Cellulose-based organic pigments
A pigment comprising dyed crystalline cellulose particles comprising a crystalline cellulose core having a surface charge, optionally one or more polyelectrolyte layers with alternating charges adsorbed on top of each other on the crystalline cellulose core, the polyelectrolyte layer closest to the core having a charge opposite the surface charge of the core, and at least one organic dye having a charge is provided.
1. A pigment comprising dyed crystalline cellulose particles comprising:
a crystalline cellulose core having a surface charge, the crystalline cellulose being nanocrystalline cellulose or microcrystalline cellulose,
one or more polyelectrolyte layers with alternating charges electrostatically adsorbed on top of each other on the crystalline cellulose core, the polyelectrolyte layer closest to the core having a charge opposite the surface charge of the core, and
at least one organic dye having a charge,
wherein:
A) when the charge of the organic dye is opposite the surface charge of the crystalline cellulose core, the organic dye is electrostatically adsorbed on an even number of polyelectrolyte layers with alternating charges, and
B) when the charge of the organic dye is the same as the surface charge of the crystalline cellulose core, the organic dye is electrostatically adsorbed on an odd number of polyelectrolyte layers with alternating charges,
wherein sufficient dye is adsorbed on the one or more polyelectrolyte layers for the pigment to impart color to a medium in which it is incorporated,
wherein the crystalline cellulose core, the one or more polyelectrolyte layers, and the dye are strong adsorbed together so that the pigment is stable, wherein the dyed crystalline cellulose particles are aggregated together into solid spherical aggregates having an average size up to about 50 microns, and
wherein the aggregates are suspended in a fluid to which they impart color.
2. The pigment of claim 1 , wherein the charge of the organic dye is opposite the surface charge of the crystalline cellulose core and the organic dye is adsorbed on an even number of polyelectrolyte layers with alternating charges adsorbed on top of each other on the crystalline cellulose core, the polyelectrolyte layer closest to the core having a charge opposite the surface charge of the core.
3. The pigment of claim 1 , wherein the charge of the organic dye is the same as the surface charge of the crystalline cellulose core and the organic dye is adsorbed on an odd number of polyelectrolyte layers with alternating charges adsorbed on top of each other on the crystalline cellulose core, the polyelectrolyte layer closest to the core having a charge opposite the surface charge of the core.
4. The pigment of claim 1 , wherein the crystalline cellulose is positively-charged microcrystalline cellulose that is microcrystalline cellulose modified with glycidyltrimethylammonium chloride functional groups, or with adsorbed cationic amylopectin.
5. The pigment of claim 1 , wherein the crystalline cellulose is negatively-charged microcrystalline cellulose that is microcrystalline cellulose with phosphate and polyphosphate functional groups, carboxymethylcellulose sodium salt, carboxymethyl cellulose sodium sulfate salt, and microcrystalline cellulose reacted with calcium alginate.
6. The pigment of claim 1 , wherein the crystalline cellulose is positively-charged nanocrystalline cellulose that is nanocrystalline cellulose with glycidyltrimethylammonium chloride functional groups, nanocrystalline cellulose reacted cationic surfactant hexadecyltrimethylammonium or cationic polyacrylamide or nanocrystalline cellulose grafted with a cationic polymer.
7. The pigment of claim 1 , wherein the crystalline cellulose is negatively charged nanocrystalline cellulose that is carboxylated nanocrystalline cellulose, sulfonated nanocrystalline cellulose, phosphonated nanocrystalline cellulose, or a salt thereof.
8. The pigment of claim 1 , wherein the dyed crystalline cellulose comprises a negatively-charged polyelectrolyte.
9. The pigment of claim 1 , wherein the dyed crystalline cellulose comprises a positively-charged polyelectrolyte that is a copolymer of acrylamide with an aminoderivative of acrylic acid or methacrylic acid ester; quaternized poly-4-vinylpyridine; poly-2-methyl-5-vinylpyridine; poly(ethyleneimine); pol-L-lysine, a poly(amidoamine); a poly(amino-co-ester), or a polyquaternium.
10. The pigment of claim 1 , wherein the dyed crystalline cellulose particles are mixed with undyed crystalline cellulose particles comprising:
the crystalline cellulose core, and
optionally one or more polyelectrolyte layers with alternating charges adsorbed on top of each other on the crystalline cellulose core, the polyelectrolyte layer closest to the core having a charge opposite the surface charge of the core,
wherein the undyed crystalline cellulose particles are free of dyes.
11. The pigment of claim 1 , comprising a mixture of dyed crystalline cellulose particles of at least two different hues.
12. The pigment of claim 1 , wherein the fluid is a cosmetically acceptable auxiliary agent.
13. A method of producing a pigment of claim 1 , the method comprising the steps of:
a) providing crystalline cellulose cores having a surface charge, an organic dye having a charge, a first polyelectrolyte having a charge opposite to the charge of the crystalline cellulose cores, and optionally a second polyelectrolyte having the same charge as the crystalline cellulose cores, the crystalline cellulose being nanocrystalline cellulose or microcrystalline cellulose,
when the charge of the organic dye is opposite the surface charge of the crystalline cellulose core,
b) adsorbing an even number of polyelectrolyte layers with alternating charges on top of each other on the crystalline cellulose core, and then
c) adsorbing the organic dye on the crystalline cellulose core, thereby producing the pigment,
or when the charge of the organic dye is the same as the surface charge of the crystalline cellulose core
b′) adsorbing an odd number of polyelectrolyte layers with alternating charges on top of each other on the crystalline cellulose core, and then
c′) adsorbing the organic dye on the crystalline cellulose core, thereby producing the pigment,
spray-drying the dyed crystalline cellulose particles, thereby aggregating the dyed crystalline cellulose particles into solid spherical aggregates having an average size up to about 50 microns, and
suspending the aggregates in a fluid thereby imparting color to said fluid,
wherein the polyelectrolyte layer closest to the core has a charge opposite the surface charge of the core.
14. The method of claim 13 , wherein step b) comprises:
b1) suspending the crystalline cellulose cores in a liquid in which the first polyelectrolyte is soluble, adding the first polyelectrolyte to the suspension, thereby adsorbing the first polyelectrolyte on the surface of the crystalline cellulose core,
b2)isolating the crystalline cellulose cores,
b3) suspending the crystalline cellulose cores in a liquid in which the second polyelectrolyte is soluble, adding the second polyelectrolyte to the suspension, thereby adsorbing the second polyelectrolyte on the surface of the crystalline cellulose core, and
b4)isolating the crystalline cellulose cores, and
b5) optionally repeating all of steps b1) to b4) one or more times.
15. The method of claim 13 , wherein step b′) comprises:
b′1) suspending the crystalline cellulose cores in a liquid in which the first polyelectrolyte is soluble, adding the first polyelectrolyte to the suspension, thereby adsorbing the first polyelectrolyte on the surface of the crystalline cellulose core, and
b′2) isolating the crystalline cellulose cores.
16. The method of claim 15 , wherein step b′) further comprises:
b′3) suspending the crystalline cellulose cores in a liquid in which the second polyelectrolyte is soluble, adding the second polyelectrolyte to the suspension, thereby adsorbing the second polyelectrolyte on the surface of the crystalline cellulose core,
b′4) isolating the crystalline cellulose cores,
b′5) optionally, suspending the crystalline cellulose cores in a liquid in which the first polyelectrolyte is soluble, adding the first polyelectrolyte to the suspension, thereby adsorbing the first polyelectrolyte on the surface of the crystalline cellulose core,
b′6) isolating the crystalline cellulose cores, and
b′7) optionally repeating all of steps b′3) to b′6) one or more times.
17. The method of claim 13 , wherein steps c) and/or c′) comprise the steps of suspending the crystalline cellulose cores in a liquid in which the dye is soluble, and adding the dye to the suspension, thereby adsorbing the organic dye directly on the surface of the crystalline cellulose core.
18. The method of claim 13 , further comprising the step f) of mixing the dyed crystalline cellulose particles with undyed crystalline cellulose particles, the undyed crystalline cellulose particles comprising:
the crystalline cellulose core, and
optionally one or more polyelectrolyte layers with alternating charges adsorbed on top of each other on the crystalline cellulose core, the polyelectrolyte layer closest to the core having a charge opposite the surface charge of the core,
the undyed crystalline cellulose particles being free of dyes.
19. The method of claim 13 , further comprising the step of mixing the dyed crystalline cellulose particles with dyed crystalline cellulose particles of a different hue.
20. The method of claim 13 , wherein the fluid is a cosmetically acceptable auxiliary agent.