an NH/N—

C═

N group distributed almost equally, in about 0.7 to 2.7 atomic %;

an oxygen in an atomic ratio of about 6.8 to 20.9% wherein at least about 51 to 62% of the oxygen is present as C═

O, COONa, or SOx group and the balance as a C—

O group, wherein SOx is an oxidized form of S;

COONa/SO3Na, in about 0.7 to 2.6 atomic %; and

wherein at least 90% of S present on the surface modified carbon black is oxidized S (SOx).

26. The method of claim 25, wherein SOx comprises at least one of a sulfone, a sulfate, or a sulfonic acid.

27. The method of claim 1, wherein the surface modified pigment is a surface modified pigment blue 15 comprising a surface oxygen content of at least about 2.5 atomic %.

28. The method of claim 1, wherein the surface modified pigment is a surface modified pigment red 122 comprising a surface oxygen content of about 8.3 to about 9.8 atomic %, wherein about 24% to about 32% of the total O exists as a C—

O bond.

29. The method of claim 1, wherein the surface modified pigment is a surface modified pigment yellow 74 comprising a surface oxygen content of about 21.6 to about 29.3 atomic %, wherein about 42% to about 48% is present as C═

O, COONa/CSO₃Na.

30. The method of claim 1, further comprising incorporating the surface modified pigment into an aqueous pigment dispersion.

31. The method of claim 1, further comprising incorporating the surface modified pigment into at least one of wood stain, a coating, an inkjet ink, a color filter, or a textile printing ink, or a combination thereof.

32. The method of claim 1, wherein the X-[Y]_n reactive group is cyanuric chloride and the secondary compound N-S-ZM is at least one of 4-aminobenzoic acid, sulfanilic acid, 4-aminophenol, taurine, oleic acid (amino), linear polyethoxy polymeric amines, propoxy polymeric amines, or combinations thereof.

33. The method of claim 2, wherein the X-[Y]_n reactive group is cyanuric chloride, the secondary compounds are 4-aminobenzoic acid and a polymeric amine.

34. The method of claim 1, wherein the surface modified pigment is a self-dispersing pigment.