Starch Extrusion Film / Adhesive and Method

Abstract

The present disclosure is directed to a continuous, low shear process for compounding and starch. In one aspect of the disclosure, the starch can be applied directly as a web, film, or layer, for example, in a tape product.

Description

[Technical Field]

[0001] The present disclosure is directed to a continuous, low shear process for the incorporation of starch and the production of films and / or adhesives and products therefrom. In one aspect of the disclosure, the starch can be applied directly as a sheet or film in a tape product. [Background technology]

[0002] Conventional tapes and adhesives (and combinations thereof), as well as packaging materials such as air cushions, may be made from or contain significant amounts of polyolefins, which are often petroleum-based polyolefins. Due to environmental concerns regarding greenhouse gas emissions and a high reliance on depleting petroleum-based resources, with the changing global trends facing most industries, a strong sustainability strategy is desired to create better tapes and adhesives, such as air cushions, tapes, and their adhesives that are compostable, renewable, and / or repulpable. Summary of the Invention

[0003] In one example, a tape is provided that includes a repulpable backing having a first major surface and an opposing second major surface, a repulpable reinforcement adjacent to the second major surface, and an adhesive layer adjacent to the repulpable reinforcement. In one aspect, alone or in combination with any one of the previous aspects, the tape is dissolvable in at least 80, at least 85, or at least 90 weight percent hot water or repulpable under pulping conditions, for example, in the FBA process discussed below.

[0004] In one aspect, the repulpable backing consists essentially of cellulose. In one aspect, alone or in combination with any one of the preceding aspects, the repulpable backing is paper. In one aspect, alone or in combination with any one of the preceding aspects, the repulpable backing is kraft paper.

[0005] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcement is directly adjacent to the repulpable backing. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable backing is extrusion laminated to the repulpable reinforcement. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable backing is adhesively laminated to the repulpable reinforcement. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable backing is adhesively laminated to the repulpable reinforcement without an adhesive. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable backing is extrusion laminated to the repulpable reinforcement without an adhesive.

[0006] In one aspect, alone or in combination with any one of the preceding aspects, the tape further comprises an optional paper layer positioned between the repulpable reinforcement and the adhesive. In one aspect, alone or in combination with any one of the preceding aspects, the paper layer and the repulpable backing are the same or different.

[0007] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises unmodified starch, modified starch, synthetic starch, crosslinked starch, or a mixture of two or more thereof. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material is a film, web, or scrim comprising unmodified starch, modified starch, synthetic starch, crosslinked starch, or a mixture of two or more thereof. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material is soluble in at least 90 weight percent hot water, e.g., 115-140°F (46-60°C), or repulpable under pulping conditions.

[0008] In one aspect, alone or in combination with any one of the preceding aspects, the repulpable reinforcement material comprises unmodified, modified, synthetic, or cross-linked starch derived from cassava, corn, potato, sweet potato, sago, tapioca, sorghum, bean, bracken, lotus, water chestnut, wheat, rice, oat, arrowroot, dent, or pea.

[0009] In one aspect, alone or in combination with any one of the preceding aspects, the repulpable reinforcing material comprises unmodified, modified, synthetic, or crosslinked starch derived from glutinous rice, waxy potato starch, and waxy corn.

[0010] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material is an extruded web, film, or layer. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises starch, modified starch, synthetic starch, thermoplastic starch, or a combination thereof.

[0011] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a starch having a total weight ratio of amylose to amylopectin of 10:90 to 90:10. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a modified starch having a total weight ratio of amylose to amylopectin of 40:60 to 0:100. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a synthetic starch having a total weight ratio of amylose to amylopectin of 40:60 to 0:100. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a thermoplastic starch having a total weight ratio of amylose to amylopectin of 40:60 to 0:100.

[0012] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcement material comprises a blend of starches having a total weight ratio of amylose to amylopectin of from 40:60 to 0:100, wherein the blend of starches comprises unmodified starch, modified starch, synthetic starch, thermoplastic starch, or combinations thereof.

[0013] In one aspect, alone or in combination with any one of the preceding aspects, the repulpable reinforcement material comprises a blend of starches comprising a first starch having an amylose to amylopectin weight ratio of from 40:60 to 0:100 in combination with a second starch having an amylose to amylopectin weight ratio of from 40:60 to 0:100, wherein at least one of the first starch and the second starch is independently unmodified, modified, synthetic, or crosslinked.

[0014] In one aspect, alone or in combination with any one of the preceding aspects, the weight ratio of starch to water-soluble material is from 50:1 to 1:50. In one aspect, alone or in combination with any one of the preceding aspects, the one or more repulpable materials are polyvinyl alcohol or polyvinyl alcohol copolymers and salts thereof, polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxides, polyhydroxyalkanoates, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polyamides, poly(meth)acrylic acid, poly(meth)acrylates and salts thereof, gelatin, methylcellulose, carboxymethylcellulose, microfibrillated cellulose, nanofibrillated cellulose, and blends and / or salts thereof, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, natural and synthetic sugar alcohols, dextrin, maltodextrin, guar gum, acacia gum, gum arabic, xanthan gum, carrageenan, algin, locust bean, gellan, copolymers thereof, blends thereof, and combinations thereof.

[0015] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a starch or modified starch in combination with polyvinyl alcohol or a polyvinyl alcohol copolymer. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a starch or modified starch in combination with polyvinyl alcohol having a degree of saponification of 80 to 99.8 mol%.

[0016] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a starch or modified starch in combination with a polyvinyl alcohol copolymer comprising one or more anionic monomers.

[0017] In one aspect, alone or in combination with any one of the preceding aspects, the one or more anionic monomers are independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleates, dialkyl maleates, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, 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.

[0018] In one embodiment, alone or in combination with any one of the preceding embodiments, the tape further comprises one or more components selected from the group consisting of plasticizers, plasticizer compatibilizers, lubricants, release agents, fillers, extenders, impact modifiers, crosslinkers, antiblocking agents, antioxidants, antiblocking agents, antifoaming agents, nanoparticles, bleaching agents, surfactants, biocides, and combinations or reaction products thereof. In one example, the filler includes microfibrillated cellulose, nanofibrillated cellulose, and mixtures thereof in any proportion.

[0019] In one embodiment, alone or in combination with any one of the preceding embodiments, the adhesive layer is a water-activated adhesive. In one embodiment, alone or in combination with any one of the preceding embodiments, the water-activated adhesive is directly adjacent to the repulpable reinforcement material.

[0020] In one embodiment, alone or in combination with any one of the preceding embodiments, the tape further includes a paper layer between the repulpable reinforcement and the adhesive. In one embodiment, alone or in combination with any one of the preceding embodiments, the water-activated adhesive is directly adjacent to the paper layer. In one embodiment, alone or in combination with any one of the preceding embodiments, the paper layer and the repulpable backing are the same or different.

[0021] In one aspect, alone or in combination with any one of the preceding aspects, the water-activated adhesive is a polyvinyl acetate emulsion adhesive, a polyethylene vinyl acetate adhesive, a poly(meth)acrylic or poly(meth)acrylic emulsion adhesive, a starch-based adhesive, or a combination or laminate thereof.

[0022] In one embodiment, alone or in combination with any one of the preceding embodiments, the water-activated adhesive is a starch-based adhesive. In one embodiment, alone or in combination with any one of the preceding embodiments, the water-activated adhesive is a starch-based adhesive in combination with an acrylamide-based adhesive or an acrylic-based adhesive. In one embodiment, alone or in combination with any one of the preceding embodiments, the water-activated adhesive includes a filler.

[0023] In one aspect, alone or in combination with any one of the preceding aspects, the adhesive layer is a pressure sensitive adhesive.

[0024] In one aspect, alone or in combination with any one of the preceding aspects, the adhesive is foamed.In one aspect, alone or in combination with any one of the preceding aspects, the tape is disposed in a roll.

[0025] In one example, a method for producing a tape is provided, comprising continuously or semi-continuously mixing a quantity of starch and an additive amount of water with a repulpable material while heating in a low shear extruder or mixing device to obtain a mixture, continuously or semi-continuously extruding the mixture, and cooling the mixture.

[0026] In one embodiment, the method further comprises preconditioning the starch prior to heating in the low shear extruder.

[0027] In one embodiment, the method further includes continuously producing a film from the mixture and contacting the film with a second major surface of a repulpable backing.

[0028] In one embodiment, alone or in combination with any one of the preceding embodiments, the high solids continuous or semi-continuous mixing is a high solids content mix of starch, the high solids comprising 25 weight percent to 75 weight percent starch. In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises applying the adhesive composition adjacent to the repulpable reinforcement material. In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises applying the adhesive composition directly adjacent to the repulpable reinforcement material.

[0029] In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises frothing the adhesive. In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises forming pellets from the mixture.

[0030] In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises remelting the pellets into a melt, producing a film from the melt, and extrusion laminating the film to the second major surface of a repulpable backing.

[0031] In one embodiment, alone or in combination with any one of the preceding embodiments, the method further includes remelting the pellets into a melt, producing a film from the melt, extrusion laminating the film to a second major surface of a repulpable backing, and applying the adhesive composition adjacent to the repulpable reinforcement material.

[0032] In one embodiment, alone or in combination with any one of the preceding embodiments, the total amount of water in a state added is 10 to 50% by weight of the mixture. In one embodiment, alone or in combination with any one of the preceding embodiments, the water in a state is liquid, vapor, or a combination of liquid and vapor.

[0033] In one embodiment, alone or in combination with any one of the preceding embodiments, heating during mixing is carried out at a temperature of less than 200°C, or less than 210°C.

[0034] In one embodiment, alone or in combination with any one of the preceding embodiments, the contacting of the film with the second major surface of the repulpable backing is continuous. In one embodiment, alone or in combination with any one of the preceding embodiments, the mixture is extruded as a continuous web, film, or layer. In one embodiment, alone or in combination with any one of the preceding embodiments, the melt is extruded using a spinneret die, a slot die, an annular die, a coextrusion die, or a combination thereof.

[0035] In one embodiment, alone or in combination with any one of the preceding embodiments, the melt is adhesively laminated to a repulpable backing before or after cooling. In one embodiment, alone or in combination with any one of the preceding embodiments, the adhesive composition is applied to the repulpable reinforcement material as a continuous web, sheet, or layer. In one embodiment, alone or in combination with any one of the preceding embodiments, the adhesive composition is applied to the repulpable reinforcement material using a spinneret die, a slot die coater, a curtain coater, a rotor damper coater, a reverse roll, roll-over-roll coating, and a knife-over-roll coating. In one embodiment, alone or in combination with any one of the preceding embodiments, the adhesive composition is applied randomly or in a pattern.

[0036] In one embodiment, alone or in combination with any one of the preceding embodiments, the method further includes adding a secondary material to the mixture. In one embodiment, alone or in combination with any one of the preceding embodiments, the secondary material includes a solid raw material selected from the group consisting of impact modifiers, tackifying resins, extenders, activators, crosslinkers, colorants, recycled waste plastics, regenerated cellulose materials, microfibrillated cellulose, nanofibrillated cellulose, clays such as bentonite, and mixtures thereof in any proportion. In one embodiment, alone or in combination with any one of the preceding embodiments, the secondary material includes recycled material. In one embodiment, alone or in combination with any one of the preceding embodiments, the secondary material further includes an activator selected from the group consisting of zinc oxide, azides, epoxides, sodium tetraborate, magnesium oxide, and combinations thereof, and a extender selected from the group consisting of clay, calcium carbonate, talc, aluminum hydrate, and combinations thereof.

[0037] In one aspect, alone or in combination with any one of the preceding aspects, the repulpable backing is paper. In one aspect, alone or in combination with any one of the preceding aspects, the repulpable backing is kraft paper.

[0038] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable backing is adhesively laminated to the repulpable reinforcement. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable backing is extrusion laminated to the repulpable reinforcement. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable backing is extrusion laminated to the repulpable reinforcement without adhesive.

[0039] In one aspect, alone or in combination with any one of the preceding aspects, the repulpable reinforcing material is soluble in at least 90 weight percent hot water after cooling or repulpable under pulping conditions.

[0040] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises modified starch or synthetic starch. In one embodiment, alone or in combination with any one of the preceding embodiments, the modified starch is one in which the modified starch has been epoxidized, alkylated, carboxylated, carboxymethylated, alkylacetylated, alkali-modified, acid-modified, bleached, oxidized, enzyme-treated, phosphorylated, phosphorylated, hydroxyalkylated, borax-treated, urea-treated, urea-formaldehyde-treated, resorcinol-formaldehyde-treated, heat-treated, dry-heat-treated, or enzyme-treated, or dextrinized.

[0041] In one aspect, alone or in combination with any one of the preceding aspects, the modified starch is a thermoplastic starch.

[0042] In one aspect, alone or in combination with any one of the preceding aspects, the repulpable reinforcement material comprises starch derived from cassava, corn, potato, sweet potato, sago, tapioca, sorghum, bean, bracken, lotus, water chestnut, wheat, rice, oat, arrowroot, dent, or pea. In one aspect, alone or in combination with any one of the preceding aspects, the repulpable reinforcement material comprises glutinous rice, waxy potato starch, and waxy corn.

[0043] In one embodiment, alone or in combination with any one of the preceding embodiments, the starch comprises a blend of starches having a total weight ratio of amylose to amylopectin of from 40:60 to 0:100. In one embodiment, alone or in combination with any one of the preceding embodiments, the starch comprises a modified starch having a total weight ratio of amylose to amylopectin of from 40:60 to 0:100. In one embodiment, alone or in combination with any one of the preceding embodiments, the starch is a blend of modified starches having a total weight ratio of amylose to amylopectin of from 40:60 to 0:100. In one aspect, alone or in combination with any one of the preceding aspects, the starch comprises a combination of a first starch having an amylose to amylopectin weight ratio of from 40:60 to 0:100 and a second starch having an amylose to amylopectin weight ratio of from 40:60 to 0:100, wherein at least one of the first starch and the second starch is independently unmodified, modified, synthetic, or cross-linked.

[0044] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcement material comprises starch or modified starch in combination with one or more repulpable materials. In one embodiment, alone or in combination with any one of the preceding embodiments, the water in the film is 2 to 25 weight percent after drying.

[0045] In one aspect, alone or in combination with any one of the preceding aspects, the weight ratio of starch to water-soluble material is from 50:1 to 1:50.

[0046] In one aspect, alone or in combination with any one of the preceding aspects, the repulpable material is polyvinyl alcohol or polyvinyl alcohol copolymers and salts thereof, polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxides, polyhydroxyalkanoates, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polyamides, gelatin, poly(meth)acrylic acid, poly(meth)acrylates and salts thereof, methylcellulose, carboxymethylcellulose and salts thereof, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, microfibrillated cellulose, modified microfibrillated cellulose, nanofibrillated cellulose, modified nanofibrillated cellulose, sugar alcohols, dextrin, maltodextrin, guar gum, acacia gum, gum arabic, xanthan gum, carrageenan, algin, locust bean, gellan, copolymers thereof, blends thereof, and combinations thereof.

[0047] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a starch or modified starch in combination with polyvinyl alcohol or a polyvinyl alcohol copolymer. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a starch or modified starch in combination with polyvinyl alcohol and a polyvinyl alcohol copolymer. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a starch and modified starch in combination with polyvinyl alcohol and a polyvinyl alcohol copolymer. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises a starch or modified starch in combination with polyvinyl alcohol or a polyvinyl alcohol copolymer having a saponification degree of 80 to 99.8 mol %.

[0048] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable reinforcing material comprises starch and / or modified starch in combination with polyvinyl alcohol and / or polyvinyl alcohol copolymers comprising one or more anionic monomers. In one aspect, alone or in combination with any one of the preceding aspects, the one or more anionic monomers are independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleates, dialkyl maleates, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, 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.

[0049] In one aspect, alone or in combination with any one of the preceding aspects, the method further includes including one or more ingredients selected from the group consisting of impact modifiers, plasticizers, plasticizer compatibilizers, lubricants, release agents, fillers, microfibrillated cellulose, modified microfibrillated cellulose, nanofibrillated cellulose, modified nanofibrillated cellulose, sugar alcohols, dextrins, maltodextrins, clays, biocides, wetting agents, bulking agents, crosslinking agents, antiblocking agents, antioxidants, anti-blocking agents, antifoaming agents, nanoparticles, bleaching agents, surfactants, and combinations or reaction products thereof.

[0050] In one aspect, alone or in combination with any one of the preceding aspects, the adhesive layer is a water-activated adhesive. In one aspect, alone or in combination with any one of the preceding aspects, the method further includes introducing an optional repulpable layer between the repulpable reinforcement material and the adhesive. In one aspect, alone or in combination with any one of the preceding aspects, the water-activated adhesive is directly adjacent to the repulpable reinforcement material. In one aspect, alone or in combination with any one of the preceding aspects, the paper layer and the repulpable backing are the same or different.

[0051] In one aspect, alone or in combination with any one of the preceding aspects, the water-activated adhesive is a polyvinyl acetate emulsion adhesive, a polyethylene vinyl acetate adhesive, a polyacrylic emulsion adhesive or a poly(meth)acrylic emulsion adhesive, a starch-based adhesive, or a combination or laminate thereof.

[0052] In one embodiment, alone or in combination with any one of the preceding embodiments, the water-activated adhesive is a starch-based adhesive. In one embodiment, alone or in combination with any one of the preceding embodiments, the adhesive layer is a pressure-sensitive adhesive.

[0053] In one embodiment, alone or in combination with any one of the preceding embodiments, the water-activated adhesive includes a filler. In one embodiment, alone or in combination with any one of the preceding embodiments, the adhesive is foamed.

[0054] In one embodiment, alone or in combination with any one of the preceding embodiments, the average molecular weight of the starch is reduced by less than 50% as measured by GPC or viscosity. In one embodiment, alone or in combination with any one of the preceding embodiments, the average molecular weight of the starch is reduced by less than 20% as measured by GPC. In one embodiment, alone or in combination with any one of the preceding embodiments, the average molecular weight of the starch is reduced by less than 10% as measured by GPC.

[0055] In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises crosslinking the adhesive composition. In one embodiment, alone or in combination with any one of the preceding embodiments, crosslinking the adhesive composition uses a process selected from the group consisting of EB crosslinking, UV crosslinking, thermal and / or chemical crosslinking, and combinations thereof.

[0056] In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises contacting the film of the composition with a paper backing. In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises applying an adhesive to the film of the composition. In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises incorporating an optional repulpable layer into the film of the composition. In one embodiment, alone or in combination with any one of the preceding embodiments, the method further comprises applying an adhesive to the paper layer.

[0057] In another example, a film is provided that includes a starch and an amount of a repulpable material.

[0058] In one embodiment, the starch film is soluble in at least 90 weight percent hot water or repulpable under pulping conditions, e.g., by the FBA process. In one embodiment, alone or in combination with any one of the preceding embodiments, the starch present in the film is alkyl-etherified starch, carboxyalkyl-etherified starch, hydroxyalkyl-etherified starch having a hydroxyalkyl group having 2 to 6 carbon atoms, and synthetic starch. In one embodiment, alone or in combination with any one of the preceding embodiments, the starch present in the film is thermoplastic starch.

[0059] In one aspect, alone or in combination with any one of the preceding aspects, the starch present in the film is derived from cassava, corn, potato, sweet potato, sago, tapioca, sorghum, bean, bracken, lotus, water chestnut, wheat, rice, oat, arrowroot, dent, or pea. In one aspect, alone or in combination with any one of the preceding aspects, the starch present in the film is waxy rice, waxy potato starch, and waxy corn.

[0060] In one embodiment, alone or in combination with any one of the preceding embodiments, the starch comprises an amylose to amylopectin weight ratio of 10:90 to 90:10. In one embodiment, alone or in combination with any one of the preceding embodiments, the starch comprises a blend of starches having a total amylose to amylopectin weight ratio of 10:90 to 90:10.

[0061] In one aspect, alone or in combination with any one of the preceding aspects, the starch comprises a modified starch having a total weight ratio of amylose to amylopectin of from 40:60 to 0:100. In one aspect, alone or in combination with any one of the preceding aspects, the starch is a blend of modified starches having a total weight ratio of amylose to amylopectin of from 40:60 to 0:100. In one aspect, alone or in combination with any one of the preceding aspects, the starch comprises a combination of a first starch having an amylose to amylopectin weight ratio of from 40:60 to 0:100 and a second starch having an amylose to amylopectin weight ratio of from 40:60 to 0:100, wherein at least one of the first starch and the second starch is independently unmodified, modified, synthetic, or crosslinked.

[0062] In one aspect, alone or in combination with any one of the preceding aspects, the repulpable material is polyvinyl alcohol or polyvinyl alcohol copolymers and salts thereof, polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxides, polyhydroxyalkanoates, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polyamides, gelatin, poly(meth)acrylic acid, poly(meth)acrylates and salts thereof, methylcellulose, carboxymethylcellulose and salts thereof, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, microfibrillated cellulose, modified microfibrillated cellulose, nanofibrillated cellulose, modified nanofibrillated cellulose, sugar alcohols, dextrin, maltodextrin, clays, biocides, humectants, dextrin, maltodextrin, guar gum, acacia gum, gum arabic, xanthan gum, carrageenan, copolymers thereof, blends thereof, and combinations thereof.

[0063] In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable material is polyvinyl alcohol or a polyvinyl alcohol copolymer. In one embodiment, alone or in combination with any one of the preceding embodiments, the repulpable material is polyvinyl alcohol in combination with a polyvinyl alcohol copolymer. In one embodiment, alone or in combination with any one of the preceding embodiments, the polyvinyl alcohol has a degree of saponification of 80 to 99.8 mol%.

[0064] In one embodiment, alone or in combination with any one of the preceding embodiments, the polyvinyl alcohol copolymer comprises one or more anionic monomers. In one embodiment, alone or in combination with any one of the preceding embodiments, the one or more anionic monomers are independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleates, dialkyl maleates, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, 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.

[0065] In one embodiment, alone or in combination with any one of the preceding embodiments, the film further comprises one or more ingredients selected from the group consisting of impact modifiers, plasticizers, plasticizer compatibilizers, lubricants, release agents, fillers, microfibrillated cellulose, modified microfibrillated cellulose, nanofibrillated cellulose, modified nanofibrillated cellulose, sugar alcohols, dextrins, maltodextrins, clays, biocides, wetting agents, bulking agents, crosslinking agents, antiblocking agents, antioxidants, anti-blocking agents, antifoaming agents, nanoparticles, bleaching agents, surfactants, and combinations or reaction products thereof.

[0066] In one embodiment, alone or in combination with any one of the preceding embodiments, the weight ratio of starch to repulpable material is from 50:1 to 1:50.

[0067] In another example, a process is provided for producing a starch film composition, the process comprising continuously or semi-continuously metering a starch film composition comprising starch, modified starch, thermoplastic starch, or a combination thereof, water in a state, and a repulpable material into a low shear extrusion device, such as a planetary roller extruder; continuously mixing the composition in a compounding section of the low shear extrusion device; and continuously discharging the starch film from the extruder.

[0068] In one aspect, the compounding section includes multiple roller barrel sections. In one aspect, alone or in combination with any one of the preceding aspects, each roller barrel section includes multiple mixing spindles.

[0069] In one embodiment, alone or in combination with any one of the preceding embodiments, the process further comprises adding water in a state to the composition in the blending section. In one embodiment, alone or in combination with any one of the preceding embodiments, the water in a state is liquid, steam, or a combination of liquid and steam. In one example, the starch is preconditioned.

[0070] In one aspect, alone or in combination with any one of the preceding aspects, the process further includes adding a secondary ingredient to the compounding section. In one aspect, alone or in combination with any one of the preceding aspects, the secondary ingredient includes a solid, liquid, or gaseous material. In one aspect, alone or in combination with any one of the preceding aspects, the solid material is selected from the group consisting of a thermoplastic elastomer, a resin, a filler, an activator, an antidegradant, a biocide, a humectant, a foaming agent, a crosslinker, and mixtures thereof.

[0071] In one embodiment, alone or in combination with any one of the preceding embodiments, the blending section further comprises a dosing unit, and the solid material is added to the blending section via the dosing unit. In order to see and understand how the present disclosure may be carried into practice, examples will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which: [Brief explanation of the drawings]

[0072] [Figure 1A] FIG. 1 is a perspective view of a roll of tape according to one embodiment of the present disclosure. [Figure 1B] 2 is an enlarged cross-sectional view of the tape of FIG. 1A illustrating these layers along line 2-2 of FIG. 1A. [Figure 2A] FIG. 1 is a perspective view of a roll of tape according to one embodiment of the present disclosure. [Figure 2B] 3 is an enlarged cross-sectional view of the tape of FIG. 2A illustrating these layers along line 3-3 of FIG. 2A. [Figure 3A] FIG. 1 is a perspective view of a roll of tape according to one embodiment of the present disclosure. [Figure 3B] 4 is an enlarged cross-sectional view of the tape of FIG. 3A illustrating these layers along line 4-4 of FIG. 3A. [Figure 4] FIG. 1 is a longitudinal cross-sectional view of a low shear extrusion apparatus according to one embodiment of the present disclosure. [Figure 5] FIG. 1 is a close-up view of an exemplary dual transverse mixing spindle. [Figure 6] FIG. 5 is a cross-sectional view of a dosing ring from the low shear extrusion apparatus of FIG. [Figure 7] FIG. 1 is a cross-sectional view of a slot die coater. [Figure 8] 1 is a longitudinal cross-sectional view of an exemplary low shear extrusion apparatus and slot die coater according to one aspect of the present invention. [Figure 9] 6 is a cross-sectional view of the exemplary low shear extrusion apparatus of FIG. 1 taken along line 6-6. DETAILED DESCRIPTION OF THE INVENTION

[0073] The present disclosure provides for the formulation and / or extrusion of starch-containing films.

[0074] In one aspect, the present disclosure provides for blending and / or extruding starches that are essentially free or free of amylose. In one aspect, the present disclosure provides for blending and / or extruding starches that are less than 40 weight percent amylose, less than 30 weight percent amylose, less than 20 weight percent amylose, less than 10 weight percent amylose, less than 9 weight percent amylose, less than 8 weight percent amylose, less than 7 weight percent amylose, less than 6 weight percent amylose, less than 5 weight percent amylose, less than 4 weight percent amylose, less than 3 weight percent amylose, less than 2 weight percent amylose, less than 1 weight percent amylose (essentially all amylopectin).

[0075] In one aspect, the present disclosure provides compounding and / or extrusion of high amylopectin content, alone or with other adjuvants, processed to substantially maintain the molecular weight and branching of the amylopectin. Compounding / extrusion applications of such starch materials can be applied to packaging applications, such as providing a robust film capable of reinforcing water-activated tape (WAT) tapes, and to providing films for use as stretch films, shrink films, duct tape backings, polyolefin tapes, air pillows / cushions, and bubble wrap for use by themselves or within shipping containers. Additionally, compounding / extrusion applications of such starch materials and film or sheet preparation are suitable for small pouches, such as those currently used in seasoning, health / hygiene, and detergent pods. In addition, compounding / extrusion applications of such starch materials can be employed to address water sensitivity requirements for certain applications by balancing the amylose / amylopectin ratio and / or by controlling the molecular weight change and / or branching of the starch during compounding and / or extrusion.

[0076] Such starch films / sheets disclosed herein are useful for providing a substrate for receiving CVD / PVD SiOx and / or AlOx coatings with improved air / water barrier properties. Such starch materials disclosed herein are configured to receive paints or varnishes. Such starch films / sheets disclosed herein may include plasticizers, fillers, other polymers, biocides, humectants, UV stabilizers, etc.

[0077] In one example, starch compositions and products made therefrom are provided that are produced using a low shear extrusion device, providing sustainable or renewable and / or repulpable products that can be used alone or in combination with sustainable or renewable and / or repulpable packaging.

[0078] As used herein, the phrase "water-activated adhesive" includes adhesives that are generally non-adhesive when dry and become adhesive upon exposure to an aqueous medium, which includes water and optionally other solvents such as alcohol.

[0079] As used herein, the phrase "water in some form" includes water in its solid, liquid, or gas and / or vapor form. Water in some form may contain additional solvents such as alcohols and other unintended impurities.

[0080] As used herein, "starch" and "starch comprising" include any synthetic or vegetable starch, or blends thereof, and combinations, blends, or grafts with one or more polymers. As used herein, "vegetable starch" is starch isolated, derived, and / or purified by any means from any vegetable source. In one example, the vegetable starch is derived from or obtained from, but is not limited to, cassava, corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, pea, and / or potato. Other sources of vegetable and non-vegetable starch can be employed.

[0081] As used herein, synthetic starch includes "modified vegetable starch," e.g., any vegetable starch that has been chemically, genetically, enzymatically, mechanically, and / or thermally modified. As used herein, synthetic starch also includes non-vegetable starches, e.g., starches prepared from carbon dioxide.

[0082] As used herein, "modified starch" includes starches that have been alkylated, carboxylated, carboxymethylated, alkylacetylated, alkali-modified, bleached, oxidized, enzyme-treated, phosphorylated, phosphorylated, hydroxyalkylated, borax-treated, urea-treated, urea-formaldehyde-treated, resorcinol-formaldehyde-treated, heat-treated, dry-heated, acid- or enzyme-thinned, or dextrinized.

[0083] As used herein, the term "repulpable" includes the 2013 Fibre Box Association Voluntary Standard for the Repulping and Regeneration of Corrugated Board Treated to Improve Performance in the Presence of Water and Steam (the "FBA Method").

[0084] As used herein, "repulpable material" includes polyvinyl alcohol or polyvinyl alcohol copolymers and salts thereof, polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxides, polyhydroxyalkanoates, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polyamides, poly(meth)acrylic acid, poly(meth)acrylates and salts thereof, gelatin, methylcellulose, carboxymethylcellulose and salts thereof, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, dextrin, maltodextrin, guar gum, acacia gum, gum arabic, xanthan gum, carrageenan, algin, locust bean, gellan, copolymers thereof, blends thereof, carbohydrates, proteins, lipids, triglycerides, and phospholipids, alone or in combination with any of the foregoing.

[0085] Non-limiting examples of low-shear extrusion equipment include planetary roller extruders (PREs), planetary roller mixers, twin-screw extruders configured with counter-rotating or co-rotating, intermeshing or non-intermeshing screws, and static mixing devices. PREs are typically used to process thermoplastics such as PVC, primarily to feed downstream units such as cast or blown film devices, glossers, or roll mills. Planetary roller extruders can be used, for example, to process heat-sensitive compounds with minimal degradation by exposing a thin layer of compound to a large surface area, thereby facilitating effective heat exchange, mixing, and temperature control. Planetary roller extruders are available in a variety of designs and sizes. The diameter of the roll cylinder is typically 30 mm to 1000 mm, or 70 mm to 500 mm, depending on the desired throughput.

[0086] Planetary roller extruders generally have a filling section and a compounding section. The filling section typically includes a conveying screw through which certain raw materials are continuously fed. The conveying screw then sends the material to the compounding section. The compounding section includes a driven main spindle and several planetary spindles that rotate around the main spindle within roll cylinders with internal helical gears. The rotational speed of the main spindle, and therefore the planetary spindles, can be varied and is one parameter controlled during the compounding process. The material is circulated between the main spindle and the planetary spindles, or between the planetary spindles and the helical gears of the roll section, to disperse the material and form a homogeneous composition.

[0087] The number of planetary spindles rotating within each roll cylinder can be varied and therefore adapted to the process requirements. The number of spindles affects the free volume within the planetary roller extruder, the residence time of the material in the process, and also determines the surface area for heat and material exchange. Due to the introduced dispersion energy, the number, geometry, and / or configuration of the planetary spindles influences the compounding results. Given a fixed diameter of the roll cylinder, a higher number of spindles allows for better homogenization and dispersion, or a higher product throughput.

[0088] The maximum number of planetary spindles that can be installed between the main spindle and the roll cylinder depends on the diameter of the roll cylinder and the diameter of the planetary spindles used. When using a relatively large barrel diameter, such as required to achieve production-scale throughput, and / or a relatively small diameter planetary spindle, the roll cylinder can be equipped with a relatively large number of planetary spindles. For example, with a barrel diameter of D=70 mm, a maximum of seven planetary spindles are typically used, whereas, for example, ten planetary spindles can be used with a barrel diameter of D=200 mm, and twenty-four planetary spindles can be used with a barrel diameter of D=400 mm. However, these examples are not intended to limit the scope of the art. For example, for larger main spindles, the number of planetary spindles can be increased if the main spindle diameter is smaller. Similarly, for larger main spindles, the number of planetary spindles can be decreased if the main spindle diameter is larger.

[0089] Referring now to the drawings, and initially to FIG. 1A , a roll 200 of tape 130 wound onto a core 118, the roll essentially comprising a paper backing 124 and a starch-containing stiffening material 122. For illustrative purposes, and referring to FIGS. 1A and 1B from top to bottom relative to the page, the tape 130 includes a paper backing 124. The paper backing 124 (also referred to as a substrate) has a first major (top) surface 132, a second major (bottom) surface 134, and first and second sides. As shown, applied to the bottom surface 134 of the backing 124 is a starch-containing stiffening material 122. The starch-containing stiffening material 122 is configured to function as an adhesive, e.g., a water-activated adhesive. For example, the starch-containing stiffening material 122 can be activated prior to use using an aqueous medium, such as water or water and alcohol. In one example, the starch-containing reinforcement material 122 is a film, web, scrim, or layer.

[0090] Referring to FIG. 2A , a roll 300 of tape 130 is shown wound onto a core 118, the roll essentially comprising a paper backing 124, a starch-containing stiffener 122, and an adhesive 114. For illustrative purposes, referring to FIGS. 2A and 2B from top to bottom relative to the page, the tape 130 includes a paper backing 124. The paper backing 124 (also referred to as a substrate) has a first major (top) surface 132, a second major (bottom) surface 134, and first and second sides. As shown, the starch-containing stiffener 122 is positioned adjacent to the paper backing 124, and the adhesive 114 is applied to the opposing surface of the starch-containing stiffener 122. In one example, the adhesive 114 is a water-activated adhesive. In another example, the adhesive 114 is a pressure-sensitive adhesive.

[0091] Referring to FIG. 3A, a roll 400 of tape 130 is wound onto a core 118, the roll essentially comprising a paper backing 124, a starch-containing stiffener 122, a paper layer 112, and an adhesive 114. For illustrative purposes, referring to FIGS. 3A and 3B from top to bottom relative to the page, the tape 130 includes a paper backing 124. The paper backing 124 (also referred to as a substrate) has a first major (top) surface 132, a second major (bottom) surface 134, and first and second sides. As shown, the starch-containing stiffener 122 is positioned adjacent to the paper backing 124. As shown in FIGS. 3A and 3B, an additional paper layer 112 is positioned adjacent to the opposing surface of the starch-containing stiffener 122. An adhesive 114 is applied to the opposing surface of the paper layer 112. In one example, the adhesive 114 is a water-activated adhesive. In another example, the adhesive 114 is a pressure-sensitive adhesive. In another example, the adhesive 114 is a repulpable pressure-sensitive adhesive. In another example, the adhesive 114 is a heat-activated adhesive. In another example, the adhesive 114 is a repulpable heat-activated adhesive.

[0092] In one example, the backing 124 and the starch-containing reinforcement material 122 are extrusion laminated. In one example, the backing 124 and the starch-containing reinforcement material 122 are extrusion laminated without additional materials, for example, one surface of the starch-containing reinforcement material 122 is activated, for example, with water, and laminated directly to the paper backing 124. In another example, the backing 124 and the starch-containing reinforcement material 122 are extrusion laminated with a softened or molten layer between them that laminates the layers together and solidifies upon curing. The softened or molten layer can be extruded between the backing 124 and the starch-containing reinforcement material 122 or coextruded with the starch-containing reinforcement material 122.

[0093] In one example, the backing 124 and the starch-containing reinforcement material 122 are adhesively laminated. In one example, the backing 124 and the starch-containing reinforcement material 122 are adhesively laminated without an adhesive, for example, one surface of the starch-containing reinforcement material 122 is activated, for example, with water, and adhered directly to the paper backing 124. In another example, the backing 124 and the starch-containing reinforcement material 122 are adhesively laminated with a layer or discontinuous pattern of adhesive between them that bonds the layers together. The adhesive can be extruded between the backing 124 and the starch-containing reinforcement material 122 or coextruded with the starch-containing reinforcement material 122.

[0094] Referring to roll 300, in one example, the adhesive 114 and the starch-containing reinforcing material 122 are extrusion laminated. In one example, the adhesive 114 and the starch-containing reinforcing material 122 are extrusion laminated without additional materials, for example, one surface of the starch-containing reinforcing material 122 is activated, for example, with water, and laminated directly to the adhesive 114. In another example, the adhesive 114 and the starch-containing reinforcing material 122 are extrusion laminated with a softened or molten layer between them that laminates the layers together and solidifies upon curing. The softened or molten layer may be extruded between the adhesive 114 and the starch-containing reinforcing material 122 or coextruded with the starch-containing reinforcing material 122.

[0095] In one example, the adhesive 114 and the starch-containing reinforcing material 122 are adhesive laminated. In one example, the adhesive 114 and the starch-containing reinforcing material 122 are adhesive laminated without an adhesive, for example, one surface of the starch-containing reinforcing material 122 is activated, for example, with water, and adhered directly to the adhesive 114. In another example, the adhesive 114 and the starch-containing reinforcing material 122 are adhesive laminated with a layer or discontinuous pattern of adhesive between them that bonds the layers together. The adhesive can be extruded between the adhesive 114 and the starch-containing reinforcing material 122 or coextruded with the starch-containing reinforcing material 122.

[0096] Referring to roll 400, in one example, the backing 124 and the starch-containing reinforcement material 122 are extrusion laminated. In one example, the backing 124 and the starch-containing reinforcement material 122 are extrusion laminated without additional materials, for example, one surface of the starch-containing reinforcement material 122 is activated, for example, with water, and laminated directly to the paper backing 124. As shown, roll 400 further includes a paper layer 112 adjacent to the opposite side of the starch-containing reinforcement material 122. In one example, the paper layer 112 and the starch-containing reinforcement material 122 are extrusion laminated. In one example, the paper layer 112 and the starch-containing reinforcement material 122 are extrusion laminated without additional materials, for example, one surface of the starch-containing reinforcement material 122 is activated, for example, with water, and laminated directly to the paper layer 112.

[0097] In one example, the paper backing 124, the starch-containing stiffener 122, and the paper layer 112 are extrusion laminated together. In one example, the paper backing 124, the starch-containing stiffener 122, and the paper layer 112 are extrusion laminated together without additional materials, for example, both surfaces of the starch-containing stiffener 122 are activated, for example, with water, and laminated directly to the paper backing 124 and the paper layer 112. The adhesive 114 is positioned adjacent to opposing surfaces of the paper layer 112. In one example, the adhesive 114 is extrusion laminated to the paper layer 112. In another example, the adhesive 114 is adhesively laminated to the paper layer 112.

[0098] In one example, the paper backing 124, the starch-containing reinforcement 122, and the paper layer 112 are adhesively laminated. In one example, the paper backing 124, the starch-containing reinforcement 122, and the paper layer 112 are adhesively laminated without an adhesive, for example, both surfaces of the starch-containing reinforcement 122 are activated, for example, with water, and directly adhered to the paper backing 124 and the paper layer 112. In another example, the paper backing 124, the starch-containing reinforcement 122, and the paper layer 112 are adhesively laminated with a layer or discontinuous pattern of adhesive therebetween that bonds one or more or all of the layers together. The adhesive may be extruded between one or more of the paper backing 124, the starch-containing reinforcement 122, and the paper layer 112, or coextruded with the starch-containing reinforcement 122.

[0099] In one example, the adhesive 114 of the roll 400 is extrusion laminated or adhesive laminated directly to the paper layer 112. In another example, the adhesive 114 and paper layer 112 are adhesive laminated with a layer or discontinuous pattern of adhesive between them that bonds the layers together. The adhesive can be extruded between the adhesive 114 and the starch-containing reinforcing material 122 or co-extruded with the starch-containing reinforcing material 122.

[0100] The above-described processing steps for rolls 200, 300, or 400 can be carried out continuously, semi-continuously, or in batches.

[0101] Optionally, there is a release layer applied to the top surface of the paper backing 124. In one example, the rolls 200, 300, 400 do not have a release layer.

[0102] Examples of strengthening starches include starches derived from cassava, corn, potato, sweet potato, sago, tapioca, sorghum, bean, bracken, lotus, water chestnut, wheat, rice, oats, arrowroot, or pea. In one example, starch derived from or modified from corn or cassava is used. In another example, starch derived from or modified from high amylose corn is used.

[0103] The strengthening starch can be a single substance or can be a mixture of two or more starches, two or more modified starches, a modified and unmodified starch, a cross-linked starch, a cross-linked starch in combination with one or more modified starches, or a non-cross-linked starch. In one embodiment, the strengthening starch is derived from corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, and / or potato. In one embodiment, the strengthening starch is derived from corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, and / or potato. In one embodiment, the strengthening starch is a blend of unmodified and modified starches selected from corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, pea, and / or potato. In one embodiment, the strengthening starch is a blend of two or more starches independently selected from unmodified, modified, or crosslinked starches of corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, pea, and / or potato. In one embodiment, the strengthening starch is a blend of two or more starches independently selected from unmodified, modified, or crosslinked starches of corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, pea, and / or potato with one or more synthetic starches.

[0104] In one example, the starch or modified starch has an amylopectin content of at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, or at least 90% by weight. In one example, the starch or modified starch has an amylose content of at least 50%, at least 55%, at least 60%, at least 70%, at least 80%, or at least 90% by weight.

[0105] Independently, an amylose-to-amylopectin weight ratio of 40:60 to 0:100 can be employed for any of the starches, modified starches, or synthetic starches. Blends of starches having a total amylopectin weight ratio of 40:60 to 0:100 can be employed. Modified starches having an amylose-to-amylopectin weight ratio of 40:60 to 0:100 or blends of modified starches having a total amylose-to-amylopectin weight ratio of 40:60 to 0:100 can be employed. Combinations of a first starch having an amylose-to-amylopectin weight ratio of 40:60 to 0:100 and a second starch having an amylose-to-amylopectin weight ratio of 40:60 to 0:100 can be employed, wherein at least one of the first and second starches is independently unmodified, modified, synthetic, or crosslinked.

[0106] Examples of modified starches include alkyl-etherified starches such as methyl-etherified starch, carboxyalkyl-etherified starches such as carboxymethyl-etherified starch, and hydroxyalkyl-etherified starches such as etherified starches having a hydroxyalkyl group having 2 to 6 carbon atoms. Alternatively, allyl-etherified starch can also be used as the modified starch.

[0107] Additional examples of modified starches include esterified starches with structural units derived from carboxylic acids, such as esterified starches with structural units derived from acetic acid; esterified starches with structural units derived from dicarboxylic acid anhydrides, such as esterified starches with structural units derived from maleic anhydride, phthalic anhydride, and octenylsuccinic anhydride; and esterified starches with structural units derived from oxoacids, such as nitrate-esterified starch, phosphate-esterified starch, and urea-phosphate-esterified starch. Other examples of these include xanthate-esterified starch, acetoacetate-esterified starch, etc. Alkoxysilane / siloxane TEOS, etc.

[0108] Examples of the crosslinked starch include formaldehyde crosslinked starch, epichlorohydrin crosslinked starch, phosphate crosslinked starch, acrolein crosslinked starch, and sodium tetraborate crosslinked starch.

[0109] In one example, the starch or modified starch film, web, scrim, or layer in its dry state has a water content of about 10-25% by weight, or about 20-25% by weight, as determined by ASTM E 203 or ISO 760.

[0110] In one example, the adhesive 114 is any conventional or below-developed adhesive suitable for box sealing tape or corrugated box sealing tape (also referred to as packaging tape). In one example, the adhesive 114 can be a water-activated adhesive. In one example, the adhesive 114 can be a water-activated adhesive used together with an amorphous polyolefin adhesive, a natural rubber adhesive, a poly(meth)acrylate adhesive, or the like. In one example, the adhesive 114 can be mixed or blended with an amorphous polyolefin adhesive, a natural rubber adhesive, a poly(meth)acrylate adhesive, or the like. In one example, the adhesive 114 can be layered on or between layers of an amorphous polyolefin adhesive, a natural rubber adhesive, a poly(meth)acrylate adhesive, or the like, such as a layer / film or pattern of pressure-sensitive adhesive and a layer / film or pattern of water-activated adhesive.

[0111] In one embodiment, adhesive 114 is a starch-containing adhesive from corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, pea, and / or potato. In one embodiment, adhesive 114 is a cross-linked starch-containing adhesive from corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, pea, and / or potato. In one embodiment, adhesive 114 is a blend of two or more independently selected unmodified starch-containing adhesives, modified starch-containing adhesives, and cross-linked starch-containing adhesives independently selected from corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, pea, and / or potato. In one embodiment, adhesive 114 is a blend of two or more independently selected unmodified, modified, and cross-linked starch-containing adhesives independently selected from corn, sorghum, wheat, sago, tapioca, legumes, barley, rice, dent, pea, and / or potato, with one or more synthetic starch-containing and non-starch-containing adhesives. Adhesive 114 can be of the same or different composition as starch-containing reinforcing material 122.

[0112] In another embodiment, adhesive 114 can be a polyvinyl alcohol, a polyvinyl alcohol copolymer, a polyvinyl alcohol blend remoistenable adhesive, or a blend of one or more polyvinyl alcohol, a polyvinyl alcohol copolymer, a polyvinyl alcohol blend remoistenable adhesive, or any of the starch adhesives previously described.

[0113] A continuous method for fabricating a starch-containing reinforcement 122 tape includes providing a paper tape including a paper backing having an adhesive defining its lower major surface and a starch-containing reinforcement 122 reinforcement structure facing the adhesive of the paper backing. The film reinforcement structure provides the water-activated paper tape with strength essentially equivalent to or greater than conventional reinforcements such as scrims, oriented films, yarns, or fibers, such as PVC, glass, carbon, PET, high molecular weight polyethylene, polyamide, and other engineering thermoplastics. The film reinforcement structure provides the water-activated paper tape with strength essentially equivalent to or greater than conventional reinforcements that pass ISTA 3A and ISTA 6A, i.e., the tape holds boxes / packages closed during shipping without tearing or breaking, thus eliminating or reducing the need for other types of reinforcement. The film reinforcement structure of the present disclosure can be used in combination with any of the conventional reinforcements described above.

[0114] In one example, the starch-containing reinforcing material 122 is adjacent to the paper backing 124 and includes co-extruding the starch-containing reinforcing material 122 directly onto the paper backing. The method may also include reducing the temperature of the starch-containing reinforcing material 122 after its extrusion and before contact with the paper backing 124.

[0115] The method may also include winding the tape onto a roll and cutting the wound tape into a plurality of rolls of film-laminated, water-activated tape.

[0116] In another example, a continuous method of making a film laminated tape may also include providing a paper backing 124 and applying an adhesive to its lower major surface before co-extruding the outermost polyolefin film and laminate layer onto the paper backing.

[0117] The above-described tapes offer the elimination of filament or yarn scrim reinforcement and may require only one layer of paper, resulting in a tape product with uniform puncture and tear properties at similar or lower overall cost than currently available corrugated cardboard sealing tapes, producing thinner tapes that offer longer lengths for a given barrel diameter, and requiring fewer roll changes in application equipment.

[0118] The tape and / or starch-containing film compositions of the present disclosure can further comprise clays, such as synthetic and natural layered silicate clays, including montmorillonite, bentonite, beidellite, mica, hectorite, saponite, nontronite, sauconite, vermiculite, ledikite, magadite, kenyaite, stevensite, volkonskoite, and mixtures thereof.

[0119] In one example, the content of clay in the resin composition is 0.1 to 5 mass%, 0.1 to 3 mass%, or further 0.5 to 2 mass%. When the resin composition contains clay in an amount within the above range, transparency, flexibility, tensile strength, impact resistance, and / or tensile properties tend to be easily improved.

[0120] In one example, the starch composition may contain additives such as fillers, processing stabilizers, weathering stabilizers, colorants, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, plasticizers, other impact modifiers, lubricants, fragrances, antifoaming agents, deodorizers, extenders, release agents, mold release agents, reinforcing agents, crosslinking agents, mildew inhibitors, biocides, moisturizing agents, preservatives, and crystallization rate retarders, as needed, within ranges that do not impair the effects of the present disclosure.

[0121] The starch composition can be produced in the form of pellets or films. As pellets, the starch composition can be stored and / or presented for extrusion or extrusion lamination into a film. As a film, the starch composition can be used in a multi-layer laminate, including at least one layer containing a starch-containing film. Additionally, the starch film has excellent strength, is biodegradable, at least partially or essentially water-soluble, and repulpable, so that it can be used in sustainable packaging films, tapes, or with packaging materials.

[0122] The tapes and compositions of the present disclosure can be produced by a manufacturing method that includes continuously mixing an amount of starch and an amount of water, optionally with other ingredients, while heating in a low shear mixer, such as a planetary rotating extruder, to obtain an extrudate, continuously extruding the extrudate, cooling the melt to form a repulpable reinforced film or pellets, contacting the film with a second major surface of a repulpable paper backing (or reworking the pellets to form a film), and applying an adhesive composition adjacent to the repulpable reinforced material.

[0123] In one aspect, the method further comprises providing a tape.

[0124] In one embodiment, alone or in combination with any one of the preceding embodiments, the contacting of the film with the second major surface of the repulpable backing is continuous.

[0125] In another example, a process for producing a starch film composition is provided, the process comprising: continuously metering a starch film composition comprising starch, modified starch, thermoplastic starch, or a combination, water, and a repulpable material into a low shear extrusion apparatus; and continuously mixing the composition in a compounding section of the low shear extrusion apparatus. In one aspect, alone or in combination with any one of the previous aspects, the compounding section comprises a main spindle surrounded by and intermeshing with a plurality of planetary spindles, at least one of the planetary spindles being a double transverse mixing spindle comprising a plurality of backcut helical flights, and continuously discharging the starch film composition from the extruder.

[0126] An exemplary low shear extrusion apparatus according to the present disclosure is illustrated and generally designated by the reference numeral 10. It will be understood that the low shear extrusion apparatus system 10 is illustrated in diagrammatic form to explain its operation in a readily understandable manner. However, in practice, the shape and size of the system 10 may differ substantially from that illustrated and still be within the scope of the claims set forth herein.

[0127] The low shear extrusion system 10 includes a feed section 12 and a compounding section 14. Primary adhesive ingredients are added to a feed throat 16 and metered into a conveying screw 18 in the filling section 12. As used herein, the term "primary ingredients" refers to those materials of the adhesive formulation that are added to the feed section 12 of the low shear extrusion system 10. Primary ingredients may include, but are not limited to, elastomers, resins, extenders, activators, antidegradants, and crosslinkers. The screw 18 conveys the primary ingredients to the compounding section 14. The compounding section 14 includes four planetary roller barrel sections 20a, 20b, 20c, and 20d separated by dosing rings 22a, 22b, and 22c, as illustrated in FIG. 4. Each roller barrel section 20 includes a 45° helical toothed cylinder 24, a 45° helical toothed main spindle 26, and a plurality of 45° helical toothed planetary spindles 28, 30. The helical gears can have any suitable angle; for example, angles between 10 and 60 degrees, and more specifically angles somewhat greater than 20 degrees, can be useful. According to certain aspects of the present disclosure, at least one of the roller barrel sections 20 includes a dual lateral planetary spindle 28. The present disclosure is not limited to the use of dual lateral planetary spindles; other spindle configurations that provide the desired level of mixing can also be used.

[0128] The maximum number of planetary spindles 28, 30 is a function of the diameters of the main spindle 26 and the helically toothed cylinder 24. The planetary spindles 28, 30 can exhibit many different tooth geometries, such as full helical flights (Planet spindles) 30, double transverse helical flights (also known as backcut spindles or Noppen spindles) 28, or zoned helical flights (Igel spindles). The number of planetary spindles selected and their geometry (e.g., open flights vs. full flights) can be manipulated to affect the dynamic release effect of each roller barrel section 20 and the release differential between the sections. Additionally, the clearance between the injection ring 22 and the main spindle 26 can be varied to change the dynamic release effect of each barrel section 20 and the release differential between the barrel sections 20.

[0129] The standard planetary spindle 30 is represented by a cylinder with grooves or flights cut at a 45° angle to the spindle axis, the same angle as the main spindle flights. The planetary spindles ride on the main spindle flights, and this exemplary design, shown in Figures 4 and 9, results in identical surface speeds for the planetary spindles 28, 30 and the main spindle 26. There is a gap between the main and planetary spindles that fills with process material. The net result is that near-zero shear distributive and dispersive mixing can occur between the main spindle 26, planetary spindles 28, 30, and the barrel wall 24. Other spindle and flight configurations can be used. For example, spindles manufactured by Rust-Mitschke-Entex (Bochum, DE) can be used, including standard Noppen, Igel, Transport, and Kombi spindles.

[0130] Another end result of the 45° angles cut into the planetary and main spindles is the positive pressure and forward motion imparted to the process material. A variation that results in less pressure, more slippage, less forward motion, longer residence time, and therefore greater mixing, is the use of a double transverse spindle 28 (also known as a noppen spindle or backcut spindle).

[0131] The dual transverse planetary spindle 28 is a spindle with openings in its flights that allow material to pass between the wall of the barrel 24 and the main spindle 26, slowing the material's rate of passage through the low shear extrusion system 10. One example of a dual transverse spindle 28 is a so-called porcupine spindle. A specific example of a dual transverse spindle 28 is shown in detail in FIG. 5 , where backcut openings 32 increase residence time and improve mixing. The dual transverse spindle 28 design is a modification of the standard planetary spindle, with additional channels cut into the flights at a 45° angle. The angle of these backcut channels can range from about 45 to 135°, more specifically about 75 to 105°, relative to the spindle flights. According to certain embodiments of the present disclosure, the backcut channels can be at an angle of about 90°. The number and depth of these channels can also vary and can be more simply defined as follows: [(total channel area cut into spindle flights / total area of ​​spindle flights) × 100%]. This value may range from about 10-90%, more specifically from about 40-60%, and in certain embodiments of the present disclosure, this value may be about 50%. Low shear extrusion devices having dual transverse spindles 28 are commercially available from Rust-Mitschke-Entex. By adjusting the number of full flights 30 and open or dual transverse spindles 28, the rate at which the material passes through the low shear extrusion device, and therefore the amount of kneading that occurs to the material, can be controlled.

[0132] Conventional low shear extrusion equipment includes at least three spindles and can include up to 24 spindles, depending on the cylinder diameter and process design. Of course, those skilled in the art will recognize that a greater number of planetary spindles can be used depending on the specific dimensions and configuration of the extruder. In one embodiment of the present disclosure, a low shear extrusion apparatus 10 is used, having a 70 mm diameter cylinder with six spindles 28, 30. According to certain aspects of the present disclosure, the double transverse spindles 28 account for more than 20%, more specifically more than 50%, of the number of planetary spindles 28, 30 in the low shear extrusion apparatus 10. FIG. 8 shows a cross-section of a planetary extruder according to certain embodiments of the present disclosure, including four double transverse planetary spindles 28 and two full-flight spindles 30. In one example, 75% full-flight spindles and 25% back-cut or Noppen spindles are used to process the starch compositions of the present disclosure.

[0133] As a result of the helical gears of the main spindle 26 interacting with the helical gears of the planet spindles 28,30, rotation of the main spindle 26 causes the planet spindles 28,30 to move rotationally.

[0134] The planetary spindles 28, 30 also mesh with the internal gear of the cylinder section 24. The main spindle 26, the planetary spindles 28, 30, and the helical gear of the cylinder section 24 convey the ingredients to be blended towards the discharge orifice 34.

[0135] The term "secondary ingredient," as used herein, refers to an ingredient or solvent introduced into the compounding section 14 of the low shear extrusion apparatus 10. Secondary liquid materials, such as liquids, molten resins, oils, solvents, plasticizers, etc., can be introduced into the compounding section 14 via an injection nozzle (not shown) through a dosing ring 22 assembly. As shown in FIG. 6 , the dosing ring 22 includes a radially extending bore 23 that allows for the metered addition of liquid to the compounding section 14. According to one embodiment of the present disclosure, the process involves delivering a solvent to the compounding section 14 of the low shear extrusion apparatus 10 through the dosing ring 22.

[0136] Secondary solid ingredients may be added to the compounding section 14 through a side feeder 36 or a twin-screw dosing unit 38. The twin-screw dosing unit 38 is typically positioned perpendicular to the axis of the compounding section 14 and is typically located near the beginning of the compounding section directly adjacent to the dosing ring 22a. The twin-screw dosing unit 38 may be employed to introduce solid ingredients such as reinforcing agents, thermoplastic elastomers, resins, extenders, activators, antidegradants, crosslinkers, etc. into the individual roller barrel sections 20.

[0137] Another embodiment of the present disclosure involves coating a starch film composition onto a paper backing using any of a variety of coating techniques, including, but not limited to, slot die coating, roll-over roll coating, gloss coating, reverse roll, and knife-over roll coating. According to certain embodiments of the present disclosure, the adhesive composition is applied to the starch film and / or any intervening paper material using a slot die applicator unit. A particularly useful method for applying the adhesive composition to a web-form material includes slot die coating using a rotating lip die or a fixed lip contact die. One particular slot die unit that can be used is a rotary lip die with a spindle that follows the die lip. An example of such a die is commercially available from SIMPLAS and is shown in FIG. 7. The rotary lip die 40 includes an inlet 42 for receiving the adhesive composition from the extruder 10. As shown in FIG. 8, the starch composition can be continuously conveyed from the planetary extruder 10 to the rotary lip die 40 applicator and applied to the web-form material through a slot 44. The rotary lip die applicator 40 further includes a rotating spindle 46 on the trailing edge of the die lip to improve the coating characteristics of the applied adhesive. An adjustable bolt 48 on the rotary lip die applicator 40 allows an operator to easily adjust the lip opening and control the thickness of the adhesive coating.

[0138] According to another aspect of the present disclosure, the starch-containing composition can be crosslinked. More specifically, the starch-containing composition can be crosslinked thermally, chemically, for example, with azides, epichlorohydrin, formaldehyde, phosphoric acid, acrolein, sodium tetraborate, epoxides, anhydrides, and / or with the aid of ionizing radiation such as electron beam or UV radiation, so that the resulting starch-containing composition provides a shear-resistant and temperature-stable film, web, scrim, or layer.

[0139] Additional advantages of certain embodiments of the new disclosure / method include: 1) targeted, effective, and efficient compounding with minimal shear of, for example, starch-containing compositions; 2) introduction of various additional materials into the compounding section; 3) introduction of solvents or water in some form into the compounding section; and 4) use of pelletizing, slot die, and annular die coating techniques to achieve web, film, or layer materials.

[0140] Blending of the starch or modified starch of the present disclosure with repulpable materials is achieved when the starch is extruded using a single screw from a feed section between the input ring and the main spindle to a blending section, where it is mixed and then blended. The degree of shear and / or chain scission of the starch can be minimized by selecting an appropriate combination of planetary spindle geometry and the number of planetary spindles employed. Reducing shear of the starch or modified starch leads to more efficient blending of the starch with repulpable materials and other solid and liquid materials, potentially minimizing molecular weight reduction.

[0141] Thus, in one example, starch, alone or in compositions with repulpable materials and other solid and liquid materials, is formulated to reduce the average or number average Mw by less than 5%, less than 10%, less than 20%, less than 30%, less than 24%, or less than 50%, as measured by GPC. This reduction is relative to the initial molecular weight of the starch when it is introduced into the low shear extrusion device. Thus, the initial molecular weight may already be reduced as a result of pre-processing the starch compared to the molecular weight of the raw starch. Thus, the molecular weight reduction referred to herein is based on the molecular weight reduction obtained by processing in a low shear extrusion device. The molecular weight reduction as described herein is calculated according to Equation I: Reduction % = (Mw(initial) - Mw(final)) / Mw(initial) x 100 (I)

[0142] Introducing various additional materials into the compounding section has several advantages. First, all such additional materials do not need to be introduced all at once into the feed section of the low shear extrusion device; i.e., they can be introduced into one or more of the roller barrel sections of the compounding section. This allows more time for the starch to be compounded before adding the repulpable material and other solid and liquid materials, increasing the mixing efficiency of the low shear extrusion device. The addition of the repulpable material and other solid and liquid materials further enhances mixing efficiency and tends to act as a lubricant, improving mixing efficiency. Additionally, the repulpable material and other solid and liquid materials can have specific heat capacities that provide the ability to act as a heat sink, i.e., to remove heat from the process, thereby minimizing the temperature of the melt during the compounding process.

[0143] In a first process step, a composition comprising starch and repulpable materials and other solid and liquid materials, along with known adjuvants such as bulking agents, antioxidants, activators, colorants, aging inhibitors, plasticizers, and tackifying resins, is produced in a low shear extrusion apparatus, the composition having a final temperature of less than 200° C., less than about 150° C., 140° C., 130° C., 120° C., 110° C., for example, about 25° C. to 175° C. The total residence time of the composition in the low shear extrusion apparatus typically does not exceed about 3 minutes, 5 minutes, 10 minutes, or more.

[0144] According to certain aspects of the present disclosure, the starch film exiting the extruder can be used immediately as a web-form material or can be pelletized for later film processing and casting, which can be done in a particularly effective and advantageous manner using a slot die applicator unit, and in particular a rotating lip slot die applicator unit.

[0145] In one example, the starch-based reinforcement material or tape comprising the starch-based reinforcement material of the present disclosure is at least 60% and up to about 99% repulpable. In one example, the starch-based reinforcement material or tape comprising the starch-based reinforcement material of the present disclosure is at least 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, or greater than 99% repulpable. In one example, the starch-based reinforcement material or tape comprising the starch-based reinforcement material of the present disclosure is at least 60% and up to about 99% repulpable in accordance with the 2013 Fibre Box Association Voluntary Standard for the Repulping and Regeneration of Corrugated Cardboard Treated for Improved Performance in the Presence of Water and Steam (the "FBA Method").

[0146] Although certain embodiments of the present disclosure have been illustrated with reference to particular combinations of elements, various other combinations may be provided without departing from the teachings of the present disclosure. Thus, the present disclosure should not be construed as limited to the specific exemplary embodiments described herein and illustrated in the figures, but may also encompass combinations of elements of these various illustrated embodiments and aspects.

Claims

1. A tape, a repulpable backing having a first major surface and an opposing second major surface; a repulpable reinforcement material adjacent the second major surface; an adhesive layer adjacent to the repulpable reinforcement material.

2. 10. The tape of claim 1, wherein the repulpable backing consists essentially of cellulose, unmodified starch, modified starch, synthetic starch, crosslinked starch, thermoplastic starch, polyvinyl alcohol or polyvinyl alcohol copolymers and salts thereof, polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxides, polyhydroxyalkanoates, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polyamides, poly(meth)acrylic acid, poly(meth)acrylates and salts thereof, gelatin, methylcellulose, carboxymethylcellulose and salts thereof, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, dextrin, maltodextrin, guar gum, acacia gum, xanthan gum, carrageenan, copolymers thereof, blends thereof, and combinations thereof.

3. 3. The tape of claim 2, wherein the repulpable backing is paper, such as kraft paper.

4. The tape of any one of claims 1 to 3, wherein the repulpable reinforcement is directly adjacent to the repulpable backing. The tape of any one of claims 1 to 3, wherein the repulpable backing is extrusion laminated or adhesive laminated to the repulpable reinforcement material, or the repulpable backing is adhesive laminated to the repulpable reinforcement material without an adhesive.

5. 5. The tape of claim 1, wherein the repulpable reinforcement material is a film, web, or scrim comprising unmodified starch, modified starch, synthetic starch, thermoplastic starch, crosslinked starch, or a mixture of two or more thereof.

6. The tape of any one of claims 1 to 5, wherein the repulpable reinforcement is at least 90 weight percent hot water soluble or repulpable under pulping conditions.

7. 7. The tape of any one of claims 1 to 6, wherein the repulpable reinforcement material comprises unmodified, modified, synthetic, thermoplastic, or cross-linked starch derived from cassava, corn, potato, sweet potato, sago, tapioca, sorghum, bean, bracken, lotus, water chestnut, wheat, rice, oat, arrowroot, dent, or pea.

8. 8. The tape of claim 1, wherein the repulpable reinforcement material comprises unmodified, modified, synthetic, thermoplastic, or cross-linked starch derived from glutinous rice, waxy potato starch, and waxy corn.

9. The tape of any one of claims 1 to 8, wherein the repulpable reinforcement is an extruded web, film, or layer.

10. 10. The tape of any one of claims 1 to 9, wherein the repulpable reinforcement material comprises a starch having a total weight ratio of amylose to amylopectin of 40:60 to 0:100, a modified starch having a total weight ratio of amylose to amylopectin of 40:60 to 0:100, a synthetic starch having a total weight ratio of amylose to amylopectin of 40:60 to 0:100, or a thermoplastic starch having a total weight ratio of amylose to amylopectin of 40:60 to 0:

100.

11. 11. The tape of any one of claims 1 to 10, wherein the repulpable reinforcement material comprises a blend of starches having a total weight ratio of amylose to amylopectin of from 40:60 to 0:100, and the blend of starches comprises unmodified starch, modified starch, synthetic starch, thermoplastic starch, or combinations thereof.

12. 12. The tape of any one of claims 1 to 11, wherein the repulpable reinforcement material comprises a blend of starches comprising a first starch having an amylose to amylopectin weight ratio of from 40:60 to 0:100 in combination with a second starch having an amylose to amylopectin weight ratio of from 40:60 to 0:100, at least one of the first starch and the second starch being independently unmodified, modified, synthetic, or crosslinked.

13. The tape of any one of claims 1 to 12, wherein the repulpable reinforcement material comprises starch or modified starch in combination with polyvinyl alcohol or a polyvinyl alcohol copolymer.

14. The tape of any one of claims 1 to 13, wherein the adhesive layer is a water-activated adhesive.

15. 15. The tape of claim 14, wherein the water-activated adhesive is a polyvinyl acetate emulsion adhesive, a polyethylene vinyl acetate adhesive, a poly(meth)acrylic or poly(meth)acrylic emulsion adhesive, a starch-based adhesive, a repulpable pressure-sensitive adhesive, or a combination or laminate thereof.

16. The tape of any one of claims 1 to 15, wherein the tape is at least 80, at least 85, or at least 90 weight percent hot water soluble or repulpable under pulping conditions.

17. A film, Starch and and a quantity of repulpable material.

18. 18. The film of claim 17, wherein the starch present in the film is an alkyl etherified starch, a carboxyalkyl etherified starch, a hydroxyalkyl etherified starch having a hydroxyalkyl group having from 2 to 6 carbon atoms, a thermoplastic starch, a synthetic starch, or derived from cassava, corn, potato, sweet potato, sago, tapioca, sorghum, bean, bracken, lotus, water chestnut, wheat, rice, oat, arrowroot, dent, or pea.

19. 19. The film of claim 17 or 18, wherein the starch comprises a blend of starches having an amylose to amylopectin weight ratio of 40:60 to 0:100, a blend of starches having a total weight ratio of amylose to amylopectin of 40:60 to 0:100, a modified starch having a total weight ratio of amylose to amylopectin of 40:60 to 0:100, a blend of modified starches having a total weight ratio of amylose to amylopectin of 40:60 to 0:100, or a combination of a first starch having an amylose to amylopectin weight ratio of 40:60 to 0:100 and a second starch having an amylose to amylopectin weight ratio of 40:60 to 0:100, wherein at least one of the first starch and the second starch is independently unmodified, modified, thermoplastic, synthetic, or crosslinked.

20. 20. The film of any one of claims 17 to 19, wherein the repulpable material is selected from the group consisting of polyvinyl alcohol or polyvinyl alcohol copolymers and salts thereof, polyethyleneimine, polyvinylpyrrolidone, polyalkylene oxides, polyhydroxyalkanoates, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polyamides, gelatin, poly(meth)acrylic acid, poly(meth)acrylates and salts thereof, methylcellulose, carboxymethylcellulose and salts thereof, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, microfibrillated cellulose, modified microfibrillated cellulose, dextrin, maltodextrin, guar gum, acacia gum, gum arabic, xanthan gum, carrageenan, algin, locust bean, gellan, copolymers thereof, blends thereof, and combinations thereof.

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