Aqueous dispersions containing multi-stage emulsion polymers
View Patent ↗Aqueous dispersions are disclosed, having a minimum film formation temperature no greater than about 50° C., that include a multi-stage emulsion polymer made by a process that includes a first polymerization stage, in which a first monomer mixture having a calculated glass transition temperature of at least about 50° C. is polymerized via free radical emulsion polymerization to obtain a first-stage emulsion polymer, and a second polymerization stage, in which a second monomer mixture, having a calculated glass transition temperature from about −30° C. to about 10° C., is polymerized via free radical emulsion polymerization, in the presence of the first-stage emulsion polymer. The dispersions are useful in a variety of coating compositions that exhibit improved block resistance.
1. An aqueous dispersion, having a minimum film formation temperature no greater than about 50° C., comprising a multi-stage emulsion polymer made by a process that comprises:
a first polymerization stage, in which a first monomer mixture having a calculated glass transition temperature of at least about 50° C. is polymerized via free radical emulsion polymerization to obtain a first-stage emulsion polymer, the first monomer mixture comprising:
from about 80 to about 99.5% by weight of one or more ethylenically unsaturated non-ionic monomers;
from 0 to about 5% by weight of one or more ethylenically unsaturated weak acid monomers;
from 0 to about 5% by weight of one or more ethylenically unsaturated strong acid monomers; and
from 0 to about 10% by weight of one or more ethylenically unsaturated monomers containing a keto group,
wherein the first monomer mixture contains at least about 0.5% by weight of at least one of the ethylenically unsaturated strong acid monomers or the ethylenically unsaturated weak acid monomers, or mixtures thereof; and
a second polymerization stage, in which a second monomer mixture having a calculated glass transition temperature from about −30° C. to about 10° C. is polymerized via free radical emulsion polymerization, in the presence of the first-stage emulsion polymer, to obtain the multi-stage emulsion polymer, the second monomer mixture comprising:
from about 80 to about 99.5% by weight of one or more ethylenically unsaturated non-ionic monomers;
from 0 to about 5% by weight of one or more ethylenically unsaturated weak acid monomers;
from about 0.5 to about 10% by weight of one or more ethylenically unsaturated strong acid monomers; and
from about 0.5% to about 10% by weight of one or more ethylenically unsaturated monomers containing a keto group.
2. The aqueous dispersion according to claim 1 , wherein the aqueous dispersion further comprises one or more of: a molecule containing multiple —NH 2 or —NH— functionality, or a polyfunctional carboxylic hydrazide containing at least two hydrazide groups per molecule.
3. The aqueous dispersion according to claim 1 , wherein the one or more non-ionic monomers of the first monomer mixture, or of the second monomer mixture, or both, comprise one or more of: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, an amino-functional monomer, an ureido-functional monomer, styrene, a substituted styrene, butadiene, ethylene, propylene, an α-olefin, vinyl acetate, vinyl butyrate, vinyl chloride, or vinylidene chloride.
4. The aqueous dispersion according to claim 1 , wherein the one or more strong acid monomers of the first monomer mixture, or of the second monomer mixture, or both, comprise one or more of: 2-acrylamido-2-methylpropane sulfonic acid, 1-allyloxy-2-hydroxypropane sulfonic acid, vinylsulfonic acid, styrene sulfonic acid, an alkyl allyl sulfosuccinic acid, sulphoethyl methacrylate, sulphoethyl acrylate, phosphoethyl methacrylate (phosphate ester of 2-hydroxyethyl methacrylate), phosphoethyl acrylate, phosphopropyl methacrylate, phosphopropyl acrylate, phosphobutyl methacrylate, phosphobutyl acrylate, a phosphate ester of polyethyleneglycol acrylate or methacrylate, a phosphate ester of polypropyleneglycol acrylate or methacrylate, a phosphoalkyl crotonate, a phosphoalkyl maleate, a phosphoalkyl fumarate, a phosphodialkyl acrylate or methacrylate, a phosphodialkyl crotonate, allyl phosphate, or a salt of any of the foregoing.
5. The aqueous dispersion according to claim 1 , wherein the one or more weak acid monomers of the first monomer mixture, or of the second monomer mixture, or both, comprise one or more of: acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, or a salt of any of the foregoing.
6. The aqueous dispersion according to claim 1 , wherein the one or more monomers containing a keto group of the first monomer mixture, or of the second monomer mixture, or both, comprise one or more of: diacetoneacrylamide, diacetonemethacrylamide, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxybutyl methacrylate, acetoacetoxybutyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxypropyl acrylate, acrylamidomethylacetylacetone, allyl acetoacetate, or vinyl acetoacetate.
7. The aqueous dispersion according to claim 2 , wherein the molecule containing multiple —NH 2 or —NH— functionality comprises one or more of: hydrazine, ethylene diamine, propanediamine, butanediamine, hexanediamine, isophorone diamine, piperazine, diethylene triamine, dipropylene triamine, triethylene tetramine, an oligomer of ethylene diamine, or a poly(ethyleneimine).
8. The aqueous dispersion according to claim 2 , wherein the polyfunctional carboxylic hydrazide comprises one or more of: adipic dihydrazide, oxalic dihydrazide, isophthalic dihydrazide, or polyacrylic polyhydrazide.
9. The aqueous dispersion according to claim 1 , wherein the aqueous dispersion further comprises adipic dihydrazide.
10. The aqueous dispersion according to claim 1 , wherein the one or more strong acid monomers of the second monomer mixture comprise phosphoethyl methacrylate (phosphate ester of 2-hydroxyethyl methacrylate), and the one or more monomers containing a keto group of the second monomer mixture comprise diacetone acrylamide.
11. The aqueous dispersion according to claim 1 , wherein the one or more strong acid monomers of the second monomer mixture are present in an amount from about 1.0 to about 5.0% by weight based on the weight of the second monomer mixture.
12. The aqueous dispersion according to claim 1 , wherein the one or more monomers containing a keto group of the second monomer mixture are present in an amount from about 2.0% to about 5.0% by weight based on the weight of the second monomer mixture.
13. The aqueous dispersion according to claim 1 , wherein the weight ratio of the first monomer mixture with respect to the second monomer mixture is from about 20:80 to about 50:50.
14. The aqueous dispersion according to claim 1 , wherein the weight ratio of the first monomer mixture with respect to the second monomer mixture is from about 30:70 to about 40:60.
15. The aqueous dispersion according to claim 1 , wherein the first monomer mixture has a calculated glass transition temperature of at least about 60° C.
16. The aqueous dispersion according to claim 1 , wherein the first monomer mixture has a calculated glass transition temperature of at least about 70° C.
17. The aqueous dispersion according to claim 1 , wherein the second monomer mixture has a calculated glass transition temperature from about −20 to about 0° C.
18. The aqueous dispersion according to claim 1 , wherein a dry film formed from the aqueous dispersion obtains a score of at least 7 on a HOT-BLOCK RESISTANCE TEST.
19. The aqueous dispersion according to claim 1 , wherein a dry film formed from the aqueous dispersion obtains a score of at least 8 on a HOT-BLOCK RESISTANCE TEST.