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EP3891213A1 - Copolymère de pvp pour l'emballage d'un produit chimique agressif - Google Patents

Copolymère de pvp pour l'emballage d'un produit chimique agressif

Info

Publication number
EP3891213A1
EP3891213A1 EP19835334.4A EP19835334A EP3891213A1 EP 3891213 A1 EP3891213 A1 EP 3891213A1 EP 19835334 A EP19835334 A EP 19835334A EP 3891213 A1 EP3891213 A1 EP 3891213A1
Authority
EP
European Patent Office
Prior art keywords
film
acid
range
water
relative humidity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19835334.4A
Other languages
German (de)
English (en)
Inventor
Paula CARRIER
Vinh Nguyen
Regan POLLOCK
Richard Vicari
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Specialty Chemicals America LLC
Original Assignee
Sekisui Specialty Chemicals America LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US16/208,298 external-priority patent/US20190169383A1/en
Application filed by Sekisui Specialty Chemicals America LLC filed Critical Sekisui Specialty Chemicals America LLC
Publication of EP3891213A1 publication Critical patent/EP3891213A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/46—Applications of disintegrable, dissolvable or edible materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • Embodiments disclosed herein relate generally to water-soluble polyvinyl alcohol based films that exhibit stability when in contact with aggressive oxidizing chemicals. More specifically, embodiments disclosed herein relate to vinyl alcohol - vinyl pyrrolidone copolymers, and the use of films from such co-polymers for applications such as unit dose packaging of aggressive oxidizing chemicals.
  • PVOH films are often used in the art to form unit dose packages, as the films exhibit good strength, impact resistance, and are soluble in water.
  • the solubility of PVOH films rapidly decreases when exposed to certain chemicals, such as oxidizing chemicals, acid chemicals, alkali chemicals, chlorine-containing substances, salts with polyvalent metals, boric acid, polyamines, insecticides, herbicides, among others.
  • certain chemicals such as oxidizing chemicals, acid chemicals, alkali chemicals, chlorine-containing substances, salts with polyvalent metals, boric acid, polyamines, insecticides, herbicides, among others.
  • Modified PVOH films having co-monomers and/or various additives, have been shown to improve the chemical resistance of the films.
  • various plasticizers, additives, and co-monomers such as N-vinylamide, carboxyl and carboxylate functional groups, and sulfonic acid functional groups.
  • US5102950 assigned to Kuraray Co., Ltd., discloses a PVOH film formed from a copolymer consisting of vinyl alcohol units, vinyl ester units, and copolymerization units containing a 2-pyrrolidone ring.
  • Other comonomers are also contemplated, including sulfonic acid groups, quaternary ammonium structures, and others.
  • plasticizers such as a polyhydric alcohol and linear sugar alcohols having 4 to 6 carbon atoms.
  • US6166117 also to Kuraray Co., Ltd., discloses a water-soluble film including a sulfonic acid group modified polyvinyl alcohol in admixture with gallic acid.
  • a sulfonic acid group modified polyvinyl alcohol in admixture with gallic acid.
  • 2-acrylamido-2-methylpropanesulfonate-modified polyvinyl alcohols are unsuitable for storage of acidic chemicals for long periods of time, as they lose their function as a water-soluble film.
  • the gallic acid is taught as necessary to achieve the desired properties.
  • embodiments disclosed herein relate to a water soluble film useful in unit dose packaging.
  • the water-soluble film may have stability when contacted with harsh chemicals, such as aggressive oxidizing chemicals, and may include: a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 1 to 20 mole percent of a pyrrolidone comonomer; and a water-soluble saccharide.
  • a unit dose package including: a polymeric dissolution packet comprising the film as described above; and a harsh chemical sealed in the polymeric dissolution packet.
  • embodiments disclosed herein relate to a unit dose package.
  • the unit dose package may include: a polymeric dissolution packet comprising a film; and a chemical sealed in the polymeric dissolution packet.
  • the film may comprise a plasticizer and a polyvinyl alcohol copolymer A consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 1 to 20 mole percent of a pyrrolidone comonomer, the copolymer having a degree of hydrolysis in the range from about 65% to about 99%.
  • the chemical may include a peroxide, a nitrate, a nitrite, a chromate, a persulfate, a borate, a bromate, a chlorate, a periodate, a chlorite, a chlorinated or brominated isocyanurate, an inorganic acid, an organic acid, a peroxy acid, or potassium superoxide, or salts and hydrates of these compounds.
  • the film may have a %dissolution by weight in water at 21°C of at least 85 wt% following exposure to the chemical and aging at a temperature in the range from about 30°C to about 54°C for at least 4 weeks, such as in the range from about 4 weeks to about 12 weeks.
  • the chemical is selected from the group consisting of dichloroisocyanuric acid, calcium hypochlorite, trichloroisocyanuric acid, l-bromo-3- chloro -5,5-dimethylhydantoin, l,3-dibromo-5,5-dimethylhydantoin, 2,3-dibromo-3- nitrilopropionamide; 2-bromo-2-nitro- 1,3 -propanediol, sodium bisulfate, tartaric acid, fumaric acid, oxalic acid, sodium percarbonate, sodium carbonate, sodium bicarbonate, cyanuric acid, and potassium monopersulfate.
  • the chemical is undiluted.
  • the plasticizer is a solid at room temperature and pressure.
  • the film may further include a polyvinyl alcohol copolymer B containing: (a) from 94 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 1 to 6 mole percent of a comonomer comprising sulfonic acid groups.
  • the film may also include an additive selected from the group consisting of dextrose, a bromine scavenger, a chlorine scavenger, ammonium chloride, citric acid, starch, potassium bicarbonate, ammonium chloride, polypropylene glycol, starch, and sodium bisulfite.
  • the film may have one or more of the following properties when tested according to ASTM D882:
  • d. have an elongation at break at equilibrium conditions of 23°C and 50% relative humidity in the range from about 100% to about 250%; e. a 100% modulus at equilibrium conditions of 23°C and 50% relative humidity in the range from about 15 to about 40 MPa;
  • the plasticizer may comprise alkoxylated trimethylol propane, trimethylol propane, or diglycerine, or a combination thereof, each individually present in an amount in the range from about 1 wt% to about 12 wt%, based on a total weight of the film. In some embodiments of the unit dose package, the plasticizer may comprise alkoxylated trimethylol propane, trimethylol propane, or diglycerine, or a combination thereof, each individually present in an amount in the range from about 2 wt% to about 4 wt%, based on a total weight of the film.
  • inventions herein are directed toward a water-soluble film having stability with harsh chemicals.
  • the film may include a plasticizer and a polyvinyl alcohol copolymer A having a degree of hydrolysis in the range from about 65% to about 99% and consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 1 to 20 mole percent of a pyrrolidone comonomer.
  • the film may have a %dis solution by weight in water at 21°C of at least 85 wt% following exposure to a chemical and aging at a temperature in the range from about 30°C to about 54°C for at least 4 weeks, such as 4 to 12 weeks, wherein the chemical is selected from the group consisting of dichloroisocyanuric acid, calcium hypochlorite, trichloroisocyanuric acid, l-bromo-3- chloro-5,5-dimethylhydantoin, l,3-dibromo-5,5-dimethylhydantoin, 2,3-dibromo-3- nitrilopropionamide; 2-bromo-2-nitro- 1,3 -propanediol, sodium bisulfate, tartaric acid, fumaric acid, oxalic acid, sodium percarbonate, sodium carbonate, sodium bicarbonate, cyanuric acid, and potassium monopersulfate.
  • the chemical is selected from the group consist
  • the film is compatible with each of dichloroisocyanuric acid, calcium hypochlorite, trichloroisocyanuric acid, l-bromo-3-chloro-5,5-dimethylhydantoin, l,3-dibromo-5,5-dimethylhydantoin,
  • 2,3-dibromo-3-nitrilopropionamide 2-bromo-2-nitro- 1 ,3-propanediol, sodium bisulfate, tartaric acid, fumaric acid, oxalic acid, sodium percarbonate, sodium carbonate, sodium bicarbonate, cyanuric acid, and potassium monopersulfate.
  • the plasticizer may comprise alkoxylated trimethylol propane, trimethylol propane, or diglycerine, or a combination thereof, each individually present in an amount in the range from about 1 wt% to about 12 wt%, based on a total weight of the film.
  • the plasticizer may comprise alkoxylated trimethylol propane, trimethylol propane, or diglycerine, or a combination thereof, each individually present in an amount in the range from about 2 wt% to about 4 wt%, based on a total weight of the film.
  • the water-soluble film has a %dissolution by weight in water at 21°C of at least 85 wt% following exposure to a chemical and aging at a temperature in the range from about 40°C to about 54°C for at least 8 weeks. In other embodiments, the film has a %dissolution by weight in water at 21°C of at least 85 wt% following exposure to a chemical and aging at a temperature in the range from about 50°C to about 54°C for at least 12 weeks, such as 12 to 20 weeks.
  • the plasticizer is a solid at room temperature and pressure. In some embodiments, the plasticizer may have at least 2 hydroxyl groups per molecule. In some embodiments, the plasticizer may be present in an amount of 1 to 10 parts per hundred parts polyvinyl alcohol copolymer A.
  • the polyvinyl alcohol copolymer A may contain from 2 to 12 mole percent of the pyrrolidone comonomer. In other embodiments, the polyvinyl alcohol copolymer A may contain from 3 to 7 mole percent of the pyrrolidone comonomer.
  • the water-soluble film may also include an additive selected from the group consisting of dextrose, a bromine scavenger, a chlorine scavenger, ammonium chloride, citric acid, starch, potassium bicarbonate, ammonium chloride, polypropylene glycol, starch, and sodium bisulfite.
  • the additive is a crystalline solid at room temperature and pressure.
  • the film may include dextrose, wherein the dextrose is present in an amount in the range from about 1 to about 10 parts per hundred parts polyvinyl alcohol copolymer A.
  • the film may include an additive selected from the group consisting of dextrose, a bromine scavenger, a chlorine scavenger, ammonium chloride, citric acid, starch, potassium bicarbonate, ammonium chloride, polypropylene glycol, starch, and sodium bisulfite.
  • the additive is a crystalline solid at room temperature and pressure.
  • the water-soluble film may further include a polyvinyl alcohol copolymer B comprising: (a) from 94 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 1 to 6 mole percent of a comonomer comprising sulfonic acid groups.
  • a polyvinyl alcohol copolymer B comprising: (a) from 94 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 1 to 6 mole percent of a comonomer comprising sulfonic acid groups.
  • inventions herein are directed toward a water-soluble film having stability with harsh chemicals.
  • the film may include a plasticizer and a polyvinyl alcohol copolymer A consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 1 to 20 mole percent of a pyrrolidone comonomer.
  • the film may have a tensile strength at equilibrium conditions of 30°C and 20% relative humidity of at least 60 MPa when tested according to ASTM D882.
  • the film may have a 10% modulus at equilibrium conditions of 30°C and 20% relative humidity of at least 40 MPa when tested according to ASTM D882.
  • the film may have an elongation at break at equilibrium conditions of 30°C and 20% relative humidity in the range from about 20% to about 80% when tested according to ASTM D882.
  • the water-soluble film may have a %dissolution by weight in water at 21°C of at least 85 wt% following exposure to a chemical and aging at a temperature in the range from about 30°C to about 54°C for at least 4 weeks, wherein the chemical is selected from the group consisting of dichloroisocyanuric acid, calcium hypochlorite, trichloroisocyanuric acid, l-bromo-3-chloro -5,5-dimethylhydantoin, 1,3-dibromo- 5,5-dimethylhydantoin, 2,3-dibromo-3-nitrilopropionamide; 2-bromo-2-nitro- 1 ,3- propanediol, sodium bisulfate, tartaric acid, fumaric acid, oxalic acid, sodium percarbonate, sodium carbonate, sodium bicarbonate, cyanuric acid, and potassium monopersulfate.
  • the chemical is selected from the group consisting of dichlorois
  • the water-soluble film may include a plasticizer that is a solid at room temperature and pressure.
  • the water-soluble film may also include an additive, wherein the additive is a crystalline solid at room temperature and pressure.
  • inventions herein are directed toward a water-soluble film having stability with multiple harsh chemicals.
  • the film may include a plasticizer and a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 1 to 20 mole percent of a pyrrolidone comonomer.
  • the film may be compatible with each of the following chemical groups: peroxides, nitrates, nitrites, chromates, persulfates, borates, bromates, chlorates, periodates, chlorites, chlorinated or brominated isocyanurates, inorganic acids, organic acids, peroxy acids, superoxides, and salts and hydrates of these compounds.
  • the water soluble film according to some embodiments herein may be compatible with each of dichloroisocyanuric acid, calcium hypochlorite, trichloroisocyanuric acid, l-bromo-3-chloro-5,5-dimethylhydantoin, l,3-dibromo-5,5- dimethylhydantoin, 2,3-dibromo-3-nitrilopropionamide; 2-bromo-2-nitro- 1 ,3- propanediol, sodium bisulfate, tartaric acid, fumaric acid, oxalic acid, sodium percarbonate, sodium carbonate, sodium bicarbonate, cyanuric acid, and potassium monopersulfate.
  • the plasticizer may include alkoxylated trimethylol propane, trimethylol propane, or diglycerine, or a combination thereof, and when present, each is individually present in an amount in the range from about 1 wt% to about 12 wt%, based on a total weight of the film.
  • the plasticizer may include alkoxylated trimethylol propane, trimethylol propane, or diglycerine, or a combination thereof, and when present, each is individually present in an amount in the range from about 2 wt% to about 4 wt%, based on a total weight of the film.
  • the film may have a %dissolution by weight in water at
  • the films according to embodiments herein may exhibit chemical compatibility and may have one or more of the following properties when tested according to ASTM D882:
  • d. have an elongation at break at equilibrium conditions of 23 °C and 50% relative humidity in the range from about 100% to about 250%; e. a 100% modulus at equilibrium conditions of 23°C and 50% relative humidity in the range from about 15 to about 40 MPa;
  • embodiments disclosed herein relate to water-soluble polyvinyl alcohol based films that exhibit resistance to aggressive oxidizing chemicals. More specifically, embodiments disclosed herein relate to vinyl alcohol copolymers including a comonomer having a pyrrolidone ring substituent group, such as vinyl pyrrolidone, and the use of films from such copolymers for applications such as unit dose packaging of aggressive oxidizing chemicals.
  • Vinyl alcohol copolymers useful in embodiments disclosed herein may be formed via the copolymerization of a vinyl ester monomer and the pyrrolidone comonomer via bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and the like.
  • Vinyl esters monomers may include various aliphatic acids, such as vinyl formate, vinyl acetate, vinyl butyrate, vinyl pivalate, isoprenyl acetate, and vinyl versatate, among others.
  • Pyrrolidone comonomers may include compounds having a polymerizable carbon-carbon double bond and a pyrrolidone ring substituent group represented by the following formula:
  • Ri, R2, R3, R4, Rs and R 6 are each individually selected from a hydrogen atom or an alkyl group, such as an alkyl group having 1 to 8 carbon atoms.
  • Examples of the group represented by the general formula (I) are 2-oxopyrrolidin-l-yl group, 3- propyl-2-oxopyrrolidin-l-yl group, 5-methyl-2-oxopyrrolidin-l-yl group, 5,5- dimethyl-2-oxopyrrolidin-l-yl group, 3,5-dimethyl-2-oxopyrrolidin-l-yl group, and the like.
  • the carbon-carbon double bond contained in the pyrrolidone comonomer may include vinyl, allyl, styryl, acryloxy, methacryloxy, vinyloxy, allyloxyl, and other groups, that are copolymerizable with the above noted vinyl esters of aliphatic acids and have a high alkali resistance at the time of copolymer hydrolysis to form the vinyl alcohol copolymer.
  • Examples of the pyrrolidone comonomers may include N- vinyl-2-pyrrolidone, N -vinyl-3 -propyl-2-pyrrolidone, N- vinyl-5-methyl-2- pyrrolidone, N- vinyl-5 ,5-dimethyl-2-pyrrolidone, N -vinyl-3 ,5-dimethyl-2- pyrrolidone, and N-allyl-2-pyrrolidone, among others.
  • the vinyl ester copolymer thus obtained may be saponified to form a vinyl alcohol copolymer.
  • the resulting vinyl alcohol copolymer may have a degree of hydrolysis in the range from about 65 to about 99%, in some embodiments; in the range from about 75 to about 95% in other embodiments, as indicated by C 13 NMR analyses.
  • the copolymer may have a relative molecular weight indicated by a characteristic viscosity in the range from about 2 to about 50 cps, in some embodiments; in the range from about 3 to about 30 cps or from about 7 to about 10 cps in other embodiments, where the viscosity is determined on a 4 wt% solution of the polymers in water, measured on a Brookfield viscometer at 20°C.
  • the saponified copolymer may have from about 1 mole% to about 20 mole% of the pyrrolidone comonomer in some embodiments. In other embodiments, the saponified copolymer may have from about 2 mole% or 3 mole% to about 15 mole% pyrrolidone comonomer, such as from about 4 mole% to about 12 mole% or from about 5 mole% to about 10 mole%.
  • the copolymer may include the pyrrolidone comonomer in an amount ranging from a lower limit of 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mole% to an upper limit of 8, 9, 10, 11, 11, 13, 14, 15, 16, 17, 18, 19, or 20 mole%, where any lower limit may be combined with any upper limit.
  • the copolymer is essentially free of other comonomers.
  • the vinyl alcohol copolymers described above may be used to form water soluble films, such as for unit dose packaging or other applications where water solubility of the film is a desired characteristic.
  • such films may advantageously be used for unit dose packaging of harsh chemicals, where the unit dose package has a useful shelf life, even when stored at elevated temperature conditions for extended periods of time, such as those that may occur in storage facilities and/or during shipping.
  • water soluble film formulations useful in embodiments herein may include a blend of the vinyl alcohol copolymer and a saccharide component.
  • the saccharide component includes at least one water soluble saccharide, i.e., has a solubility in water at 25°C of at least 0.1 moles per liter.
  • the saccharide component may include oligosaccharides, disaccharides, monosaccharides, or combinations thereof.
  • the saccharide component does not include polysaccharides (starches) or sugar alcohols. Non-limiting examples include glucose (dextrose), galactose, sucrose, fructose, lactose, maltose, mannose, trehalose, and combinations thereof.
  • the saccharide component is preferably a mono- or di saccharide, and is preferably crystalline.
  • the saccharide component may be a solid at room temperature and pressure, and may be a crystalline solid.
  • the film formulations generally include the vinyl alcohol copolymer as the primary component.
  • the saccharide component may be present in amounts ranging from about 1 wt% to 40 wt% in some embodiments; from about 1 wt% to about 25 wt%, from about 1 wt% to about 10 wt%, or from about 1 wt% to about 5 wt% in other embodiments.
  • the saccharide component may be present in an amount ranging from a lower limit of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 wt% to an upper limit of 10, 15, 20, 25, 30, 35 or 40 wt%, where any lower limit may be combined with any upper limit.
  • the films may further include a chlorine scavenger or a bromine scavenger in amounts in the range from about 0.25 wt% to about 5 wt%, such as from about 0.5 wt% to about 2.5 wt%, or from about 1 wt% to about 2 wt%.
  • Suitable chlorine scavengers may include thiosulfate salts, such as sodium thiosulfate.
  • chlorine scavengers useful in embodiments herein may include: polymers such as polyethylene imines, polyamines, polyamineamides and polyacrylamides; anions selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, nitrite, etc.; and antioxidants like carbamate, ascorbate, etc. and mixtures thereof.
  • Conventional non-chlorine scavenging anions like sulfate, bisulfate, carbonate, bicarbonate, nitrate, chloride, borate, phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, salicylate, etc.
  • chlorine scavengers useful in embodiments herein include ammonium sulfate (preferred), and primary and secondary amines of low volatility such as ethanolamines, amino acids and their salts, polyamino acids and their salts, fatty amines, glucoseamine and other aminated sugars. Specific examples include tris(hydroxymethyl) aminomethane, monoethanol amine, diethanol amine, sarcosine, glycine, iminodiacetic acid, lysine, ethylenediamine diacetic acid, 2,2,6,6-tetramethyl piperinol, and 2,2,6,6-tetramethyl piperinone.
  • plasticizers in addition to the saccharide component (the inclusion of the saccharide component may have some plasticizing effect on the film).
  • plasticizers useful in embodiments disclosed herein may include polyethylene glycol (PEG), polypropylene glycol, polyglycerol, trimethylene glycol, trimethylol propane, alkoxylated trimethylol propane, 2,2,4-trimethyl- 1, 3 -pentanediol, pentaerythritol, or glycerine.
  • additives useful in embodiments herein may include biocides, fillers, extenders, antiblocking agents, anti-slipping agents, detackifying agents, anti-foaming agents, UV stabilizers, lubricants, release agents, pigments, and dyes, among other additives.
  • additives may include at least one of starch, diisopropanol amine (DIPA), ammonium chloride, sodium bisulfite, citric acid, potassium bicarbonate, and ammonium chloride.
  • DIPA diisopropanol amine
  • Plasticizers and additives may each be used, in some embodiments, in amounts ranging from about 0.1 to about 25 wt%, such as in the range from about 1 to about 20 wt% or from about 1 to about 15 wt%, from about 1 to about 10 wt%, or from 1 to about 5 wt% in other embodiments.
  • the plasticizers and/or additives may be individually present in an amount ranging from a lower limit of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20 wt% to an upper limit of 5, 6, 7, 8, 9, 10, 12, 15, 18, 20, or 25 wt%, where any lower limit may be combined with any upper limit.
  • the plasticizers and/or additives used may be a solid at room temperature.
  • the plasticizers and/or additives may have a relatively high molecular weight, such as greater than about 100 or 120 g/mol, and/or may contain multiple hydroxyl groups, such as 2, 3, 4, or more hydroxyl groups per molecule, for example.
  • the high molecular weight and high melting point may contribute to hindered migration of a harsh chemical within a film composition, for example, and such plasticizers and additives may thus impart desirable physical, mechanical, and chemical characteristics to the resulting films.
  • room temperature solid or crystalline plasticizers and additives may more effectively hinder migration of chemicals into the film, improving the stability and structure of the film while concurrently maintaining solubility of the water-soluble polymer.
  • High molecular weight plasticizers and additives, and/or those with significant hydrogen bonding capability, such as those with 2, 3, 4, or more hydroxyl groups, may likewise contribute to hindered migration, for example.
  • the plasticizer used may include alkoxylated trimethylol propane, trimethylol propane, diglycerine, or a combination thereof, each individually present in an amount in the range from about 1 wt% to about 12 wt%, based on a total weight of the film.
  • the plasticizer used may include alkoxylated trimethylol propane, trimethylol propane, diglycerine, or a combination thereof, each individually present in an amount in the range from about 2 wt% to about 4 wt%, based on a total weight of the film.
  • Films formed from the vinyl alcohol copolymers described above, including pyrrolidone comonomers, may have physical properties that contribute to the performance of the resulting film, such as when used in harsh chemical packaging, for example.
  • the properties of the resulting films may depend upon a variety of factors, including composition (comonomer content, plasticizer content, additive content), film thickness, polymer molecular weight, as well as the environment in which the film is tested in (temperature, relative humidity). Exemplary physical properties of films useful in some embodiments herein are provided in the Table below.
  • a 40-60 micron film as described herein may have a 10% modulus at equilibrium conditions of 30°C and 20% relative humidity of at least 40 MPa, such as a 10% modulus at equilibrium conditions of 30°C and 20% relative humidity in the range from about 45 to 100 MPa, such as in the range from 50 to 75 MPa.
  • a 40-60 micron film as described herein may have a tensile strength at equilibrium conditions of 30°C and 20% relative humidity of at least 60 MPa, such as from about 70 to about 150 MPa, or from about 80 to about 130 MPa.
  • a 40-60 micron film as described herein may have an elongation at break at equilibrium conditions of 30°C and 20% relative humidity in the range from about 25% to about 100%, such as from about 20% to about 80%, or from about 25% to about 65%.
  • a 40-60 micron film as described herein may have an elongation at break at equilibrium conditions of 23°C and 50% relative humidity of less than 250%, such as from about 100% to about 250%, or from about 150% to about 220%.
  • a 40-60 micron film as described herein may have a 100% modulus at equilibrium conditions of 23 °C and 50% relative humidity of at least 15 MPa, such as in the range from about 15 to about 40 MPa, or in the range from about 18 to about 36 MPa.
  • a 40-60 micron film as described herein may have an elongation at break at equilibrium conditions of 10°C and 70% relative humidity of less than 300%, such as in the range from about 15% to about 260%, or in the range from about 20% to about 250%, or in the range from about 25% to about 200%.
  • a 40-60 micron film as described herein may have a 100% modulus at equilibrium conditions of 10°C and 70% relative humidity of at least 9 MPa, such as in the range from about 9 to about 25 MPa, or in the range from about 10 to about 15 MPa.
  • a 40-60 micron film as described herein may have a combination of two or more of the above-described property ranges.
  • the vinyl alcohol copolymers described above may be used in admixture with one or more additional polyvinyl alcohol copolymers to form films and unit dose packages, among other useful products.
  • the additional polyvinyl alcohol copolymers may include, for example, polyvinyl alcohol copolymers including comonomers containing sulfonic acid groups.
  • Examples of the comonomers containing sulfonic acid groups may include vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-l- methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2- methacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, and salts thereof, among others, where the comonomers may be incorporated into the polymer in amounts ranging from about 1 to about 6 mole% (94 to 99 mole percent of vinyl alcohol and vinyl ester monomer), such as in the range from about 2 to about 5 mole% or from about 3 to about 4.25 mole% in other embodiments.
  • blends of the pyrrolidone containing polyvinyl alcohol copolymers and sulfonic acid group containing polyvinyl alcohol copolymers may result in improved unit dose packaging, where it its theorized that the AMPS containing copolymer may provide for enhanced solubility while the pyrrolidone containing copolymer may provide for color stability and/or flexibility of the film, even after exposure to harsh chemicals for extended periods of time at elevated temperatures.
  • the blends of the pyrrolidone containing polyvinyl alcohol copolymers and sulfonic acid group containing polyvinyl alcohol copolymers may contain from 10 to 90 wt% of the pyrrolidone containing polyvinyl alcohol copolymers and from 90 to 10 wt% of the sulfonic acid group containing polyvinyl alcohol copolymer in some embodiments; from 15 to 85 wt% of the pyrrolidone containing polyvinyl alcohol copolymers and from 85 to 15 wt% of the sulfonic acid group containing polyvinyl alcohol copolymer in other embodiments; and from 20 to 80 wt% wt% of the pyrrolidone containing polyvinyl alcohol copolymers and from 80 to 20 wt% of the sulfonic acid group containing polyvinyl alcohol copolymer in yet other embodiments, the above percentages based on the total amount of polyvinyl alcohol copoly
  • the blends may include from about 20 to 30 wt% of the pyrrolidone containing polyvinyl alcohol copolymers and from about 70 to 80 wt% of the sulfonic acid group containing polyvinyl alcohol copolymer, based on the total amount of polyvinyl alcohol copolymers.
  • the water- soluble film may include the pyrrolidone containing polyvinyl alcohol copolymers (A) and the sulfonic acid group containing polyvinyl alcohol copolymer (B) at a weight ratio A:B in the range from about 1:4 to about 4:1, such as at a weight ratio of A:B in the range from about 1:2.5 to about 1:3.25.
  • the blends may include the pyrrolidone containing polyvinyl alcohol copolymer in an amount ranging from a lower limit of 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt% to an upper limit of 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 wt%, based on the total amount of polyvinyl alcohol copolymers, where any lower limit may be combined with any upper limit.
  • the blends may include the sulfonic acid group containing polyvinyl alcohol copolymer in an amount ranging from a lower limit of 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, or 85 wt% to an upper limit of 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 wt%, based on the total amount of polyvinyl alcohol copolymers, where any lower limit may be combined with any upper limit.
  • the components of the film formulations may be blended together prior to film fabrication by any suitable means.
  • the saccharide component and/or chlorine scavenger may be dissolved in and/or blended with the vinyl alcohol copolymer or an aqueous solution of the vinyl alcohol copolymer.
  • the blend may then be used to produce water soluble films.
  • Suitable film forming methods may include film casting, wet process film formation, dry process film formation, film extrusion, melting film formation, coating process and blown film methods, among others.
  • the film may be formed by a solution casting processes.
  • An aqueous solution of the film may be prepared at about 10 to 30 percent solids by weight.
  • the solution may then be added to a trough on a metal forming belt and a doctor blade spreads the solution out on the belt to a predetermined thickness.
  • the belt is then passed through an oven to evaporate the water, which dries the film to a moisture content of about 6 to 15%.
  • the polymer films may be fabricated to thickness in ranges of from about 10 to 200 microns, for example, such as from about 20 to 150 microns, or from about 50 to about 100 microns. [0059]
  • the water soluble films that may be produced with the vinyl alcohol copolymers described herein are useful for any purpose where water solubility is an advantage.
  • the films are particularly suitable for unit-dose packaging of harsh oxidizing chemicals, such as may be found in agricultural chemicals, microbiocides and the like, where the chemicals in unit dose packaged form may be placed into water so that the contents are dissolved or dispersed in the water. This is accomplished without the necessity of the user directly touching the harmful chemicals, and without the need to measure the chemicals, as the unit dose package contains a known quantity of the chemical.
  • Examples of chemicals that may be packaged using films according to embodiments herein may include: peroxides such as barium peroxide, sodium carbonate peroxide, calcium peroxide, hydrogen peroxide, lithium peroxide, magnesium peroxide, strontium peroxide, zinc peroxide, and sodium peroxide; ketone peroxides such as acetone peroxide, methyl ethyl ketone peroxide, and benzoyl peroxide; nitrates such as aluminum nitrate, potassium nitrate, silver nitrate, calcium nitrate, sodium nitrate, cupric nitrate, lead nitrate, magnesium nitrate, strontium nitrate, nickel nitrate, and guanidine nitrate; nitrites such as sodium nitrite; chromates and dichromates such as potassium dichromate, sodium dichromate, and ammonium dichromate; sulfates and persulfates such as sodium bisulfate
  • the films are particularly suitable to produce unit dose packaging for sanitizing chemicals such as those used to disinfect pools, spas, and potable water.
  • Sanitizing chemicals include chlorine-containing compounds which produce hypochlorous acid when contacted with water.
  • Hypochlorous acid is the effective sanitizing agent, and the amount of hypochlorous acid which can be produced by a sanitizing chemical relative to chlorine gas (Ck) is referred to as“available chlorine content.”
  • the sanitizing agents may be provided as powder, granules, tablets, liquid, gel, or any other suitable form.
  • Sanitizing agents include hypochlorite salts such as sodium hypochlorite, calcium hypochlorite, and lithium hypochlorite; chlorinated isocyanurates such as dichloroisocyanuric acid (also referred to as “dichlor” or dichloro-s-triazinetrione, 1 ,3-dichloro- 1 ,3,5-triazinane-2,4,6-trione) and trichloroisocyanuric acid (also referred to as “trichlor” or l,3,5-trichloro-l,3,5- triazinane-2,4,6-trione). Salts and hydrates of the sanitizing compounds are also contemplated.
  • hypochlorite salts such as sodium hypochlorite, calcium hypochlorite, and lithium hypochlorite
  • chlorinated isocyanurates such as dichloroisocyanuric acid (also referred to as “dichlor” or dichloro-s-tri
  • dichloroisocyanuric acid may be provided as sodium dichloroisocyanurate, sodium dichloroisocyanurate acid dihydrate, among others.
  • Bromine containing sanitizing agents may also be suitable for use in unit dose packaging applications, such as l,3-dibromo-5,5-dimethylhydantoin (DBDMH), 2,2- dibromo-3-nitrilopropionamide (DBNPA), dibromocyano acetic acid amide, 1-bromo- 3-chloro-5,5-dimethylhydantoin; and 2-bromo-2-nitro- 1,3-propanediol (BNPD,
  • the films described above may be formed into unit dose packaging by adding a predetermined amount of the harsh chemical, in granular, powder, liquid or tablet form, to the film and hermetically sealing the film around the oxidizing chemical to produce a dissolution packet that includes the active chemical agent.
  • the films described above may exhibit stability when in contact with harsh chemicals, including aggressive oxidizing chemicals.
  • Stability refers to the films ability to maintain various physical and chemical properties, even under elevated temperature and long-term storage conditions, including a high degree of water- solubility, such as >85 wt% dissolution at 21°C, low discoloration, and chemical resistance.
  • polyvinyl alcohol (PVOH) copolymers may be useful in harsh chemical packaging.
  • the composition may include a water-soluble saccharide, such as dextrose, and a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer, and (b) from 1 to 20 mole percent of a pyrrolidone comonomer, such as N-vinyl pyrrolidone.
  • the polyvinyl alcohol copolymer may have a degree of hydrolysis in the range from about 65% to about 99%.
  • Film compositions disclosed herein may exhibit stability, including low discoloration and solubility in water, even after exposure to harsh chemicals and heat aging.
  • the film compositions disclosed herein may exhibit essentially no yellowing when exposed to a harsh chemical and aged at a temperature in the range from about 5°C to about 54°C for at least 4 weeks, such as at a temperature in the range from about 30°C to about 54°C for at least 4 weeks, at least 8 weeks, or at least 12 weeks.
  • Essentially no yellowing refers to maintenance of a clear color, or the occurrence of a slight haze to a light yellowing in color due to reaction of the polyvinyl alcohol copolymer with the harsh chemical during the heat aging period.
  • film compositions disclosed herein may nonetheless retain a high degree of solubility in water, after heat aging.
  • the film compositions may have a percent dissolution by weight in water at 21°C of at least 85 wt%, even following exposure to a harsh chemical and aging at a temperature in the range from about 5°C to about 54°C for at least 4 weeks, such as 4 to 12 weeks.
  • Some embodiments may retain a percent dissolution by weight in water at 21°C of at least 90 wt%, even following exposure to a harsh chemical and aging at a temperature in the range from about 30°C to about 54°C for at least 6 weeks, 8 weeks, 12 weeks, or longer.
  • polyvinyl alcohol copolymers and film compositions disclosed herein may be useful in unit dose packages, including unit dose packages for harsh chemicals.
  • the unit dose package may include a polymeric dissolution packet and a harsh chemical, where the polymeric dissolution packet includes: from 60 to 95 weight percent of a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 4 to 12 mole percent of a pyrrolidone comonomer; from 1 to 40 weight percent dextrose; and from 1 to 5 weight percent polyethylene glycol.
  • a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 4 to 12 mole percent of a pyrrolidone comonomer; from 1 to 40 weight percent dextrose; and from 1 to 5 weight percent polyethylene glycol.
  • the unit dose package may include a polymeric dissolution packet and a harsh chemical, where the polymeric dissolution packet includes: from 60 to 95 weight percent of a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 4 to 12 mole percent of a pyrrolidone comonomer; from 1 to 10 weight percent dextrose; and from 1 to 20 weight percent polyethylene glycol.
  • Such dissolution packets may be suitable for harsh chemicals such as dichloroisocyanuric acid, trichloroisocyanuric acid, and calcium hypochlorite, among others.
  • the unit dose package may include a polymeric dissolution packet and a harsh chemical, where the polymeric dissolution packet includes: from 60 to 95 weight percent of a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 4 to 12 mole percent of a pyrrolidone comonomer; from 1 to 40 weight percent dextrose; and from 1 to 15 weight percent of at least one of trimethylol propane and alkoxylated trimethylol propane.
  • a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 4 to 12 mole percent of a pyrrolidone comonomer; from 1 to 40 weight percent dextrose; and from 1 to 15 weight percent of at least one of trimethylol propane and alkoxylated trimethylol propane.
  • the unit dose package may include a polymeric dissolution packet and a harsh chemical, where the polymeric dissolution packet includes: from 60 to 95 weight percent of a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 4 to 12 mole percent of a pyrrolidone comonomer; from 1 to 10 weight percent dextrose; and from 1 to 20 weight percent of at least one of trimethylol propane and alkoxylated trimethylol propane.
  • a polyvinyl alcohol copolymer consisting essentially of: (a) from 80 to 99 mole percent of vinyl alcohol and vinyl ester monomer; and (b) from 4 to 12 mole percent of a pyrrolidone comonomer; from 1 to 10 weight percent dextrose; and from 1 to 20 weight percent of at least one of trimethylol propane and alkoxylated trimethylol propane.
  • the polymeric dissolution packet may further include from 0.5 to 3 weight percent of at least one of ammonium chloride, citric acid, starch, potassium bicarbonate, and sodium bisulfite, and/or from 0.5 to 10 weight percent glycerine, such as 0.5 to 5 weight percent glycerine.
  • Such a dissolution packet may be suitable for harsh chemicals such as l-bromo-3-chloro-5,5-dimethylhydantoin, 2-bromo-2- nitro- 1,3 -propanediol, l,3-dibromo-5,5-dimethylhydantoin, 2,3-dibromo-3- nitrilopropionamide, and dibromocyano acetic acid amide, among others.
  • harsh chemicals such as l-bromo-3-chloro-5,5-dimethylhydantoin, 2-bromo-2- nitro- 1,3 -propanediol, l,3-dibromo-5,5-dimethylhydantoin, 2,3-dibromo-3- nitrilopropionamide, and dibromocyano acetic acid amide, among others.
  • Film compositions disclosed herein may be exhibit stability, including low discoloration and a high degree of solubility in water, even after exposure to harsh chemicals and heat aging.
  • Such findings are in direct contrast to prior art teachings indicating that pyrrolidone containing polymers and sulfonate containing polymers are unsuitable for such applications, teaching instead that intricate tetrapolymers and specific additives are necessary.
  • the compositions disclosed herein unexpectedly provide for the desired stability without requiring such intricate measures.
  • compositions described herein were tested to determine their performance characteristics when used in harsh chemical packaging. The testing was performed according to the following test description. Films are prepared from the formulations by casting an aqueous solution of the composition onto a glass plate, which is leveled by gravity and allowed to dry to a moisture content in the range from about 6 wt% to about 15 wt%. An amount of the solution is added to the plate to provide for a film with a target thickness, which may depend on the sample target, such as 38 micron (about 1.5 mil), 50 micron (about 2 mil), 63 micron (about 2.5 mil), and 76 micron (about 3.0 mil), as noted in the tables below.
  • the water in the solution is allowed to evaporate, and the resulting films are cut into an approximately 7.6 cm by 7.6 cm square (a 3-inch by 3-inch square) or a 7.6 cm by 6.3 cm rectangle (a3-inch by 2.5- inch rectangle), as indicated.
  • the film is then folded in half and three sides of the film are heat-sealed using a hand held heat-sealing gun.
  • the resulting pouch is then filled with 15-20 grams of a harsh chemical, which may be in granular form, for example, and the fourth side of the pouch is heat sealed.
  • the filled pouches are stored side-by- side in low density polyethylene bags between blue paper towels (to check for bleaching).
  • the filled pouches are then stored at selected temperature conditions and ambient humidity, and aged for a selected time period.
  • the filled pouches are cut open and the chemical is removed.
  • the film thickness is measured and color recorded, and the film is tested for water solubility.
  • a sample of the film is mounted in a slide frame and placed in a 500 ml beaker filled with 400 ml water.
  • the beaker is placed on a magnetic stirrer, and the water is stirred with a magnetic stir bar such that a vortex is created.
  • the water temperature is maintained as noted, such as at about 21°C.
  • the frame is secured in the beaker with a clamp which is supported by a platform such that stirring water pushes against the film.
  • the film begins to balloon or wave. The disintegration time is recorded when the film balloon bursts.
  • the frame After disintegration, the frame remains in water and the dissolution time is recorded as the total time (inclusive of disintegration time) when no residual strings of film and no film particles remain on the frame. Following 15 minutes, the dissolution test is terminated and the percentage of the film dissolved is measured via filtration across a 325 mesh screen.
  • Plasticizer G : Glycerin; Digly: diglycerine; PEG: Polyethylene glycol (number average MW 200 - 1000); TMP: trimethylolpropane; PG: Propylene glycol; ATMP : Alkoxylated- trimethylolpropane;
  • D Dextrose
  • CC Citric acid
  • KC Potassium chloride
  • NH4CI Ammonium Chloride
  • St Starch
  • Eryt Pentaerythritol
  • DIPA Diisopropanolamine
  • NaBS Sodium bisulfite (used as additive and chemical) 3 Chemical: Dichlor: Dichloroisocyanuric acid; CalHypo: Calcium hypochlorite; Trichlor: Trichloroisocyanuric acid; BCDMH: l-bromo-3-chloro -5,5- dimethylhydantoin; DBDMH: l,3-dibromo-5,5-dimethylhydantoin; DBNPA: 2,3- dibromo-3-nitrilopropionamide; BNPD (Bronopol) : 2-bromo-2-nitro-l,3- propanediol;
  • Tables 3 and 4 provide the test conditions and results for the samples and comparative samples.
  • Table 5 summarizes some of the test results for samples and comparative samples used with a dichlorinated harsh chemical, such as dichloroisocyanuric acid, dichloro-s-triazinetrione or l,3-dichloro-l,3,5-triazinane-2,4,6-trione.
  • Table 6 summarizes test conditions and results for some of the samples and comparative samples used with a trichlorinated harsh chemical, such as trichloroisocyanuric acid or l,3,5-trichloro-l,3,5-triazinane-2,4,6-trione.
  • a trichlorinated harsh chemical such as trichloroisocyanuric acid or l,3,5-trichloro-l,3,5-triazinane-2,4,6-trione.
  • Table 7 summarizes test conditions and results for some of the samples and comparative samples used with calcium hypochlorite as the harsh chemical.
  • Tables 8 and 9 summarize test conditions and results for some of the samples and comparative samples used with a bromicide, l-bromo-3-chloro-5, 5- dimethylhydantoin (BCDMH), and a bronopol, 2-bromo-2-nitro- 1,3-propanediol (BNPD).
  • BCDMH 5- dimethylhydantoin
  • BNPD 2-bromo-2-nitro- 1,3-propanediol
  • Tables 10 and 11 summarize test conditions and results for some of the samples and comparative samples used with l,3-dibromo-5,5-dimethylhydantoin (DBDMH), 2,2-dibromo-3-nitrilopropionamide (DBNPA), or dibromocyano acetic acid amide.
  • Table 10 - DBDMH l,3-dibromo-5,5-dimethylhydantoin
  • DBNPA 2,2-dibromo-3-nitrilopropionamide
  • Table 10 - DBDMH dibromocyano acetic acid amide
  • vinyl alcohol - vinyl pyrrolidone copolymers may be suitable for use in packaging harsh chemicals. Specifically, various samples retained a clear appearance, indicating a high film stability (i.e., high resistance to attack by the harsh chemicals). Further, even where some color formation occurred, the samples retained excellent water solubility and physical strength. Accordingly, samples assessed as A or“slightly yellow” were deemed compatible with the packaged chemicals, since there are many applications where slight discoloration is not of concern for a customer as long as the film maintains its requisite solubility and other physical properties. Film compositions disclosed herein may thus be suitable for use as a harsh chemical packaging film, even where significant aging times may lapse at elevated temperatures prior to use of the packet by an end consumer.
  • the vinyl alcohol copolymers containing pyrrolidone comonomers may be advantageously used in admixture with polyvinyl alcohol copolymers including comonomers containing sulfonic acid groups.
  • Films and unit dose packages were formed with a mixture of VOH-NVP copolymer (5 mole% NVP) and VOH-AMPS copolymer (4 mole% AMPS), as formulated in Table 12.
  • the unit dose packages were contacted with various chemicals and tested according to the procedures described above (2,2-dibromo-3-nitrilopropionamide (DBNPA) at 54°C), the results of which are shown in Table 13, and various comparisons are shown in Tables 14A and B.
  • DBNPA 2,2-dibromo-3-nitrilopropionamide
  • compositions described in Table 15, as well as those in Tables 1 and 2 were tested to determine their performance characteristics when used in additional harsh chemical packaging, using the test method outlined above. The tests were performed for comparative purposes, as well as to determine suitability of the compositions for storing additional harsh chemicals. Table 16 provides the test conditions and results for the various compositions tested. Table 16.
  • plasticizer(s), additives(s), and the chemical stored may have a significant impact on the suitability of a film for harsh chemical storage and handling.
  • Common or preferred plasticizers such as glycerine, for example, have been found to be inappropriate for use with some harsh chemicals, resulting in poor film performance.
  • plasticizers generally considered less optimal, such as those that are a solid at room temperature, trimethylol propane for example, have been found to perform extremely well, as exemplified by the numerous examples above.
  • compositions according to embodiments herein may be used, successfully, for long term storage of a wide variety of harsh chemicals, even at elevated temperatures.
  • Films made according to embodiments herein may be compatible with each of the following chemical groups: peroxides, nitrates, nitrites, chromates, persulfates, borates, bromates, chlorates, periodates, chlorites, chlorinated or brominated isocyanurates, inorganic acids, organic acids, peroxy acids, superoxides, and salts and hydrates of these compounds.
  • films according to embodiments herein may be compatible with each of dichloroisocyanuric acid, calcium hypochlorite, trichloroisocyanuric acid, l-bromo-3-chloro -5,5-dimethylhydantoin, 1,3-dibromo- 5,5-dimethylhydantoin, 2,3-dibromo-3-nitrilopropionamide; 2-bromo-2-nitro- 1 ,3- propanediol, sodium bisulfate, tartaric acid, fumaric acid, oxalic acid, sodium percarbonate, sodium carbonate, sodium bicarbonate, cyanuric acid, and potassium monopersulfate.
  • “Compatible” as used herein refers to the film exhibiting stability during storage of a chemical, including no or minimal package film discoloration, maintenance of flexibility and structural integrity of the film, and exhibiting acceptable water solubility, following extended exposure to the chemical.
  • the type and amount of additives and plasticizers used may impact convertibility of the admixture into a useful film.
  • the films produced need to have desirable mechanical and physical properties, as well as the aforementioned chemical resistance.
  • Films as described herein may have a modulus, elasticity, and tensile strength, as described above, that are suitable for converting the films into end products, such as unit dose packs.
  • Some embodiments may utilize plasticizers and/or additives that are solid at room temperature, thus imparting desirable physical, mechanical, and chemical characteristics to the resulting films.
  • plasticizers and/or additives may more effectively hinder migration of the harsh chemicals into the film, improving the stability and structure of the film while concurrently maintaining solubility of the water-soluble polymer.
  • High molecular weight plasticizers and additives, and/or those with significant hydrogen bonding capability, such as those with 2, 3, 4, or more hydroxyl groups, may likewise contribute to hindered migration, for example.
  • embodiments disclosed herein relate to water-soluble polyvinyl alcohol compositions and films formed therefrom that exhibit resistance to aggressive oxidizing chemicals.
  • embodiments disclosed herein may provide for water soluble film compositions that exhibit stability, retaining a high degree of water solubility, a high degree of film integrity, and a high degree of flexibility, as well as low discoloration, even following extended exposure to harsh chemicals at elevated temperatures.
  • Such films may thus be suitable for use in unit dose packaging of harsh chemicals, providing an extended shelf life, handling safety, and other benefits as may be readily envisioned by one skilled in the art.

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Abstract

L'invention concerne un film hydrosoluble utile dans un emballage de produit chimique à dose unitaire. Le film peut comprendre : un saccharide hydrosoluble et un copolymère d'alcool polyvinylique consistant essentiellement en : (a) de 80 à 99 pour cent en moles de monomère d'alcool vinylique et d'ester vinylique; et (b) de 1 à 20 pour cent en moles d'un comonomère de pyrrolidone. De telles compositions peuvent être utilisées pour fournir un film hydrosoluble satisfaisant simultanément aux exigences vis-à-vis de la solubilité dans l'eau, de la biodégradabilité et des propriétés physiques, même lorsqu'il est utilisé pour emballer une large gamme de produits chimiques oxydants agressifs.
EP19835334.4A 2018-12-03 2019-12-03 Copolymère de pvp pour l'emballage d'un produit chimique agressif Withdrawn EP3891213A1 (fr)

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US16/208,298 US20190169383A1 (en) 2012-10-22 2018-12-03 Pvp copolymer for harsh chemical packaging
PCT/US2019/064199 WO2020117777A1 (fr) 2018-12-03 2019-12-03 Copolymère de pvp pour l'emballage d'un produit chimique agressif

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JPH02124945A (ja) 1988-07-27 1990-05-14 Kuraray Co Ltd 水溶性フイルム
EP0884352B1 (fr) 1997-06-11 2001-09-05 Kuraray Co., Ltd. Feuille hydrosoluble
US6608121B2 (en) 2000-08-07 2003-08-19 Kuraray Co., Ltd. Water-soluble resin composition and water-soluble film
EP1251147B1 (fr) 2001-04-20 2004-09-08 Kuraray Co., Ltd. Film soluble dans l'eau et emballage l'utilisant
US6821590B2 (en) 2003-02-14 2004-11-23 Monosol, Llc Starch-loaded polyvinyl alcohol copolymer film
US7022656B2 (en) 2003-03-19 2006-04-04 Monosol, Llc. Water-soluble copolymer film packet
US7745517B2 (en) 2006-05-02 2010-06-29 Sekisui Specialty Chemicals America, Llc Polyvinyl alcohol films with improved resistance to oxidizing chemicals
TWI548655B (zh) * 2012-10-22 2016-09-11 積水特殊化學美國有限責任公司 用於嚴苛化學品包裝的聚乙烯吡咯啶酮（ｐｖｐ）共聚物
EP3190063B1 (fr) * 2014-09-01 2021-08-18 Sekisui Chemical Co., Ltd. Film d'emballage soluble dans l'eau
JP6397323B2 (ja) * 2014-12-15 2018-09-26 積水化学工業株式会社 多層薬剤包装用フィルム
US20160369072A1 (en) * 2015-06-16 2016-12-22 Sekisui Specialty Chemicals America, Llc Water-soluble film for packaging chemicals and water-soluble film package

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