Water-soluble sheets for recreational water treatment

Abstract

Disclosed herein is a water-soluble sheet for use in a recreational water system comprises a sheet comprising a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent, as well as its preparation and use for the treatment of a recreational water system.

Description

WATER-SOLUBLE SHEETS FOR RECREATIONAL WATER TREATMENT Related Application

[0001] This application claims priority to and the benefit of U.S. Provisional Patent Application No.63 / 643,953, filed on May 8, 2024. Summary

[0002] Disclosed herein is a water-soluble sheet for use in a recreational water system comprises a sheet comprising a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent, as well as its preparation and use for the treatment of a recreational water system. Background

[0003] Recreational water facilities, such as swimming pools, hot tubs, and water parks, require regular maintenance to ensure the safety and quality of the water. Traditional methods of water treatment often involve the use of liquid or powder chemicals, which can be cumbersome to handle and measure accurately as well as be messy if spilled and difficult to clean up. Consumers would prefer water treatment products that are simpler and less messy than the current conventional products.

[0004] An increasing focus for both customers and industries is on sustainability and environmental impact of manufactured consumer products. Water minimization is a key focus, as more highly concentrated products can offer higher performance as well as lower costs for transportation due to lower mass and better space efficiency. This has led to several segments of consumer home cleaning products, such as laundry, glass, surface, and toilet cleaners to explore waterless methods of application. Sheets consisting of a water-soluble matrix acting as a carrier for surfactants, enzymes, and / or fragrances have emerged as a popular alternative to conventional liquid cleaning products. In addition to the environmental impact benefits, consumers appreciate the ability to apply the product as a premeasured unit, and avoid messes, spills, and residue that can accompany liquid products.

[0005] Recreational water treatment products differ from conventional household cleaners in that typically significantly much larger volumes of water – hundreds of gallons for spas, thousands to tens-of-thousands for pools – must be treated, necessitating either a larger volume applied or a more concentrated product than is typical of other product classes for consumer use that have been successfully adapted to a water-soluble sheet format. However, there are several classes of recreational water products that do not require high levels of functional compounds to be present in the water to achieve their desired benefit. Thesefunctional chemistries differ from the surfactant / enzyme / fragrance functional actives common to other home cleaning products, making them distinct and novel.

[0006] There is a need for a more convenient and effective approach to recreational water treatment.

[0007] Water-soluble sheets comprising polyvinyl alcohol (PVA) offer an innovative solution to this problem. PVA is a water-soluble synthetic polymer that has been widely used in various applications. By utilizing PVA sheets for recreational water treatment, facility managers and owners can simplify the process of water treatment.

[0008] PVA sheets for recreational water treatment consist of thin, flexible sheets made from polyvinyl alcohol. PVA is a suitable material for this application due to its excellent water solubility and compatibility with various chemicals commonly used in water treatment. The PVA sheets are designed to dissolve rapidly and completely upon contact with water, releasing the chemicals they contain.

[0009] The active chemicals incorporated into the PVA sheets can vary depending on the specific needs of the recreational water facility. Chemicals used in these sheets may include, for example, a clarifier, a corrosion inhibitor, a pH adjuster, a sanitizer, a waterline cleaner, and the like. The chemicals are formulated to be compatible with PVA and to dissolve effectively, ensuring proper water treatment.

[0010] One of the key advantages of using PVA sheets for recreational water treatment is their convenience and ease of use. End users need only to place the appropriate number of PVA sheets into the water, and the sheets will dissolve, releasing the necessary chemicals. This eliminates the need for complex measuring and handling of liquid or powder chemicals, making water treatment more user-friendly, less messy and more efficient.

[0011] Furthermore, PVA sheets offer precise and controlled chemical dosing. Each sheet contains a pre-determined amount of chemicals, ensuring consistent and accurate dosing with each use. This helps to maintain optimal water quality and prevent over or under-dosing, which can lead to ineffective treatment or potential health risks.

[0012] PVA sheets can also be customized to address specific water treatment requirements. By adjusting the formulation of the sheet material and the active chemicals, manufacturers can create sheets that effectively address various water quality issues. This versatility allows recreational water end-users to tackle different challenges, such as controlling bacterial growth, maintaining pH balance, and preventing the formation of algae.

[0013] In conclusion, PVA sheets for recreational water treatment provide a convenient, efficient, and precise alternative to traditional liquid or powder chemicals. Byutilizing PVA's water solubility and compatibility with water treatment chemicals, facility managers and owners can streamline the process of water treatment, ensuring optimal water quality and safety for recreational water users. Definitions

[0014] The phrase "a" or "an" entity as used herein refers to one or more of that entity. For example, an agent refers to one or more agents or at least one agent. As such, the terms "a" (or "an"), "one or more", and "at least one" can be used interchangeably herein. The use of the definite article ("the") to refer to "an entity" refers to one or more of that entity. For example, when the expression "the agent" refers to the previously recitation of "an agent" it is understood that the expression "the agent" refers to one or more agents.

[0015] The terms "optional" or "optionally" as used herein means that a subsequently described agent may be absent from a composition disclosed herein, or that an event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances in which it does not. In instances where "optional" or "optionally" relates to an agent, one may alternatively read, e.g., optional to include an amount of agent present in an amount of from 0% to some stated numerical value.

[0016] Numerical values included herein reflect, e.g., amounts of an identified agent, which may be expressed as a range or a single number. It is understood that the numerical values may be associated with a certain variation (or experimental error) associated with mass balances, instrumentation, and the like. Accordingly, a numerical value reported herein may be associated with a degree of uncertainty which may be ±10% of the stated value or less, e.g., ±5%, ±2%, ±1%, ±0.5%, and the like.

[0017] Numerical ranges may be employed to describe amounts of materials and / or one more agent present for a water-soluble sheet disclosed herein. For instance, a numerical range may include numerical lower and upper limits (e.g., 5% to 80%), which includes all integer values in between.

[0018] Unless specified otherwise, the expression "%" refers to "% m / m," which refers to the percent amount of the mass of a material and / or an agent (e.g., g) per mass (e.g., g) of the water-soluble sheet.

[0019] The expression "Da" refers to "Dalton," which is an atomic mass unit, which is 1 / 12 the mass of carbon-12.

[0020] The expression "CAS" refers to the "Chemical Abstract Service," which when associated with a number (e.g., CAS 68610-92-4) refers to the Chemical Abstract Service Registry number.Detailed Description

[0021] A first embodiment relates to a water-soluble sheet for use in a recreational water system comprises a sheet comprising a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent.

[0022] The polyvinyl alcohol may be present in an amount of 5% to 95% based on the mass of the water-soluble sheet and all values in between, including, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, and 90%. For instance, the polyvinyl alcohol may be present an amount of from: (i) 5% to 75%, (ii) 5% to 30%, or (iii) 50% to 75% based on the mass of the water-soluble sheet.

[0023] In one aspect, the polyvinyl alcohol may be any suitable grade so long as it is capable of dissolving in the recreational water. Specific polyvinyl alcohol (PVA) grades include, but are not limited to high viscosity (e.g., PVA having a molecular mass of about 200 kDa), a medium viscosity (e.g., PVA having a molecular mass of about 130 kDa), and a low viscosity (e.g., PVA having a molecular mass of about 20 kDa).

[0024] In another aspect, the PVA contemplated herein may comprise a measurable mol-% amount of monomeric vinyl acetate, where the amount of monomeric vinyl acetate is less than about 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, 24 mol%, 23 mol%, 22 mol%, 21 mol%, 20 mol%, 19 mol%, 18 mol%, 17 mol%, 16 mol%, 15 mol%, 14 mol%, 13 mol%, 12 mol%, 11 mol%, 10 mol%, 9 mol%, 8 mol%, 7 mol%, 6 mol%, 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, and 0 % mol.

[0025] PVA may be prepared by saponifying polyvinyl acetate in the presence of one or more of a saponification catalyst. See, e.g. Vacca. Additionally, PVA may be obtained commercially and used as as. Examples of various commercially available PVAs include Ghosenol™, Mowiol™, Poval™, Selvol™.

[0026] In another aspect, the water-soluble sheet may further comprise a functional ingredient, which comprises one or more of a disintegrant, a non-aqueous solvent, and water.

[0027] For instance, a disintegrant may be present in the water-soluble sheet in an amount of from 0% to 70% by mass of the water-soluble sheet and all values in between, including, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, and 65%.

[0028] Examples of disintegrants include, but are not limited to, an alginic acid or a salt thereof (e.g., calcium alginate, sodium alginate, etc.), a carboxymethylcellulose or a salt thereof (e.g., carboxymethylcellulose calcium and carboxymethylcellulose sodium), a cellulose (e.g., powdered cellulose, microcrystalline cellulose, and the like), an C1-C3 alkyl cellulose(e.g., methylcellulose, ethylcellulose, propylcellulose), a hydroxy C1-C3 alkyl cellulose (e.g., hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose), a chitosan or a salt thereof, a starch (e.g., corn starch, pregelatinized starch, and the like), colloidal silicon dioxide, croscarmellose sodium, crospovidone, docusate sodium, glycine, guar gum, magnesium aluminum silicate, polacrilin potassium, povidone, sodium starch glycolate. It may be convenient for the water-soluble sheet to include one or more disintegrants, including, for example, a starch and a cellulose.

[0029] In one aspect, the non-aqueous solvent may be present in the water-soluble sheet in an amount of from 0% to 50% by mass of the water-soluble sheet and all values in between, including, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, and 45%.

[0030] Generally, the non-aqueous solvent exhibits water miscibility. Examples of non-aqueous solvents include, but are not limited to, a C1-C4alkanol (e.g., methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol), a C2-C4 alkanediol (e.g., glycerol, ethylene glycol, propylene glycol (including 1,2-propanediol and 1,3-propanediol), butylene glycol (including 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol)), benzyl alcohol, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, a polyethylene glycol (e.g., PEG 200, PEG 300, PEG 400, etc.), and the like. A non-aqueous solvent (e.g., glycerin) may be incorporated into a water-soluble sheet as a part of the manufacturing process and / or to improve flexibility.

[0031] In yet another aspect, the water may be present in the water-soluble sheet in an amount of from 0% to 30% by mass of the water-soluble sheet and all values in between, including, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, and 25%.

[0032] Examples of water include, but are not limited to, potable water, purified water, deionized water, distilled water, and the like. Water may be incorporated into a water-soluble sheet as a part of the manufacturing process, to improve flexibility, and / or as a part of a salt hydrate.

[0033] In one aspect, the water-soluble sheet may comprise one or more of a recreational water system agent, such as, for example, an alkaline agent, antifoaming agent, clarifier agent / flocculant, colorant, corrosion inhibitor, fragrant, halogen source, pH adjuster, a sanitizer, a water hardness agent, a water softness agent, a waterline cleaning agent, or a combination thereof.

[0034] In one aspect, the water-soluble sheet may be used to adjust the pH of the recreational water to achieve a value in the range from 6 to 8, including all values in between,such as 6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, and 7.8. Accordingly, the water-soluble sheet may comprise an alkaline agent in an amount of from 5% to 80% based on the mass of the water- soluble sheet and all values in between, including, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75%. For instance, the alkaline agent may be present an amount of from: (i) 5% to 75%, (ii) 5% to 30%, or (iii) 50% to 75% based on the mass of the water-soluble sheet.

[0035] Examples of alkaline agents include, but are not limited to sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, sodium citrate, sodium phosphate, or a combination thereof.

[0036] In another aspect, the water-soluble sheet may comprise an antifoaming agent in an amount of from 0% to 10% by mass of the water-soluble sheet and all values in between, including, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, and 9%. For instance, the antifoaming agent may be present in an amount of from 0.1% to 1% based on the mass of the water-soluble sheet.

[0037] Suitable examples of antifoaming agents include, but are not limited to, cyclomethicone (e.g., CAS No.69430-24-6), dimethicone (e.g., CAS 9006-65-9 (Dow Corning Q7-9120)), oleyl alcohol (e.g., CAS 143-28-2), polypropylene glycol 2000, simethicone (e.g., CAS 8050-81-5 (e.g., Dow Corning Q7-2243 LVA, Dow Corning Q7-2587, or Xiameter AFE- 0200)), and the like.

[0038] The water-soluble sheet disclosed herein may include a clarifier agent, a flocculant, or a combination thereof in an amount of from 5% to 80% by mass of the water- soluble sheet and all values in between, including, for example, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75% by mass of the water- soluble sheet. For instance, the clarifier agent, flocculant, or a combination thereof may be present in an amount of from: (i) 5% to 10%, (ii) 10% to 15%, (iii) 15% to 20%, (iv) 20% to 25%, (v) 25% to 30%, (vi) 30% to 35%, (vii) 35% to 40%, (viii) 40% to 45%, (ix) 45% to 50%, (x) 50% to 55%, (xi) 55% to 60% based on the mass of the water-soluble sheet.

[0039] Examples of clarifying agents include, but are not limited to a cationic polymer (e.g., polydiallyldimethylammonium chloride (polyDADMAC, e.g., CAS 26062-79-3)); a quaternized polymer (e.g., a quaternized hydroxyethyl cellulose (Polyquaternium-10, e.g., CAS 68610-92-4, CAS 81859-24-7, etc., see Sayre); a quaternized cellulose (see, e.g., Udoetok, Song, Wang); a quaternized starch (see, e.g., Yeh and Chiu); a quaternized chitosan (see, e.g., Pathak); a quaternized polylysine (see, e.g., Fleischel); a poly(butylmethacrylate; (trimethylaminoethyl) methacrylate, methyl methacrylate (1:2:1); a poly(ethyl acrylate, methylmethacrylate, trimethylammonioethyl methacrylate chloride (1:1:0.2, CAS 33434-24-1, e.g., Eudragit RL 100, Eudragit RL PO, Eudragit RL 30 D, Eudragit RL 12.5)); a poly(ethyl acrylate, methyl methacrylate, trimethylammonioethyl methacrylate chloride) (1:2:0.1, CAS 33434-24- 1); a copolymer of DADMAC and acrylic acid; a copolymer of DADMAC and methacrylic acid; a copolymer of DADMAC and methylmethacrylate; a copolymer of DADMAC and acrylamide; a quaternized ammonium group in the polymer chain (e.g., a quaternized water- soluble chelating polymer (see, e.g., Dobrawa, e.g., a quaternized poly(ethyleneimine)), a poly(oxyethylene-(dimethyliminio)ethylene(dimethylimino)ethylene dichloride, e.g., CAS 31512-74-0, a polyhexamethylene biguanide (PHMB or salts thereof, e.g., CAS 28757-47-3 and CAS 32289-58-0 (HCl)), poly(oxyethylene(diC2-3alkylimino)- hydroxypropylene(dialkylimino)-ethylene dichloride) polymer)).

[0040] A flocculant may comprise a multivalent cation, such as, for example, cations of aluminum, iron, calcium, and magnesium. Examples of flocculants include, but are not limited to, aluminum sulfate (Al2(SO4)3) or a hydrate thereof; aluminum chloride or a hydrate thereof (e.g., aluminum chlorohydrate (e.g., AlnCl3n-m•(OH)m, where n is 2 and m is 5); polyaluminum chloride (PACl) and aluminum chlorohydrate (ACH), as well as combinations thereof; ferric chloride (FeCl3) or a hydrate thereof; ferric sulfate (Fe(SO4)3) or a hydrate thereof; ferrous sulfate (Fe(SO4)2) or a hydrate thereof; and the like.

[0041] The water-soluble sheet disclosed herein may include a colorant in an amount of from 0% to 40% by mass of the water-soluble sheet and all values in between, including, for example, 0.001%, 0.002%, 0.004%, 0.006%, 0.008%, 0.01%, 0.012%, 0.014%, 0.016%, 0.018%, 0.020%, 0.022%, 0.024%, and so on up to 0.4%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, and 35%.

[0042] Examples of colorants include, but are not limited to C.I. 74120, 74300, and 74320, C.I. pigment blue 29, C.I. acid blue 249, C.I. direct blues 86 and 87, C.I. ingrain blues 1, 2, 3, and 5, C.I. pigment blues 15:1, 15:2, 15:3, and 17, C.I. pigment greens 7 and 37, and C.I. solvent blues 24, 25, and 55, C.I. vat blue 6 and 11, C.I. vat blue 42, C.I. acid yellow 23, and mixtures thereof.

[0043] In another aspect, the water-soluble sheet may comprise a corrosion inhibitor in an amount of from 5% to 50% by mass of the water-soluble sheet and all values in between, including, for example, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, and 45%. For instance, the corrosion inhibitor may be present an amount of from: (i) 5% to 10%, (ii) 10% to 15%, (iii) 15% to 20%, (iv) 20% to 25%, or (v) 25% to 50% based on the mass of the water-soluble sheet.

[0044] A corrosion inhibitor relates generally to an agent capable of reducing corrosion (e.g., metal corrosion) in the recreational water system. Examples of corrosion inhibitors include, but are not limited to, sodium hexametaphosphate, an anionic polymer (e.g., an acrylate, a copolymer of (meth)acrylate and a coumarate vinyl analog (Udabe)), a phosphonate salt (e.g., hydroxyethylidene diphosphonic acid (HEDP) or a salt thereof (e.g., sodium HEDP), 2-phosphonobutane 1,2,4-tricarboxylic acid (PBTC) or a salt thereof, 2- carboxyethylphosphonic acid (2CEPA) or a salt thereof), a carboxylate salt (e.g., citric acid or a salt thereof (e.g., sodium citrate such as trisodium citrate)), or a combination thereof. See, e.g., Al-Amiery and Deyab.

[0045] The water-soluble sheet disclosed herein may include a fragrant in an amount of from 0% to 40% by mass of the water-soluble sheet and all values in between, including, for example, 0.001%, 0.002%, 0.004%, 0.006%, 0.008%, 0.01%, 0.012%, 0.014%, 0.016%, 0.018%, 0.020%, 0.022%, 0.024%, and so on up to 0.4%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, and 35%. For instance, the fragrant may be present an amount of from: (i) 1% to 5%, (ii) 2% to 15%, (iii) 15% to 20%, (iv) 20% to 25%, or (v) 25% to 40% based on the mass of the water-soluble sheet.

[0046] A fragrant may be synthetic or natural (such as a plant extract). Examples of plant extracts include, but not limited to extracts of aloe vera, apple (e.g., Malus pumila Mill), arjuna (e.g., Terminalia arjuna), bitter leaf (e.g., Vernonia amygdalina), black seed (e.g., Nigella sativa), buffalo thorn (e.g., Ziziphus mucronate), cinnamon (e.g., Cinnamomum cassia), clove (e.g., Syzygium aromaticum), cloves (e.g., Syzygium aromaticum), eucalyptus (e.g., Eucalyptus globules), garlic (e.g., Allium sativum Linn.), ginger (e.g., Zingiber officinale Rosc.), gum arabic tree (e.g., acacia nilotica), jewelweed (e.g., Impatiens capensis), lemon grass (e.g., Cymbopogon citratus), mango (e.g., Mangifera indica), neem (e.g., Azadirachta indica A. Juss.), oregano (e.g., Origanum vulgare), papaya (e.g., Carica papaya), pepper (e.g., Piper nigrum), physic nut (e.g., Jatropha curcas), radish tree (e.g., Moringa oleifera), thyme (e.g., Thymus vulgaris), turmeric (e.g., Curcuma longa Linn.), verbena (e.g., Verbena officinalis), yucca (e.g., Yucca schidigera), etc.

[0047] In certain aspects, the water-soluble sheet may be used to increase the free available chlorine of the recreational water, in which case the water-soluble sheet may comprise a halogen source in an amount of from 5% to 80% based on the mass of the water-soluble sheet and all values in between, including, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75%. For instance, the halogen source may be presentan amount of from: (i) 5% to 75%, (ii) 5% to 30%, or (iii) 50% to 75% based on the mass of the water-soluble sheet.

[0048] Examples of halogen sources include, but are not limited to calcium hypochlorite, sodium hypochlorite, sodium dichloroisocyanurate, trichloroisocyanuric acid, sodium bromide, a halogenated hydantoin (e.g., 1,3-dibromo-5,5-dimethylhydantoin, bromo- chloro-dimethylhydantoin, 1,3-dichloro-dimethylhydantion, 1,3-dichloro-5-ethyl-5- methylhydantoin, 1,3-dibromo-5-ethyl-5-methylhydantoin, 1-bromo-3-chloro-5-methyl-5- ethylhydrantoin), and the like.

[0049] In certain aspects, it may be desirable to admix and / or coat the halogen source with a stabilizing agent, such as a silicate (e.g., sodium silicate (e.g., sodium metasilicate, sodium orthosilicate, sodium pyrosilicate)), a polysaccharide, a polymaleic acid, a polyacryclic acid, a polyacrylamide, a polyvinyl alcohol or a derivative thereof (e.g., PVA or a vinyl alcohol / sulfonic acid copolymer (e.g., VYTEK®) alternatively in admixture with dextrose), a polyethylene glycol (e.g., PEG 200, PEG 300, PEG 400), aluminum sulfate or hydrate thereof (e.g., aluminum sulfate dodecahydrate), magnesium sulfate or a hydrate thereof (e.g., magnesium sulfate tetrahydrate, magnesium sulfate heptahydrate, etc.), sodium borate or hydrate thereof (e.g., sodium tetraborate decahydrate, sodium metaborate octahydrate, etc.). See, e.g., Saeman, Lei, Jones, and Martin, and Vicari.

[0050] Given that a water-soluble sheet may be used to adjust the pH of the recreational water to achieve a value in the range from 6 to 8 (e.g., 7.2 to 7.6), the water-soluble sheet may comprise a pH adjuster in an amount of from 5% to 80% based on the mass of the water-soluble sheet and all values in between, including, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75%. For instance, the pH adjuster may be present an amount of from: (i) 5% to 75%, (ii) 5% to 30%, or (iii) 50% to 75% based on the mass of the water-soluble sheet.

[0051] Examples of pH adjusters include, but are not limited to sodium bisulfate, boric acid, cyanuric acid, citric acid, sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, sodium citrate, sodium phosphate, sodium borate or hydrate thereof (e.g., sodium tetraborate decahydrate, sodium metaborate octahydrate, etc.), and the like.

[0052] In certain aspects, the water-soluble sheet may be used to sanitize the recreational water, in which case the water-soluble sheet may comprise a sanitizer in an amount of from 2% to 80% based on the mass of the water-soluble sheet and all values in between, including, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75%. For instance, the sanitizer may be presentan amount of from: (i) 5% to 75%, (ii) 2% to 30%, or (iii) 50% to 75% based on the mass of the water-soluble sheet.

[0053] A sanitizer relates generally to an agent capable of decreasing microbial content in the recreational water. Examples of sanitizers include, but are not limited to, a quaternized amine (e.g., benzylalkonium chloride, alkylbenzyldimethyl ammonium chlorides (where the alkyl includes a C2-C18 alkyl)), a polyquaternium (e.g., polyquaternium-5, polyquaternium-7, polyquaternium-10, and the like), an inorganic metal salt (e.g., salts of copper and / or silver), sodium tetraborate or a hydrate thereof. One will appreciate that a halogen source (described above) may function as a sanitizer, and thus, in certain aspects, the water-soluble sheet may comprise a halogen source and / or a sanitizer.

[0054] In certain aspects, the water-soluble sheet may be used to increase the hardness of the recreational water, in which case the water-soluble sheet may comprise a water hardness agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet and all values in between, including, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75%. For instance, the water hardness agent may be present an amount of from: (i) 5% to 75%, (ii) 5% to 30%, or (iii) 50% to 75% based on the mass of the water-soluble sheet.

[0055] Examples of water hardness agents include, but are not limited to calcium chloride, magnesium chloride, calcium sulfate, magnesium sulfate, and the like.

[0056] Use of a water-soluble sheet comprising one or more water hardness agents permits increasing the water hardness (e.g., concentration of calcium and / or magnesium) to achieve a desired value in a range from about 60 ppm to about 200 ppm, including for example, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 180 ppm, and 190 ppm.

[0057] In certain aspects, the water-soluble sheet may be used to decrease the hardness of the recreational water, in which case the water-soluble sheet may comprise a water softness agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet and all values in between, including, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75%. For instance, the water softness agent may be present an amount of from: (i) 5% to 75%, (ii) 5% to 30%, or (iii) 50% to 75% based on the mass of the water-soluble sheet.

[0058] Examples of water softness agents include, but are not limited to, sodium tetraborate, boric acid, sodium hexametaphosphate, and the like.

[0059] In certain aspects, the water-soluble sheet may be used to introduce an agent to reduce the evaporative loss of water from the body of the recreational water, in which case the water-soluble sheet may comprise an evaporative-loss agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet and all values in between, including, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75%. For instance, the evaporative loss agent may be present an amount of from: (i) 5% to 75%, (ii) 5% to 30%, or (iii) 50% to 75% based on the mass of the water-soluble sheet.

[0060] Examples of evaporative loss agents include, but are not limited to, linear, branched, and unsaturated C4-C24 alcohols (e.g. butyl alcohol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, behenyl alcohol, lignoceryl alcohol, oleyl alcohol, and the like). Linear, branched, and unsaturated fatty alcohols, and blends thereof, can also function as evaporative-loss agents), waxes (e.g. beeswax, lanolin, carnauba wax, castor wax, jojoba oil, tallow tree wax), paraffins, oils (e.g. organic and mineral oils), and the like.

[0061] Use of a water-soluble sheet comprising one or more water softness agents permits decreasing the water hardness (e.g., concentration of calcium and / or magnesium) to achieve a desired value in a range from about 60 ppm to about 200 ppm, including for example, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, 160 ppm, 180 ppm, and 190 ppm.

[0062] In certain aspects, the water-soluble sheet may be used to clean the waterline of the recreational water, in which case the water-soluble sheet may comprise a waterline cleaning agent in an amount of from 0% to 40% by mass of the water-soluble sheet and all values in between, including, for example, 0.001%, 0.002%, 0.004%, 0.006%, 0.008%, 0.01%, 0.012%, 0.014%, 0.016%, 0.018%, 0.020%, 0.022%, 0.024%, and so on up to 0.4%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, and 35%.

[0063] The waterline cleaning agent provides a cleansing function and comprises one or more surfactants (e.g., an amphoteric surfactant (e.g., a C8-C20 alkyl dimethyl betaine (e.g., lauryl dimethyl betaine)), an anionic surfactant (a C8-C20alkyl sulfonate (e.g., sodium dodecyl sulfate), sodium lauroyl isethionate, sodium lauroyl glutamate, docusate sodium, and the like)), a cationic surfactant (e.g., a C8-C20 trimethylammonium bromide (e.g., tetradecyltrimethylammonium bromide, n-dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, and the like)), a non-ionic surfactant (e.g., glyceryl monooleate, 2-hydroxyethyl-12-hydroxyoctadecanoate, a polyoxyethylene sorbitan fatty acidester (e.g., Tween 20, Tween 40, Tween 60, Tween 80), cocamidopropyl betaine), or a combination thereof), one or more enzymes (such as, an amylase, a cellulase, a lipase, a mannanase, a protease, a pectate lyase, an oxidoreductase, or a combination thereof), and water. Commercial cleansing agents are available (e.g., Tergazyme®, which may be dissolved in about 70% v / v-80% v / v water). Any suitable cleansing agent may be used. See, e.g., Christensen, Deinhammer, Hede, and Teasdale.

[0064] A water-soluble sheet disclosed herein may be suitably dimensioned depending on the application. For instance, each of the length and width of a water-soluble sheet may be about 5.1 cm (≈2 inches) to about 102 cm (≈40 inches) and all values in between, such as 6 cm, 7 cm, 8 cm, 9 cm, 10 cm, 11 cm, 12 cm, 13 cm, 14 cm, etc. The thickness may range from about 0.1 mm (≈3.9 mil) to about 5 mm (≈196 mil). The total mass of a water-soluble sheet may range from about 1 g to about 20 g.

[0065] Solid PVA has a density of from about 1.2 g / mL to about 1.3 g / mL at 25°C. A water-soluble sheet for use in a recreational water system disclosed herein comprises a sheet comprising a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent. The inclusion of one or more of a functional ingredient and one or more of a recreational water system agent may result in a sheet that has density less than about 1 g / mL, about 1 g / mL, or greater than about 1 g / mL. One will appreciate that modification of the density of the water-soluble sheet provides the added functional capacity to modify delivery of the one or more recreational water system agent to various portions of the water column (e.g., on (or below) the surface of the recreational water.

[0066] A second embodiment relates to a process for preparing a water-soluble sheet, which comprises dissolving a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent in a casting liquid comprising a non-aqueous solvent, water, or a combination thereof to obtain a casting solution, casting the casting solution onto a suitable casting plate / roller to obtain a casted sheet, drying the casted sheet at a suitable temperatures (e.g., about 60°C to about 100°C) to obtain a dried, casted sheet.

[0067] The proportions of non-aqueous solvent and water may be chosen depending on the PVA, the functional ingredient, and the recreational water system agent. See, e.g., Selvol™ SPG.

[0068] One will appreciate that the drying process may not result in removal of all the casting liquid, in which case a so-formed water-soluble sheet may include a residual amount of the non-aqueous solvent, water, or a combination thereof.

[0069] In one aspect of the second embodiment, the casting liquid comprises a non- aqueous solvent, such as glycerin, a polyethylene glycol (e.g., PEG 200, PEG 300, PEG 400, etc.), or a combination thereof. See, e.g., Brant.

[0070] In another aspect of the second embodiment, the process further comprises one or more of slitting, cutting, and stacking the dried, casted sheet to form the water-soluble sheet.

[0071] In yet another aspect of the second embodiment, the process further comprises perforating the dried, casted sheet to form a perforated water-soluble sheet, optionally slitting, and winding the sheet around a suitable roll core.

[0072] A third embodiment relates to a method for treating a recreational water system, which comprises adding one or more of a water-soluble sheet disclosed herein to the recreational water system.

[0073] When placed in contact with water, the water-soluble sheet disclosed herein will dissolve and release its ingredients into the water system providing the necessary treatment and benefit to water system.

[0074] The number of sheets depends on the desired outcome, as well as the dosage amount of recreational water system agent in each sheet. For instance, an end user may be interested to adjust the pH of the recreational water of a value of 7.2 to 7.6. Accordingly, an end user may add one or more of a water-soluble sheet comprising a pH adjuster to the recreational water system. The number of sheets may vary depending on the size of the sheet and the amount of pH adjuster in each sheet. In that regard, an end user may add 4 water- soluble sheets to the recreational water, wait for a suitable time, measure the pH of the recreational water, and add one or more additional water-soluble sheets comprising a pH adjuster to the recreational water system. Given that each sheet will include a fixed dosage of one or more of a recreational water system agent (e.g., a pH adjuster), an end user may consult written materials (or a mobile application) associated with the water-soluble sheet product to determine the number of sheets based on the volume of the recreational water system and the observed parameter (e.g., pH of the recreational water, free available chlorine, and the like).

[0075] Examples of recreational water systems, include, for example, a lagoon, a water park, a natural pond, a swimming pool (e.g., a residential pool or an Olympic pool), a pop-up pool, a hot tub, a whirlpool bath, a jacuzzi, a wave pool, a swim spa, and the like. Pop-up pools can be as small as 1000 gallons. Large residential pools are about 50,000 gallons at the high end. Olympic size pools are even larger. Spas have a volume of about 100 gallons to about 1500 gallons (or more), such as 3000 gallons.

[0076] The expression "comprising" may be replaced by the expressions "consisting essentially of," "consisting substantially of," and "consisting of."

[0077] Accordingly, a variation of any one of the embodiments disclosed herein relates to a water-soluble sheet for use in a recreational water system consisting essentially of a sheet comprising a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent; including all aspects disclosed herein, as well as its preparation and use.

[0078] Further, another variation of any one of the embodiments disclosed herein relates to a water-soluble sheet for use in a recreational water system consisting substantially of a sheet comprising a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent; including all aspects disclosed herein, as well as its preparation and use.

[0079] And yet another variation of any one of the embodiments disclosed herein relates to a water-soluble sheet for use in a recreational water system consisting of a sheet comprising a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent; including all aspects disclosed herein, as well as its preparation and use. Examples

[0080] The following examples are prepared (Exs.1 and 3-4) or were prepared (Exs.2 and 5-7) according to the compositional makeup shown below.Abbreviations: PVA (polyvinyl alcohol), AS (approximate size), and AM (approximate mass). †Ingredients including a range of 0% may be excluded or may be included in an amount greater than 0% either singly or in combination with the respective identified ingredients as a means to modify the physical handling, manufacturability, stability, aesthetics, dissolution properties, or treatment performance of the example sheets. Additional Aspects

[0081] Aspect 1. A water-soluble sheet for use in a recreational water system comprises a sheet comprising a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent.

[0082] Aspect 2. The water-soluble sheet of Aspect 1, wherein the polyvinyl alcohol is present in an amount of from 5% to 95% based on the mass of the water-soluble sheet.

[0083] Aspect 3. The water-soluble sheet of Aspect 1, wherein the polyvinyl alcohol is present in an amount of from 5% to 75% based on the mass of the water-soluble sheet.

[0084] Aspect 4. The water-soluble sheet of Aspect 1, wherein the polyvinyl alcohol is present in an amount of from 5% to 30% based on the mass of the water-soluble sheet.

[0085] Aspect 5. The water-soluble sheet of Aspect 1, wherein the polyvinyl alcohol is present in an amount of from 50% to 75% based on the mass of the water-soluble sheet.

[0086] Aspect 6. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system chemical agents comprise one or more of an alkaline agent, antifoaming agent, clarifier agent / flocculant, colorant, corrosion inhibitor, fragrant, halogen source, pH adjuster, a sanitizer, a water hardness agent, a water softness agent, an evaporative-loss agent, a waterline cleaning agent, or a combination thereof.

[0087] Aspect 7. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises an alkaline agent.

[0088] Aspect 8. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises an alkaline agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

[0089] Aspect 9. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises an antifoaming agent.

[0090] Aspect 10. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises an antifoaming agent in an amount of from 0% to 10% by mass of the water-soluble sheet.

[0091] Aspect 11. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a clarifier agent, a flocculant, or a combination thereof.

[0092] Aspect 12. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a clarifier agent, a flocculant, or a combination thereof in an amount of from 5% to 80% by mass of the water-soluble sheet.

[0093] Aspect 13. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a colorant.

[0094] Aspect 14. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a colorant in an amount of from 0% to 40% by mass of the water-soluble sheet.

[0095] Aspect 15. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a corrosion inhibitor.

[0096] Aspect 16. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a corrosion inhibitor in an amount of from 5% to 50% by mass of the water-soluble sheet.

[0097] Aspect 17. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a fragrant.

[0098] Aspect 18. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a fragrant in an amount of from 0% to 40% by mass of the water-soluble sheet.

[0099] Aspect 19. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a halogen source, a coated halogen source, or a combination thereof.

[0100] Aspect 20. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a halogen source, a coated halogen source, or a combination thereof in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

[0101] Aspect 21. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a pH adjuster.

[0102] Aspect 22. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a pH adjuster in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

[0103] Aspect 23. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a sanitizer.

[0104] Aspect 24. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a sanitizer in an amount of from 2% to 80% based on the mass of the water-soluble sheet.

[0105] Aspect 25. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a water hardness agent.

[0106] Aspect 26. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a water hardness agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

[0107] Aspect 27. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a water softness agent.

[0108] Aspect 28. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a water softness agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

[0109] Aspect 29. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises an evaporative loss agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

[0110] Aspect 30. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a waterline cleaning agent.

[0111] Aspect 31. The water-soluble sheet of any one of the preceding aspects, wherein the one or more of a recreational water system agent comprises a waterline cleaning agent in an amount of from 0% to 40% by mass of the water-soluble sheet.

[0112] Aspect 32. A method for treating a recreational water system, which comprises adding one or more of a water-soluble sheet of any one of Aspects 1-31 to the recreational water system. Cited Information

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[0146] Subject matter disclosed herein is hereby incorporated by reference, including U.S. Provisional Patent Application No. 63 / 643,953, filed on May 8, 2024. In the event that incorporated subject matter conflicts with the subject matter herein, the subject matter herein will control.

Claims

Claims 1. A water-soluble sheet for use in a recreational water system comprises a sheet comprising a polyvinyl alcohol, optionally one or more of a functional ingredient, and one or more of a recreational water system agent.

2. The water-soluble sheet of claim 1, wherein the polyvinyl alcohol is present in an amount of from 5% to 95% based on the mass of the water-soluble sheet.

3. The water-soluble sheet of claim 1, wherein the polyvinyl alcohol is present in an amount of from 5% to 75% based on the mass of the water-soluble sheet.

4. The water-soluble sheet of claim 1, wherein the polyvinyl alcohol is present in an amount of from 5% to 30% based on the mass of the water-soluble sheet.

5. The water-soluble sheet of claim 1, wherein the polyvinyl alcohol is present in an amount of from 50% to 75% based on the mass of the water-soluble sheet.

6. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system chemical agents comprise one or more of an alkaline agent, antifoaming agent, clarifier agent / flocculant, colorant, corrosion inhibitor, fragrant, halogen source, pH adjuster, a sanitizer, a water hardness agent, a water softness agent, an evaporative loss agent, a waterline cleaning agent, or a combination thereof.

7. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises an alkaline agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

8. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises an antifoaming agent in an amount of from 0% to 10% by mass of the water-soluble sheet.

9. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a clarifier agent, a flocculant, or a combination thereof in an amount of from 5% to 80% by mass of the water-soluble sheet.

10. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a colorant in an amount of from 0% to 40% by mass of the water- soluble sheet.

11. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a corrosion inhibitor in an amount of from 5% to 50% by mass of the water-soluble sheet.

12. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a fragrant in an amount of from 0% to 40% by mass of the water- soluble sheet.

13. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a halogen source, a coated halogen source, or a combination thereof in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

14. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a pH adjuster in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

15. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a sanitizer in an amount of from 2% to 80% based on the mass of the water-soluble sheet.

16. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a water hardness agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

17. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a water softness agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

18. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises an evaporative loss agent in an amount of from 5% to 80% based on the mass of the water-soluble sheet.

19. The water-soluble sheet of claim 1, wherein the one or more of a recreational water system agent comprises a waterline cleaning agent in an amount of from 0% to 40% by mass of the water-soluble sheet.

20. A method for treating a recreational water system, which comprises adding the water-soluble sheet of claim 1 to the recreational water system.

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