US20080176985A1 - Water-soluble film - Google Patents

Water-soluble film Download PDF

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Publication number
US20080176985A1
US20080176985A1 US11/733,595 US73359507A US2008176985A1 US 20080176985 A1 US20080176985 A1 US 20080176985A1 US 73359507 A US73359507 A US 73359507A US 2008176985 A1 US2008176985 A1 US 2008176985A1
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Prior art keywords
film
pvoh
chitosan
water
range
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US11/733,595
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English (en)
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Andrew P. Verrall
Solomon E. Brown
Dennis A. Beckholt
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Monosol LLC
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Monosol LLC
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Priority claimed from US11/559,262 external-priority patent/US20080110370A1/en
Application filed by Monosol LLC filed Critical Monosol LLC
Priority to US11/733,595 priority Critical patent/US20080176985A1/en
Assigned to MONOSOL, LLC reassignment MONOSOL, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BECKHOLT, DENNIS A., BROWN, SOLOMON E., VERRALL, ANDREW P.
Priority to US12/513,024 priority patent/US8268914B2/en
Priority to HK09110421.9A priority patent/HK1132755B/xx
Priority to JP2009537318A priority patent/JP5620105B2/ja
Priority to CA2669397A priority patent/CA2669397C/en
Priority to EP07854627.2A priority patent/EP2087028B1/en
Priority to CN200780042158.3A priority patent/CN101535385B/zh
Priority to PL07854627T priority patent/PL2087028T3/pl
Priority to PCT/US2007/084566 priority patent/WO2008064014A2/en
Publication of US20080176985A1 publication Critical patent/US20080176985A1/en
Priority to JP2014137515A priority patent/JP2014177654A/ja
Abandoned legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof

Definitions

  • the disclosure relates generally to water-soluble structures such as films. More particularly, the disclosure relates to water soluble-films which are soluble only in particular pH ranges, which find utility in the packaging of detergent additives such as rinse additives.
  • Water-soluble polymeric films are known in the art and are described in several references. Such polymeric films are commonly used in packaging materials to simplify dispersing, pouring, dissolving, and dosing a material to be delivered. Water-soluble film packages of such polymeric materials can be directly added to a mixing vessel, advantageously avoiding contact with toxic or messy materials, and allowing accurate formulation in the mixing vessel. Soluble pre-measured polymeric film pouches aid convenience of consumer use in a variety of applications, particularly those involving wash additives.
  • rinse additive refers to those materials which are intended for use, or are most efficacious in a rinse portion of a wash cycle and are intended to improve a property, such as the aesthetics, feel, appearance, sanitation or cleanliness of fabrics or wares which can be washed in machine washing apparatus.
  • wash additives are preferably rinse-added after an alkaline detergent wash has occurred, and include but are not limited to fabric softeners, brighteners, anti-redeposition agents, bleaches, and surfactant rinse aids for dishwashing. It is desirable to effectuate the release of the additives during the rinse portion, rather than during the wash portion, of the wash cycle.
  • One aspect of the disclosure provides a method of making a water-soluble film, including the steps of slurrying a PVOH polymer in a dilute aqueous solution of chitosan; adding any optional ingredients to the slurry, including plasticizers, antioxidants, UV stabilizers, surfactants, crosslinking agents, lubricants, and extenders; heating the slurry with agitation to thereby solubilize the PVOH; adding an alkali metal or ammonium bisulfite or metabisulfite to the solution and optionally agitating the solution to thereby solubilize the alkali metal or ammonium bisulfite or metabisulfite, cooling the solution; and casting the solution and drying off solvent to thereby obtain a water-soluble polymer film.
  • Another aspect of the disclosure provides a water-soluble film including a mixture of PVOH, chitosan in an amount up to 20 wt %, and an alkali metal or ammonium bisulfite or metabisulfite.
  • Still another aspect of the disclosure provides a water-soluble film including a mixture of PVOH, chitosan, and an alkali metal or ammonium bisulfite or metabisulfite wherein the weight ratio of PVOH to chitosan in a range of about 12:1 to about 3:1.
  • Yet another aspect of the disclosure provides a sealed packet including a film according to the disclosure herein.
  • compositions, films, and packets described herein are susceptible of embodiments in various forms, the description hereafter includes specific embodiments with the understanding that the disclosure is illustrative, and is not intended to limit the invention to the specific embodiments described herein.
  • FIG. 1 shows a two-compartment pouch made from a film according to the disclosure herein and a conventional PVOH film and containing an ADW detergent in one compartment and a rinse additive in the other compartment.
  • the film-forming composition described herein includes a combination of polyvinyl alcohol (PVOH), chitosan, and an alkali metal or ammonium bisulfite or metabisulfite.
  • the components can be formulated by the teachings herein to create an article, such as film, which is soluble in aqueous solutions having a predetermined pH threshold.
  • Such films find utility in, for example, creation of sealed packets for delayed release of cleaning actives or rinse additives such as those found in automatic dishwashing detergent compositions or laundry detergent compositions.
  • the sealed packets can be made from any suitable method, including such processes and features such as heat sealing and adhesive sealing (e.g., with use of a water-soluble adhesive).
  • the major components of the composition are PVOH, chitosan, and an alkali metal or ammonium bisulfite or metabisulfite.
  • the PVOH has a degree of hydrolysis of greater than 88%, more preferably at least 92% and more preferably 98% or less, for example in a range of about 92% to about 98%.
  • the PVOH is fully hydrolyzed (e.g., 99% to 100%).
  • the molecular weight of the PVOH is not particularly limited, but a medium molecular weight PVOH having a 4% aqueous solution viscosity of about 20 cps to about 30 cps (e.g., 28 cps) at 20° C.
  • the PVOH is preferably present in a range of about 50% by weight, based on the total weight of the film (wt %) to about 90 wt %, on a dry basis, for example about 60 wt % to about 80 wt %, or about 70 wt %.
  • Chitosan (poly[-(1,4)-2-amino-2-deoxy-D-glucopiranose]) is a partially or fully deacetylated form of chitin, a naturally occurring polysaccharide present in shellfish, for example.
  • chitin is a polysaccharide consisting of beta-(1,4)2-acetamido-2-deoxy-D-glucose units, some of which are deacetylated:
  • the degree of deacetylation usually varies between 8 and 15 percent, but depends on the species from which the chitin is obtained, and the method used for isolation and purification.
  • Chitin is not one polymer with a fixed stoichiometry, but a class of polymers of N-acetylglucosamine with different crystal structures and degrees of deacetylation, and with fairly large variability from species to species.
  • the polysaccharide obtained by more extensive deacetylation of chitin is chitosan:
  • chitosan is a generic term for a group of polymers of acetylglucosamine, but with a degree of deacetylation of generally between 50 and 95 percent.
  • Chitosan is the beta-(1,4)-polysaccharide of D-glucosamine, and is structurally similar to cellulose, except that the C-2 hydroxyl group in cellulose is substituted with a primary amine group in chitosan.
  • chitosan is soluble in dilute aqueous acids, usually carboxylic acids, as the chitosonium salt. Solubility in dilute aqueous acid is therefore a simple way to distinguish chitin from chitosan.
  • Chitosan is available in different molecular weights (polymers e.g., 50,000 Daltons (Da); oligomers e.g., 2,000 Da), viscosity grades, and degrees of deacetylation (e.g., 40% to 98%). Chitosan is generally regarded as non-toxic and biodegradable. The degree of acetylation has a significant effect on the amine group pKa, and hence solubility behavior, and the rheological properties of the polymer. The amine group on the mostly deacetylated polymer has a pKa in the range of 5.5 to 6.5, depending on the source of the polymer. At low pH, the polymer is soluble, with the sol-gel transition occurring at approximate pH 7. Both natural chitosan and synthetic poly-D-glucosamines are contemplated for use.
  • the degree of acetylation of the chitosan will influence the pH value at which the film begins to dissolve. As the degree of acetylation increases, the pH above which the film dissolves increases.
  • the degree of acetylation of the chitosan is preferably about 70% or less, for example in ranges such as about 55% to about 65%, or about 60% to about 65% (e.g., 64%) to provide a film with a pH solubility trigger of about 9.2 or 9.3.
  • This material can be obtained by a reacetylation reaction, using acetic anhydride, of commercially available 85% to 95% deacetylated chitosan in aqueous acetic acid, by methods known in the art.
  • the molecular weight of the chitosan is not particularly limited but a weight average molecular weight of about 150,000 Da to about 190,000 Da is preferred.
  • Chitosan is preferably present in a range of about 1 wt % to about 20 wt %, and the following specific contents are contemplated: up to 15 wt %, up to 12 wt %, up to 10 wt %, up to 8 wt %, 4 wt % to 12 wt %, and 6 wt % to 10 wt %.
  • the weight ratio of PVOH to chitosan is contemplated to be in a range of about 12:1 to about 3:1, or about 8:1 to about 10:1, for example about 9:1. It is surprising that use of such low levels of chitosan can provide the desired pH-triggering ability for dissolving the film.
  • Different spectrophotometers may be used: for instance the BECKMAN DU 640, the KONTRON UVIKOV 810 and the PERKIN ELMER 550 SE.
  • degree of acetylation lower than 0.11, correct the final result with a coefficient deduced from the correction curve.
  • the alkali metal or ammonium bisulfite or metabisulfite in the example described below functions by reacting with terminal aldehyde groups on the PVOH to form hydroxysulfonic acid salt adducts, and so prevents Schiff base reactions between PVOH aldehyde groups and chitosan amine groups. It is posited that such Schiff base formation, which occurs over time in the finished film, represents a type of crosslink and it has been observed that, in the absence of an alkali metal or ammonium bisulfite or metabisulfite, the film gradually loses its water solubility until it is completely insoluble at all pHs in approximately two weeks.
  • contemplated as an aspect of the invention is a film or other solid water-soluble article made by mixing an aqueous solution of PVOH, chitosan, and an alkali metal or ammonium bisulfite or metabisulfite, and subsequently drying off the water, for example by the specific process described below.
  • the alkali metal or ammonium bisulfite or metabisulfite preferably is present in the film in an amount up to about 1 wt %, for example about 0.01 wt % to about 1 wt %, or more preferably about 0.02 wt % to about 0.25 wt %.
  • sodium bisulfite preferably is used in an amount in a range of about 0.02 wt % to about 0.2 wt %, e.g., 0.1 wt %.
  • the alkali metal or ammonium bisulfite or metabisulfite can be present in an amount up to about 0.9% based on the weight of the PVOH used in the film, for example about 0.005% to about 0.9%, or 0.006% to about 0.8% depending on the type of alkali metal or ammonium bisulfite or metabisulfite.
  • sodium bisulfite is preferably is used in an amount in a range of about 0.01% to about 0.22%, e.g., 0.1%, based on the weight of PVOH.
  • an alkali metal or ammonium bisulfite or metabisulfite in a preferred amount of up to 1 wt % in the film can provide both prolonged stability and bleaching/decolorization.
  • the alkali metal or ammonium bisulfite or metabisulfite can be added in excess of 1% in any amount which does not negatively affect the performance of the composition (e.g., film-forming ability, tensile strength, dissolution ability) for a desired application.
  • the amount of alkali metal or ammonium bisulfite or metabisulfite is preferably about 20 wt % or less, for example 15 wt % or less, 10 wt % or less, 5 wt % or less, or 2 wt % or less.
  • the film composition and film can contain other auxiliary film agents and processing agents, such as, but not limited to, plasticizers, lubricants, release agents, fillers, extenders, crosslinking agents, antiblocking agents, antioxidants, detackifying agents, antifoams, nanoparticles such as layered silicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium bisulfite or others), and other functional ingredients, in amounts suitable for their intended purpose.
  • the amount of such secondary agents is preferably up to about 10 wt %, more preferably up to about 5 wt %, e.g., up to 4 wt %.
  • crosslinking agents include, but are not limited to, borax, borates, boric acid, citric acid, maleic acid, oxalic acid, malonic acid, succinic acid, cupric salts, water-soluble polyamide-epichlorohydrin, and combinations thereof.
  • Preferred crosslinking agents include boric acid and water-soluble polyamide-epichlorohydrin, particularly boric acid.
  • a water-soluble polyamide-epichlorohydrin is available under the trade name POLYCUP 172 by Hercules, Inc. of Wilmington, Del.
  • the crosslinking agent preferably is present in an amount up to about 10 wt %, for example about 0.1 wt % to about 10 wt %, or 0.1 wt % to about 5 wt %, depending on the type of crosslinking agent.
  • boric acid preferably is used in an amount in a range of about 0.3 wt % to about 0.7 wt %, e.g., 0.5 wt %.
  • the crosslinking agent can be present in an amount up to about 10% based on the weight of the PVOH used in the film, for example about 0.1% to about 10%, or 0.1% to about 5%, depending on the type of crosslinking agent.
  • boric acid preferably is used in an amount in a range of about 0.5% to about 0.9%, e.g., 0.7%, based on the weight of PVOH.
  • a completely water-impermeable PVOH film can be formed that is soluble in hot water at a predetermined pH.
  • Plasticizers include, but are not limited to, glycerin, sorbitol, and 2-methyl-1,3-propanediol. Combinations of glycerin and sorbitol are preferred. In preferred embodiments glycerin is used in an amount from about 10 wt % to about 20 wt % or 12 wt % to about 18 wt %, e.g., about 15 wt %. In preferred embodiments sorbitol is used in an amount from about 1 wt % to about 10 wt % or 2 wt % to about 8 wt %, e.g., about 3 wt %.
  • a film can be made by the composition described herein according to any suitable method.
  • the following method is preferred: disperse all ingredients except PVOH and the alkali metal or ammonium bisulfite or metabisulfite in a cold solution of chitosan (e.g., 2 wt %), slurry the PVOH in the resulting solution, heat (e.g., to 95° C.) with agitation to solubilize the PVOH, and then cool to 85° C. Add the alkali metal or ammonium bisulfite or metabisulfite after a period of time delay, mix, cast the solution, and dry to yield a film. It will be understood by a person of ordinary skill in the art that other useful structures can be made by different operations, such as molding.
  • the resulting film preferably is formulated to be insoluble in highly alkaline solutions (e.g., pH greater than 9.3, preferably greater than 10).
  • highly alkaline solutions e.g., pH greater than 9.3, preferably greater than 10.
  • the resulting film also preferably has sufficient wet strength to withstand agitation in an automatic washing apparatus for the intended use during pre-rinse phases of washing.
  • Use of a film embodiment according to the description can provide a pH-dependent water-soluble film. Use of a film embodiment according to the description can also provide a pH-dependent, water-soluble release means.
  • the film is useful for containing a detergent composition comprising cleaning actives.
  • the cleaning actives may take any form such as powders, gels, pastes, liquids, tablets or any combination thereof.
  • Inorganic and organic bleaches are suitable cleaning actives for use herein.
  • Inorganic bleaches include perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection. Alternatively, the salt can be coated.
  • Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for use herein.
  • the percarbonate is most preferably incorporated into the products in a coated form which provides in-product stability.
  • a suitable coating material providing in product stability comprises mixed salt of a water-soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1,466,799.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:99 to 1:9, and preferably from 1:49 to 1:19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na 2 SO 4.n.
  • n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Another suitable coating material providing in product stability comprises sodium silicate of SiO 2 :Na 2 O ratio from 1.8:1 to 3.0:1, preferably 1.8:1 to 2.4:1, and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of SiO 2 by weight of the inorganic perhydrate salt, such as potassium peroxymonopersulfate.
  • Other coatings which contain magnesium silicate, silicate and borate salts, silicate and boric acids, waxes, oils, and fatty soaps can also be used advantageously
  • Typical organic bleaches are organic peroxyacids including diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid.
  • Dibenzoyl peroxide is a preferred organic peroxyacid herein.
  • the diacyl peroxide, especially dibenzoyl peroxide should preferably be present in the form of particles having a weight average diameter of from about 0.1 to about 100 microns, preferably from about 0.5 to about 30 microns, more preferably from about 1 to about 10 microns. Preferably, at least about 25% to 100%, more preferably at least about 50%, even more preferably at least about 75%, most preferably at least about 90%, of the particles are smaller than 10 microns, preferably smaller than 6 microns.
  • organic bleaches include the peroxy acids, particular examples being the alkylperoxy acids and the arylperoxy acids.
  • Preferred representatives are: (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diper
  • Bleach activators are typically organic peracid precursors that enhance the bleaching action in the course of cleaning at temperatures of 60° C. and below.
  • Bleach activators suitable for use herein include compounds which, under perhydrolysis conditions, give aliphatic peroxoycarboxylic acids having preferably from 1 to 10 carbon atoms, in particular from 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Suitable substances bear O-acyl and/or N-acyl groups of the number of carbon atoms specified and/or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also triethylace
  • Bleach catalysts preferred for use herein include the manganese triazacyclononane and related complexes (U.S. Pat. No. 4,246,612, U.S. Pat. No. 5,227,084); Co, Cu, Mn and Fe bispyridylamine and related complexes (U.S. Pat. No. 5,114,611); and pentamine acetate cobalt(III) and related complexes (U.S. Pat. No. 4,810,410).
  • a complete description of bleach catalysts suitable for use herein can be found in WO 99/06521, pages 34, line 26 to page 40, line 16.
  • a preferred surfactant for use in automatic dishwashing is low foaming by itself or in combination with other components (i.e. suds suppressers).
  • Preferred for use herein are low and high cloud point nonionic surfactants and mixtures thereof including nonionic alkoxylated surfactants (especially ethoxylates derived from C 6 -C 18 primary alcohols), ethoxylated-propoxylated alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B—see WO-A-94/22800), ether-capped poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-polyoxypropylene polymeric compounds such as PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Mich.; amphoteric surfactants such as
  • Surfactants suitable for use herein are disclosed, for example, in U.S. Pat. No. 3,929,678, U.S. Pat. No. 4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-93/08874.
  • Surfactants are typically present at a level of from about 0.2% to about 30% by weight, more preferably from about 0.5% to about 10% by weight, most preferably from about 1% to about 5% by weight of a detergent composition.
  • Builders suitable for use herein include water-soluble builders such as citrates, carbonates, silicate and polyphosphates, e.g. sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate and mixed sodium and potassium tripolyphosphate salts.
  • Enzymes suitable herein include bacterial and fungal cellulases such as CAREZYME and CELLUZYME (Novo Nordisk A/S); peroxidases; lipases such as AMANO-P (Amano Pharmaceutical Co.), M1 LIPASE and LIPOMAX (Gist-Brocades) and LIPOLASE and LIPOLASE ULTRA (Novo); cutinases; proteases such as ESPERASE, ALCALASE, DURAZYM and SAVINASE (Novo) and MAXATASE, MAXACAL, PROPERASE and MAXAPEM (Gist-Brocades); ⁇ and ⁇ amylases such as PURAFECT OX AM (Genencor) and TERMAMYL, BAN, FUNGAMYL, DURAMYL, and NATALASE (Novo); pectinases; and mixtures thereof. Enzymes are preferably added herein as prills, granulates, or cogranulates at levels typically in the range
  • Suds suppressers suitable for use herein include nonionic surfactants having a low cloud point.
  • Cloud point as used herein, is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the “cloud point” (See Kirk Othmer, pp. 360-362).
  • a “low cloud point” nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30° C., preferably less than about 20° C., and even more preferably less than about 10° C., and most preferably less than about 7.5° C.
  • Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
  • low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., BASF Poly-Tergent® SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g., BASF Poly-Tergent® SLF18B series of nonionics, as described, for example, in U.S. Pat. No. 5,576,281).
  • Preferred anti-redeposition polymers herein include acrylic acid containing polymers such as SOKALAN PA30, PA20, PA15, PA10 and SOKALAN CP10 (BASF GmbH), ACUSOL 45N, 480N, 460N (Rohm and Haas), acrylic acid/maleic acid copolymers such as SOKALAN CP5 and acrylic/methacrylic copolymers.
  • Preferred soil release polymers herein include alkyl and hydroxyalkyl celluloses (U.S. Pat. No. 4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and nonionic and anionic polymers based on terephthalate esters of ethylene glycol, propylene glycol and mixtures thereof.
  • Heavy metal sequestrants and crystal growth inhibitors are also suitable for use in the detergent, for example diethylenetriamine penta(methylene phosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate, hydroxy-ethylene-1,1-diphosphonate, nitrilotriacetate, ethylenediaminotetracetate, ethylenediamine-N,N′-disuccinate in their salt and free acid forms.
  • diethylenetriamine penta(methylene phosphonate) ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra(methylene phosphonate)
  • ethylene diphosphonate hydroxy-ethylene-1,1-diphosphonate
  • nitrilotriacetate ethylenediaminotetracetate
  • ethylenediamine-N,N′-disuccinate in their salt and free acid
  • Suitable for use in a detergent is also a corrosion inhibitor such as organic silver coating agents (especially paraffins such as WINOG 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for example benzotriazole and benzimadazole—see GB-A-1137741) and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
  • organic silver coating agents especially paraffins such as WINOG 70 sold by Wintershall, Salzbergen, Germany
  • nitrogen-containing corrosion inhibitor compounds for example benzotriazole and benzimadazole—see GB-A-1137741
  • Mn(II) compounds particularly Mn(II) salts of organic ligands.
  • enzyme stabilizers such as calcium ion, boric acid and propylene glycol.
  • use of a film embodiment according to the description can provide a water-soluble delivery system for a wash additive, which will remain insoluble during wash conditions and will rapidly and fully solubilize during rinse conditions to release a rinse additive.
  • Use of a film embodiment according to the description can also provide a means for delivery of a rinse additive, which means may be added during a wash portion of a wash cycle and which will deliver the rinse additive during a rinse portion of a wash cycle.
  • Suitable rinse additives are known in the art.
  • Commercial rinse aids for dishwashing typically are mixtures of low-foaming fatty alcohol polyethylene/polypropylene glycol ethers, solubilizers (for example cumene sulfonate), organic acids (for example citric acid) and solvents (for example ethanol).
  • solubilizers for example cumene sulfonate
  • organic acids for example citric acid
  • solvents for example ethanol
  • the film described herein can also be used to make a packet which contains two or more compartments made of the same film or containing a combination with of films of other polymeric materials. Additional films can, for example, be obtained by casting, blow-molding, extrusion or blown extrusion of the polymeric material, as known in the art.
  • Preferred polymers, copolymers or derivatives thereof suitable for use as the additional film are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum.
  • More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC), and combinations thereof.
  • the level of polymer in the pouch material for example a PVOH polymer, is at least 60%.
  • the polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.
  • PVOH films known under the trade reference MONOSOL M8630, as sold by MONOSOL LLC of Portage, Ind., US, and PVOH films of corresponding solubility and deformability characteristics.
  • Other films suitable for use herein include films known under the trade reference PT film or the K-series of films supplied by Aicello, or VF-HP film supplied by Kuraray.
  • a 75 ⁇ m film was cast from the following formulation, all components in wt %, solids basis:
  • a 75 ⁇ m film was prepared from this formulation by the following procedure: slurry the PVOH in a 2 wt % chitosan solution (cold), add all other ingredients except sodium bisulfite, heat to 95° C. with agitation to solubilize the PVOH, cool to 85° C., add sodium bisulfite after a period of seven hours and agitate to solubilize, cast solution, and dry.
  • the packet was constructed as shown in FIG. 1 in cross-section, wherein the film 10 according to the example enclosed a rinse aid 14 and the conventional PVOH film 12 enclosed the ADW detergent 18.
  • the packets were tested in an ADW machine where maximum temperatures varied between 40° C. and 65° C.
  • the film according to the example was insoluble and had sufficient wet strength that it did not break or disintegrate during the main wash cycle (pH 10.5 to 10.7) and it was soluble in the second rinse cycle (at about pH 9.3).
  • the film according to the example was stored at ambient conditions in a ZIPLOC polyethylene bag for 21 days, and tested in an ADW machine as described above. The film was insoluble and had sufficient wet strength that it did not break or disintegrate during the main wash cycle and it was soluble in the second rinse cycle.
  • the film when tested as described above was insoluble throughout the complete wash and rinse cycle.
  • the PVOH was a partially hydrolyzed PVOH (degree of hydrolysis 88%), the film dissolved during the main wash cycle.
  • a 75 ⁇ m film was cast from the following formulation, all components in wt %, solids basis:
  • a 75 ⁇ m film was prepared from this formulation by the following procedure: disperse all ingredients except the PVOH and sodium bisulfite in a 2 wt % chitosan solution (cold), slurry the PVOH in the resulting solution, heat to 95° C. with agitation to solubilize the PVOH, cool to 85° C., add the sodium bisulfite after a period of ten hours, mix to solubilize, cast solution, and dry.
  • the packet was constructed as shown in FIG. 1 in cross-section, wherein the film 10 according to the example enclosed a rinse aid 14 and the conventional PVOH film 12 enclosed the ADW detergent 18.
  • the packets were tested in an ADW machine where maximum temperatures varied between 40° C. and 65° C.
  • the film according to the example was insoluble and had sufficient wet strength that it did not break or disintegrate during the main wash cycle (pH 10.5 to 10.7) and it was soluble in the second rinse cycle (at about pH 9.3).
  • the film according to the example was stored at ambient conditions in a ZIPLOC polyethylene bag for 21 days, and tested in an ADW machine as described above. The film was insoluble and had sufficient wet strength that it did not break or disintegrate during the main wash cycle and it was soluble in the second rinse cycle.
  • the film when tested as described above was insoluble throughout the complete wash and rinse cycle.
  • the film when using a similarly formulated film except that the PVOH had a degree of hydrolysis of 88% the film dissolved during the main wash cycle.
  • compositions are described as including components or materials, it is contemplated that the compositions can also consist essentially of, or consist of, any combination of the recited components or materials, unless described otherwise.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Wrappers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
US11/733,595 2006-11-13 2007-04-10 Water-soluble film Abandoned US20080176985A1 (en)

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US11/733,595 US20080176985A1 (en) 2006-11-13 2007-04-10 Water-soluble film
PCT/US2007/084566 WO2008064014A2 (en) 2006-11-13 2007-11-13 Water-soluble film
PL07854627T PL2087028T3 (pl) 2006-11-13 2007-11-13 Folia rozpuszczalna w wodzie
JP2009537318A JP5620105B2 (ja) 2006-11-13 2007-11-13 水溶性フィルム
HK09110421.9A HK1132755B (en) 2006-11-13 2007-11-13 Water-soluble film
US12/513,024 US8268914B2 (en) 2006-11-13 2007-11-13 Water-soluble film
CA2669397A CA2669397C (en) 2006-11-13 2007-11-13 Water-soluble film
EP07854627.2A EP2087028B1 (en) 2006-11-13 2007-11-13 Water-soluble film
CN200780042158.3A CN101535385B (zh) 2006-11-13 2007-11-13 水溶性膜
JP2014137515A JP2014177654A (ja) 2006-11-13 2014-07-03 水溶性フィルム

Applications Claiming Priority (3)

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US11/559,262 US20080110370A1 (en) 2006-11-13 2006-11-13 Water-soluble film
US88583807P 2007-01-19 2007-01-19
US11/733,595 US20080176985A1 (en) 2006-11-13 2007-04-10 Water-soluble film

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US20170130016A1 (en) * 2015-04-03 2017-05-11 Jiangnan University Method For Preparing Chitosan Complex Film
US9809365B2 (en) 2014-09-12 2017-11-07 Aicello Corporation Water-soluble film, packaging bag, content release body, and method for producing water-soluble film
EP3348604A4 (en) * 2015-09-11 2019-05-15 The Nippon Synthetic Chemical Industry Co., Ltd. WATER-SOLUBLE FILM AND PACKING BODY FOR CHEMICAL
CN110790885A (zh) * 2019-08-30 2020-02-14 武汉理工大学 一种聚乙烯醇/壳聚糖季铵盐抗菌自愈水凝胶及其制备方法和应用

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US9809365B2 (en) 2014-09-12 2017-11-07 Aicello Corporation Water-soluble film, packaging bag, content release body, and method for producing water-soluble film
US20170130016A1 (en) * 2015-04-03 2017-05-11 Jiangnan University Method For Preparing Chitosan Complex Film
US10442904B2 (en) * 2015-04-03 2019-10-15 Jiangnan University Method for preparing chitosan complex film
EP3348604A4 (en) * 2015-09-11 2019-05-15 The Nippon Synthetic Chemical Industry Co., Ltd. WATER-SOLUBLE FILM AND PACKING BODY FOR CHEMICAL
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HK1132755A1 (en) 2010-03-05
US20100105821A1 (en) 2010-04-29
PL2087028T3 (pl) 2015-04-30
US8268914B2 (en) 2012-09-18
JP2010509491A (ja) 2010-03-25
WO2008064014A3 (en) 2008-07-10
JP2014177654A (ja) 2014-09-25
EP2087028B1 (en) 2014-10-29
WO2008064014A2 (en) 2008-05-29
JP5620105B2 (ja) 2014-11-05
EP2087028A2 (en) 2009-08-12
CA2669397C (en) 2013-03-19

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