Water-soluble polyvinyl alcohol film with plasticizer blend, related methods, and related articles
Disclosed herein are water-soluble films including a polyvinyl alcohol (PVOH) polymer and a combination of at least three plasticizers. The combination of plasticizers includes dipropylene glycol as a first plasticizer, a sugar alcohol such as sorbitol as a second plasticizer, and a polyol such as glycerin as a third plasticizer. When the PVOH polymer and plasticizers are blended in particular proportions and/or selected with regard to various criteria related to physical and chemical film properties, the resulting water-soluble film formed from the PVOH resin blend exhibits beneficial combinations four) of aged tensile strength, aged melting transition delta elevation, aged adhesion value, and/or resistance to seal peeling, which provide strong film seals that retain their water-solubility characteristics.
1. A water-soluble film comprising:
a polyvinyl alcohol (PVOH) polymer;
dipropylene glycol as a first plasticizer;
a sugar alcohol as a second plasticizer; and
a polyol as a third plasticizer, the third plasticizer being different from the first plasticizer and the second plasticizer;
wherein:
the first plasticizer is present in the water-soluble film in an amount in a range of 13 wt. % to 46 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film;
the second plasticizer is present in the water-soluble film in an amount in a range of 13 wt. % to 58 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film;
the third plasticizer is present in the water-soluble film in an amount in a range of 28 wt. % to 73 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film; and
the water-soluble film has at least two of the three properties (a), (b), and (c):
(a) an aged melting transition delta elevation of 11° C. or less as measured by the Aged Melting Transition Delta Test;
(b) an aged adhesion value of at least 1900 g/s as measured by the Aged Adhesion Test; and
(c) an aged tensile strength of at least 30 MPa as measured by the Aged Tensile Strength Test.
2. The water-soluble film of claim 1 , wherein the sugar alcohol is selected from the group consisting of isomalt, maltitol, sorbitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol, and mannitol.
3. The water-soluble film of claim 2 , wherein the sugar alcohol is sorbitol.
4. The water-soluble film of claim 1 , wherein the polyol is selected from the group consisting of glycerin, diglycerin, ethylene glycol, diethylene glycol, triethyleneglycol, tetraethylene glycol, polyethylene glycols up to 400 MW, neopentyl glycol, propylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, and polyether polyols.
5. The water-soluble film of claim 4 , wherein the polyol is glycerin.
6. The water-soluble film of claim 1 , wherein the sugar alcohol is sorbitol, and the polyol is glycerin.
7. The water-soluble film of claim 1 , comprising:
the polyvinyl alcohol (PVOH) polymer;
dipropylene glycol as the first plasticizer;
sorbitol as the second plasticizer; and
glycerin as the third plasticizer;
wherein the first, second, and third plasticizers are present in the water-soluble film in a combined amount in a range of 5 parts to 50 parts total plasticizer per 100 parts total resin (phr) in the water-soluble film.
8. The water-soluble film of claim 1 , wherein the water-soluble film is substantially free from plasticizers other than the first, second, and third plasticizers.
9. The water-soluble film of claim 1 , wherein the water-soluble film comprises a solid plasticizer which has a melting point above 50° C.
10. The water-soluble film of claim 9 , wherein the solid plasticizer is also the second plasticizer.
11. The water-soluble film of claim 1 , wherein the first, second, and third plasticizers are present in the water-soluble film in a combined amount in a range of 5 parts to 40 parts total plasticizer per 100 parts total resin (phr) in the water-soluble film.
12. The water-soluble film of claim 11 , wherein the first, second, and third plasticizers are present in the water-soluble film in a combined amount in a range of 10 phr to 40 phr.
13. The water-soluble film of claim 11 , wherein the first, second, and third plasticizers are present in the water-soluble film in a combined amount in a range of 20 phr to 35 phr.
14. The water-soluble film of claim 1 , wherein:
the water-soluble film has an aged tensile strength of at least 25 MPa as measured by the Aged Tensile Strength Test; and
the water-soluble film has a seal tear value of at least 170% as measured by the Sum Seal Tear Test.
15. The water-soluble film of claim 14 , wherein the water-soluble film has an aged tensile strength of at least 30 MPa as measured by the Aged Tensile Strength Test.
16. The water-soluble film of claim 1 , wherein:
the first plasticizer is present in the water-soluble film in an amount in a range of 13 wt. % to 38 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film;
the second plasticizer is present in the water-soluble film in an amount in a range of 16 wt. % to 58 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film; and
the third plasticizer is present in the water-soluble film in an amount in a range of 28 wt. % to 71 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film.
17. The water-soluble film of claim 1 , wherein:
the first plasticizer is present in the water-soluble film in an amount in a range of 13 wt. % to 45 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film;
the second plasticizer is present in the water-soluble film in an amount in a range of 19 wt. % to 52 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film; and
the third plasticizer is present in the water-soluble film in an amount in a range of 35 wt. % to 65 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film.
18. The water-soluble film of claim 1 , wherein:
the first plasticizer is present in the water-soluble film in an amount in a range of 13 wt. % to 39 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film;
the second plasticizer is present in the water-soluble film in an amount in a range of 22 wt. % to 38 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film; and
the third plasticizer is present in the water-soluble film in an amount in a range of 39 wt. % to 64 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film.
19. The water-soluble film of claim 1 , wherein:
the first plasticizer is present in the water-soluble film in an amount in a range of 13 wt. % to 19 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film;
the second plasticizer is present in the water-soluble film in an amount in a range of 41 wt. % to 52 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film; and
the third plasticizer is present in the water-soluble film in an amount in a range of 35 wt. % to 44 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film.
20. The water-soluble film of claim 1 , wherein the water-soluble film has at least two of the three properties (a), (b), and (c):
(a) an aged melting transition delta elevation of 12° C. or less as measured by the Aged Melting Transition Delta Test;
(b) an aged adhesion value of at least 1300 g/s as measured by the Aged Adhesion Test; and
(c) an aged tensile strength of at least 25 MPa as measured by the Aged Tensile Strength Test.
21. The water-soluble film of claim 1 , wherein the water-soluble film has at least two of the three properties (a), (b), and (c):
(a) an aged melting transition delta elevation of 11° C. or less as measured by the Aged Melting Transition Delta Test;
(b) an aged adhesion value of at least 2500 g/s as measured by the Aged Adhesion Test; and
(c) an aged tensile strength of at least 32.5 MPa as measured by the Aged Tensile Strength Test.
22. The water-soluble film of claim 20 , wherein the water-soluble film has all three of the properties (a), (b), and (c).
23. The water-soluble film of claim 1 , wherein the water-soluble film further comprises one or more components selected from the group consisting of plasticizers other than the first, second, and third plasticizers, plasticizer compatibilizers, lubricants, release agents, fillers, extenders, cross-linking agents, antiblocking agents, antioxidants, detackifying agents, antifoams, nanoparticles, bleaching agents, surfactants, and combinations thereof.
24. The water-soluble film of claim 1 , wherein the PVOH polymer comprises a PVOH homopolymer consisting essentially of vinyl alcohol monomer units and optionally vinyl acetate monomer units.
25. The water-soluble film of claim 1 , wherein the PVOH polymer comprises a PVOH copolymer comprising an anionic monomer unit, a vinyl alcohol monomer unit, and optionally a vinyl acetate monomer unit.
26. The water-soluble film of claim 25 , wherein the anionic monomer is selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anyhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anyhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the foregoing, esters of the foregoing, and combinations thereof.
27. The water-soluble film of claim 25 , wherein the anionic monomer is selected from the group consisting of acrylamido methylpropanesulfonic acids, alkali metal salts thereof, and combinations thereof.
28. The water-soluble film of claim 25 , wherein the anionic monomer is selected from the group consisting of monomethyl maleate, alkali metal salts thereof, and combinations thereof.
29. The water-soluble film of claim 1 , wherein the PVOH polymer comprises a polymer blend comprising two or more different PVOH homopolymers.
30. The water-soluble film of claim 1 , wherein the PVOH polymer comprises a polymer blend comprising two or more different PVOH copolymers.
31. The water-soluble film of claim 30 , wherein the polymer blend comprises a first PVOH copolymer comprising a first anionic monomer unit, and a second PVOH copolymer comprising a second anionic monomer unit different from the first anionic monomer unit.
32. The water-soluble film of claim 31 , wherein:
the first anionic monomer is selected from the group consisting of acrylamido methylpropanesulfonic acids, alkali metal salts thereof, and combinations thereof; and
the second anionic monomer is selected from the group consisting of monomethyl maleate, alkali metal salts thereof, and combinations thereof.
33. The water-soluble film of claim 32 , wherein:
the first PVOH copolymer is present in an amount in a range of 10 wt. % to 80 wt. % of total PVOH polymers in the film; and
the second PVOH copolymer is present in an amount in a range of 20 wt. % to 90 wt. % of total PVOH polymers in the film.
34. The water-soluble film of claim 1 , wherein the PVOH polymer has a degree of hydrolysis in a range of 75% to 99%.
35. The water-soluble film of claim 1 , wherein the PVOH polymer has a 4% solution viscosity at 20° C. in a range of 4 cP to 24 cP.
36. The water-soluble film of claim 1 , wherein the water-soluble film further comprises a water-soluble polymer which is other than a PVOH polymer.
37. The water-soluble film of claim 36 , wherein the water-soluble polymer is selected from the group consisting of polyethyleneimines, polyvinyl pyrrolidones, polyalkylene oxides, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polyamides, gelatines, methylcelluloses, carboxymethylcelluloses and salts thereof, dextrins, ethylcelluloses, hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins, starches, modified starches, guar gum, gum Acacia, xanthan gum, carrageenan, polyacrylates and salts thereof, copolymers thereof, blends thereof, and combinations thereof.
38. An article comprising:
a water-soluble film of claim 1 comprising a first surface of said film solvent-sealed to a second surface of the same film or to a surface of a second film of claim 1 .
39. An article comprising:
a water-soluble film of claim 1 in the form of a pouch defining an interior pouch volume.
40. The article of claim 39 , further comprising a composition contained in the interior pouch volume.
41. A water-soluble film comprising:
a polyvinyl alcohol (PVOH) polymer;
dipropylene glycol as a first plasticizer;
a sugar alcohol as a second plasticizer; and
a polyol as a third plasticizer, the third plasticizer being different from the first plasticizer and the second plasticizer;
wherein:
the first plasticizer is present in the water-soluble film in an amount in a range of 10 wt. % to 65 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film;
the second plasticizer is present in the water-soluble film in an amount in a range of 10 wt. % to 65 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film;
the third plasticizer is present in the water-soluble film in an amount in a range of 25 wt. % to 80 wt. % relative to the combined amount of the first, second, and third plasticizers in the water-soluble film;
the first, second, and third plasticizers are present in the water-soluble film in a combined amount in a range of 10 phr to 40 phr; and
the water-soluble film has all three properties (a), (b), and (c):
(a) an aged melting transition delta elevation of 12° C. or less as measured by the Aged Melting Transition Delta Test,
(b) an aged adhesion value of at least 1300 g/s as measured by the Aged Adhesion Test, and
(c) an aged tensile strength of at least 25 MPa as measured by the Aged Tensile Strength Test.
42. The water-soluble film of claim 41 , wherein:
the second plasticizer comprises sorbitol; and
the third plasticizer comprises glycerin.