Methods for preparing highly viscous ionomer-poly(vinylalcohol) coatings
View Patent ↗Disclosed are methods to form coatings on a substrate, the coatings comprising a blend of a poly(vinyl alcohol) composition comprising a poly(vinyl alcohol) characterized by a hydrolysis level of from about 85 to about 93 mole % and a 4 weight % aqueous viscosity at 20° C. of about 16 to about 75 centipoise; and an ionomer comprising a parent acid copolymer that comprises ethylene and about 18 to about 30 weight % of acrylic acid or methacrylic acid, the acid copolymer having a melt flow rate from about 200 to about 1000 g/10 min., wherein about 50% to about 70% of the carboxylic acid groups of the copolymer are neutralized to carboxylic acid salts comprising potassium cations, sodium cations or combinations thereof. Multilayer structures comprising the blend composition on a substrate are also disclosed.
1. A method to form a coating comprising a blend of ionomer and poly(vinyl alcohol) on a substrate, the method comprising
(1) providing a blend composition comprising
(a) about 99 to about 1 weight %, based on the combination of (a) and (b), of a poly(vinyl alcohol) composition comprising a poly(vinyl alcohol) characterized by a hydrolysis level of from about 85 to about 93 mol % and a 4 weight % aqueous viscosity at 20° C. of from 16 to about 75 centipoise (cp); and
(b) about 1 to about 99 weight %, based on the combination of (a) and (b), of an ionomer composition comprising a parent acid copolymer that comprises copolymerized units of ethylene and about 18 to about 30 weight % of copolymerized units of acrylic acid or methacrylic acid, based on the total weight of the parent acid copolymer, the acid copolymer having a melt flow rate (MFR) from about 200 to about 1000 g/10 min., measured according to ASTM D1238 at 190° C. with a 2160 g load, wherein about 50% to about 70% of the carboxylic acid groups of the copolymer, based on the total carboxylic acid content of the parent acid copolymer as calculated for the non-neutralized parent acid copolymer, are neutralized to carboxylic acid salts comprising potassium cations, sodium cations or combinations thereof; wherein the ionomer disperses readily in 80 to 100° C. water without need for additional dispersants or reagents;
(2) providing a substrate; and
(3) coating the blend composition onto the substrate.
2. The method of claim 1 comprising an ionomer wherein the cations of the carboxylate salts consist essentially of sodium cations.
3. The method of claim 1 comprising an ionomer wherein the cations of the carboxylate salts consist essentially of potassium cations.
4. The method of claim 1 wherein (b) is present in the combination of (a) and (b) in an amount from about 10 to about 95 weight %, (a) being present in a complementary amount.
5. The method of claim 1 wherein (b) is present in the combination of (a) and (b) in an amount from about 60 to about 95 weight %, (a) being present in a complementary amount.
6. The method of claim 1 wherein the poly(vinyl alcohol) is characterized by a 4 weight % aqueous viscosity at 20° C. of about 20 to about 75 cp.
7. The method of claim 6 wherein the poly(vinyl alcohol) is characterized by a 4 weight % aqueous viscosity at 20° C. of about 20 to about 60 cp.
8. The method of claim 1 wherein the acid copolymer has a MFR from about 250 to about 400 g/10 min.
9. The method of claim 1 wherein the acid copolymer is an ethylene methacrylic acid dipolymer having about 18 to about 25 weight % of copolymerized units of methacrylic acid.
10. The method of claim 1 wherein the ionomer composition has a MFR from about 1 to about 20 g/10 min.
11. The method of claim 1 wherein the ionomer composition comprises at least 11 weight % methacrylic acid salt and has a MFR of at least 1 g/10 min.
12. The method of claim 1 wherein the substrate is paper, paperboard, cardboard, pulp-molded shape, textile, material made from a synthetic fiber spun fabric, film, open-cell foam, closed-cell foam, or metallic foil.
13. The method of claim 12 wherein the substrate is paper, paperboard, cardboard, or pulp-molded shape.
14. The method of claim 1 wherein the blend composition is provided in the form of an aqueous dispersion comprising water and about 0.001 to about 50 weight % of the combination of (a) and (b); the blend composition is coated onto the substrate as the aqueous dispersion and the method further comprises (4) drying the coated substrate at a temperature of about 20 to about 150° C.
15. The method of claim 14 wherein providing the blend composition comprises (1a) providing an aqueous poly(vinyl alcohol) solution comprising water and the poly(vinyl alcohol) composition of (a); (1b) providing an ionomer composition comprising the ionomer composition of (b); (1c) mixing the ionomer composition with the aqueous poly(vinyl alcohol) composition solution optionally with heating; and (1d) optionally cooling the heated aqueous blend dispersion to a temperature of about 20 to 30° C., wherein the combination remains dispersed in the liquid phase.
16. The method of claim 15 wherein (1a) comprises heating a mixture of water and the poly(vinyl alcohol) composition to provide the aqueous poly(vinyl alcohol) solution, optionally followed by cooling to a temperature of about 20 to about 30° C.; and (1b) comprises providing an aqueous ionomer composition by mixing a solid ionomer composition with water heated to a temperature from about 80 to about 100° C. to provide a heated aqueous ionomer composition dispersion; optionally followed by cooling to a temperature of about 20 to about 30° C., wherein the ionomer remains dispersed in the aqueous phase.
17. The method of claim 14 wherein providing the blend composition comprises (1a) heating a mixture of water and a poly(vinyl alcohol) composition described above to provide an aqueous poly(vinyl alcohol) solution optionally followed by cooling to a temperature of about 20 to about 30° C.; (1b) providing the ionomer composition comprising the ionomer in solid form; (1c) heating the aqueous poly(vinyl alcohol) solution to a temperature from about 80 to about 100° C. (under low shear conditions); (1d) contacting the solid ionomer composition with the heated aqueous poly(vinyl alcohol) solution; (1e) continuing heating at a temperature from about 80 to about 100° C. until the solid ionomer composition has completely dispersed; and (1f) optionally cooling to a temperature of about 20 to 30° C.
18. The method of claim 14 wherein providing the blend composition comprises (1a) heating a combination of the poly(vinyl alcohol) with water to provide an aqueous poly(vinyl alcohol) composition solution; (1b) providing the ionomer composition comprising the ionomer in solid form; (1c) contacting the solid ionomer composition with the aqueous poly(vinyl alcohol) solution to provide a mixture; (1d) heating the mixture to a temperature from about 80 to about 100° C. until the solid ionomer composition has completely dispersed; and (1e) optionally cooling to a temperature of about 20 to 30° C.
19. The method of claim 1 wherein the blend composition is provided in the form of a preformed ionomer-PVOH film comprising the combination of (a) and (b); (3) comprises (3a) producing a prelaminate structure comprising the ionomer-PVOH film layer adjacent to the substrate; and (3b) laminating the ionomer-PVOH film layer to the substrate at a temperature from about 50 to about 150° C., optionally with applied pressure; and the method further comprises (4) cooling the coated substrate to a temperature of about 20 to about 30° C.
20. The method of claim 1 wherein (b) is present in the combination of (a) and (b) in an amount from about 50 to about 70 weight %, (a) being present in a complementary amount.
21. The method of claim 1 wherein the ionomer composition does not include ammonium ions.
22. The method of claim 1 wherein the viscosity of the ionomer-PVOH blend dispersion is higher than the viscosity of the PVOH dispersion without ionomer.
23. The method of claim 22 wherein the viscosity of the ionomer-PVOH blend dispersion at a 1:4 ratio of ionomer to PVOH is at least 25% higher than the viscosity of the PVOH dispersion without ionomer.
24. The method of claim 22 wherein the viscosity of the ionomer-PVOH blend dispersion at a 4:1 ratio of ionomer to PVOH is about 4 to about 20 times higher than the viscosity of the PVOH dispersion without ionomer.