WO1987003453A1 - Edible film barrier resistant to water vapor transfer - Google Patents

Edible film barrier resistant to water vapor transfer Download PDF

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Publication number
WO1987003453A1
WO1987003453A1 PCT/US1986/002641 US8602641W WO8703453A1 WO 1987003453 A1 WO1987003453 A1 WO 1987003453A1 US 8602641 W US8602641 W US 8602641W WO 8703453 A1 WO8703453 A1 WO 8703453A1
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WO
WIPO (PCT)
Prior art keywords
film
lipid
base film
layer
hydrophilic polymer
Prior art date
Application number
PCT/US1986/002641
Other languages
French (fr)
Inventor
Owen R. Fennema
Susan Lea Kamper
Jeffrey J. Kester
Original Assignee
Wisconsin Alumni Research Foundation
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
Application filed by Wisconsin Alumni Research Foundation filed Critical Wisconsin Alumni Research Foundation
Publication of WO1987003453A1 publication Critical patent/WO1987003453A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23PSHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P20/00Coating of foodstuffs; Coatings therefor; Making laminated, multi-layered, stuffed or hollow foodstuffs
    • A23P20/20Making of laminated, multi-layered, stuffed or hollow foodstuffs, e.g. by wrapping in preformed edible dough sheets or in edible food containers
    • AHUMAN NECESSITIES
    • A21BAKING; EDIBLE DOUGHS
    • A21DTREATMENT, e.g. PRESERVATION, OF FLOUR OR DOUGH, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS; PRESERVATION THEREOF
    • A21D13/00Finished or partly finished bakery products
    • A21D13/30Filled, to be filled or stuffed products
    • A21D13/34Filled, to be filled or stuffed products the filling forming a barrier against migration
    • AHUMAN NECESSITIES
    • A21BAKING; EDIBLE DOUGHS
    • A21DTREATMENT, e.g. PRESERVATION, OF FLOUR OR DOUGH, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS; PRESERVATION THEREOF
    • A21D13/00Finished or partly finished bakery products
    • A21D13/40Products characterised by the type, form or use
    • A21D13/41Pizzas
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23PSHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P20/00Coating of foodstuffs; Coatings therefor; Making laminated, multi-layered, stuffed or hollow foodstuffs
    • A23P20/10Coating with edible coatings, e.g. with oils or fats
    • A23P20/105Coating with compositions containing vegetable or microbial fermentation gums, e.g. cellulose or derivatives; Coating with edible polymers, e.g. polyvinyalcohol

Definitions

  • the present invention relates to edible film barrier materials that can be used to stabilize water vapor pressure and moisture gradients existing between individual components of a multic ⁇ ponent food product separated by the edible film.
  • "Moisture” as used herein shal l refer to liquid water diffused or condensed in various quantities, so that unfrozen pizza sauce or pie filling may be referred to as moist.
  • Deleterious changes in the quality of food products can occur with inadvertent alteration of the water content of the food product.
  • the driving force for water transfer in food products is primarily water partial pressure gradients existing between the food product and the environment or between c ⁇ rtponents of a multic ⁇ ponent food product.
  • water potentially can migrate via liquid diffusion driven by such forces as water concentration gradients or capillary forces.
  • vapor pressure shall be understood as "partial pressure of water,” unless expressly indicated otherwise.
  • the partial pressures involved can be expressed in terms of water activity, (a w ), which equals the partial pressure of water exerted by the food material divided by the partial pressure of pure water at the same temperature.
  • Carbohydrate compounds are capable of forming structurally continuous coatings, but these compounds are generally hydrophilic and hence are less effective in retarding water transfer in foods. Therefore, in the past, lipids have been used in conjunction with carbohydrates in order to form a continuous coating to prevent water transfer in foods.
  • Patent Nos. 3,471,303 and 3,471,304 to Hamdy, et al. disclosed two types of coating compositions having as one constituent a cellulose ether.
  • the cellulose ether was plasticized by various fatty acid derivatives such as (1) an ester of a linear polysaccharide having alpha-glucoside linkages and a fatty acid having between 8 to 26 carbon atcms, or (2) a glyceride containing a fatty acid having between 6 to 20 carbon atoms, together with a fatty acid metal salt wherein the fatty acid contains between 16 and 22 carbon at ⁇ s.
  • the coating composition in the Hamdy patents could be extruded as a non-layered, molten sheet over the food to be coated, and then dried.
  • U.S. Patent No. 3,997,674 to Ukai, et al. disclosed an aqueous solution used to coat foods such as fresh fruits.
  • the coating solution contained a water soliible high polymer such as methylcellulose and also hydrophobic substances such as waxes or oils.
  • the food product was coated and then dried.
  • Drying a food coating after application on a food has several disadvantages. It is difficult to control the thickness of such coatings. Furthermore, drying coated foods adds time and hence cost to the manufacture of such foods. Therefore, it would be advantageous to provide off-the-shelf, pre-formed films that could effectively retard or prevent water transfer between components having different a w values or different moisture contents in a multicomponent food product.
  • an edible film for retarding water transfer among components of a multicomponent food product includes a base film having a hydrophilic polymer layer and a base film lipid layer.
  • the base film lipid layer has a hydrophobic surface presented away from the hydrophilic polymer layer.
  • An additional lipid layer is laminated to the hydrophobic surface of the base film lipid layer.
  • a method for making an edible film for retarding water transfer among components of a multicomponent food product includes, the following steps. First, a film-forming liquid is prepared by dissolving an edible hydrophilic polymer and mixing an edible lipid in an aqueous solvent system. Then, the film-forming liquid is plated on a supporting surface to a selected depth and dried to gel the polymer and form a base film. The depth of film-forming liquid selected is one sufficient to contain enough polymer and lipid to result in a dried base film of a desired thickness and to contain enough lipid to form a substantially uniform lipid layer covering that surface of the base film which is presented away from the supporting surface.
  • a base film may be formed having a hydrophilic polymer layer and a base film lipid layer having a hydrophobic surface presented away from the hydrophilic polymer layer. Finally, an additional edible lipid is applied to the hydrophobic surface of the base film lipid layer to form an additional lipid layer.
  • a multiccmponent food product includes a first component and a second component having water vapor pressures and moisture characteristics such that water transfer would tend to occur from the second component to the first component.
  • the edible film of the invention is located between the first and second components, with the additional lipid layer oriented toward the second component.
  • An object of the present invention is to provide an edible, pre-formed, dry film that can retard moisture and water vapor transfer among components of a multiccmponent food product during extended storage times and over changing temperatures and humidities, and yet can be absorbed in the food product or otherwise be rendered unobjectionable during heating or other preparation of the food product.
  • a further object of the present invention is to provide a method for making edible pre-formed films capable of retarding moisture and water vapor transfer among components of a multicomponent food product over extended storage times.
  • Another object of the present invention is to provide a food product and method to make a food product that includes a plurality of components having different vapor pressures or moisture contents together with edible films separating individual components, which films can maintain existing vapor pressure and moisture gradients for substantial periods of time and thereby retard water transfer among the food components.
  • the present invention includes an edible film for retarding water transfer among components of a rrailticcmponent food product.
  • the film has a base film having a hydrophilic polymer layer and a solid or semi-solid, edible lipid layer adhered to the hydrophilic polymer layer.
  • the lipid layer of the base film is enhanced with an additional hydrophobic layer.
  • the films of the invention may be quite thin, ranging from a practical mip-imum thickness of approximately 0.024 mm to as much as at least 0.10 mm.
  • the base film's hydrophilic polymer layer can be formed from any edible, water-soluble, film-forming carbohydrate that displays thermal gelation in the solvent system used. Suitable polymers include, by way of example only, cellulose ethers such as hydroxypropyl methylcellulose and methylcellulose.
  • the base film's lipid layer is conprised of solid or semi-solid, edible lipids such as hydrogenated oils (e.g., palm oil and soybean oil), saturated fatty acids, and edible waxes (e.g., beeswax and paraffin wax).
  • the exposed surface of the lipid layer is hydrophobic.
  • the base film itself is an effective barrier to water transfer. When the base film.
  • the base film can maintain the existing vapor pressure or moisture gradient for substantial periods of time, effectively retarding water transfer among the feed components.
  • a one-step method can be used for making a base film according to the present invention.
  • water, a water-soluble, lipid-dissolving solvent such as an alcohol, a hydrophilic polymer, and a lipid are combined to make a fito-forming liquid.
  • the lipid-dissolving solvent is present in quantities effective to dissolve at least a portion of the lipid and not to interfere with the dissolving and gelling of the polymer.
  • an alcohol is used, the usual and preferred alcohol is ethanol.
  • the film-forming liquid is warmed, if necessary, to melt lipids having high melting points.
  • the film-forming liquid is then spread on a supporting surface such as a flat, smooth plate, preferably to a depth of between approximately 0.25 and 0.75 mm. This may be done by any appropriate means for spreading a liquid, including brushing, dipping, spraying, or the use of spreading means comparable to those used in conventional thin layer chromatography.
  • the plate is then dried tor a time sufficient to form a cohesive layer on the plate. A substantial portion of the lipids situate themselves at the surface of the drying film-fonning liquid. The result is a distinguishable lipid layer demonstrating hydrophobic qualities.
  • the process of spreading the film-forming liquid and drying it so as to form a base film shall be referred to herein as "plating.”
  • Various concentrations of ingredients may be employed in preparing the film-forming liquid, and the liquid may be spread at various thicknesses. Excessive amounts of solvents may lead to inefficient or inconvenient drying periods. Bcwever, there is no theoretical point at which the ccsx:entrations of polymer and lipid have bec ⁇ re too small to allow formation of a base film.
  • the lipid concentration must be sufficient to allow substantially complete coverage of the surface of the base film as it is drying so as to form a hydrophobic surface and must not be so great as to substantially interfere with the formation of a cohesive polymer layer.
  • Concentrations and spreading thicknesses are ⁇ c adjusted as to produce a dried base film having the strength and handling characteristics desired.
  • a base film minimum thickness of approximately 0.013 mm generally is necessary.
  • Base film thicknesses of 0.018 to 0.045 mm have been found. to be preferred in many applications, although thicker base films may be made as well.
  • a fatty acid such as stearic or palmitic acid
  • a lipid concentration of at least approximately 0.25 mg/cm 2 is necessary. Concentrations of 0.50 to 0.80 mg/cm 2 are preferred.
  • the plate After drying, the plate is cooled, and the film is removed from the plate. If the base film is to be used directly as a water transfer barrier, it can then be positioned on the food material or stored until the food components are assembled.
  • the base films so formulated are generally less fragile and easier to remove frcm the plate. Additional, desirable effects can be achieved if the alcohol or other lipid-dissolving solvent forming a part of the solvent system of the film-forming liquid is added in sufficient quantities and if the base film is dried at sufficiently high temperatures. A concentration of such a solvent can be achieved sufficient to create a solvent system capable of solubilizing seme lipids that would otherwise be in an emulsion form. For example, an alcohol concentration in excess of 55% is sufficient if ethanol is used.
  • lipid-dissolving solvent in this manner shall be referred to herein as the "dissolved lipid process.”
  • Lipid globules in a suspension not subject to the dissolved lipid process just described are believed to be larger than the lipid globules formed when the gelation process helps to preserve dispersion of the lipid. It is believed that the smallness of the lipid globules formed when the dissolved lipid process is used contributes to the uniform distribution of lipids at the base film surface and to the resulting creation of a more effective moisture and water vapor-impervious hydrophobic layer. Examination of samples of such base film with the scanning electron microscope has revealed that the lipids at the hydrophobic surface form a lipid layer that does not have a sharply defined boundary with respect to the hydrophilic polymer.
  • the lipid and the hydrophilic polymers form layers that mutually interpenetrate to seme extent, with fingers of lipid extending into the hydrophilic polymer layer and vice versa, thereby enhancing cohesion of the two components.
  • an edible film utilizing a base film made by the dissolved lipid process as described is preferred and believed to exhibit superior mechanical strength and flexibility and water transfer barrier characteristics.
  • the aqueous solvent system used to prepare the film-forming liquid may alternatively contain an amount of water-soluble, lipid-dissolving solvent insufficient to dissolve any significant quantity of the base film lipid. Indeed the aqueous solvent system may be entirely without such a lipid-dissolving solvent.
  • the lipid is held within the film-forming solution as a suspension. If the lipid is sufficiently divided within the suspension, it is believed that gelation of the hydrophilic polymer may occur in such a manner as to entrap sane of the lipid within the hydrophilic polymer and, at any rate, will lead to a boundary between the hydrophilic polymer and the base film lipid layer that is characterized by sufficient interpenetration that an at least minimally adequate base film is formed capable of being incorporated in a film for retarding water transfer exhibiting the advantages of the invention.
  • Temperature control is important in preparing a base film by the described method.
  • Film-forming liquids containing lipids with high melting points require high temperatures to melt and disperse the lipid.
  • excessively high temperatures can result in a low viscosity of the film-forming liquid and poor control over base film thickness during plating.
  • excessively high temperatures must be avoided during plating, because extremely rapid vaporization of the alcohol or other lipid-dissolving solvent can occur, resulting in bubbles in the film-forming liquid and possible pin holes in the dried base film. Nevertheless, the film-forming liquid must be warm enough to prevent solidification of the lipids curing plating.
  • the lipid layer of the base film is enhanced with an additional hydrophobic lipid layer to create a film composed of two layers that are laminated together.
  • the base film shall be deemed to constitute the "bottom" layer of the edible film of the invention.
  • the additional lipid layer is laminated to the base layer by any suitable means for applying an additional lipid layer to the hydrophobic surface.
  • the additional lipid layer may be applied by brushing, dipping, spraying, or otherwise spreading or distributing a liquid or semi-liquid lipid over the hydrophobic surface of the base film.
  • the additional lipid layer is then solidified. The solidification may be accomplished by cooling a lipid that has been warmed above its melting temperature.
  • a lipid held in an appropriate solution may he deposited by evaporating the solvent.
  • the additional lipid layer may be made of any lipid of the sort described above.
  • other lipid raterials such as fatty acids and triglycerides can be used for forming the additional lipid layer
  • solidified natural waxes such as beeswax and refined, paraffin waxes are preferred. Upon solidification, such waxes form an amorphous cr microcrystalline layer that is particularly effective to bar water vapor transfer.
  • Especially suitable waxes include beeswax, candelilla wax, carnauba wax, rice bran wax, and the refined paraffin and microcrystalline waxes obtained from petroleum, all 'of which are described in the Food Chemical Codex. If such an edible, food-grade wax is utilized as the additional lipid layer, a thickness of at least approximately 0.011 mm is used, and a thickness in the range of 0.026 mm to 0.047 mm is preferred.
  • the desirable wax content thus is approximately in the range 2.5 mg to 4.5 mg of wax per square centimeter of base film.
  • the minimum wax content is approximately 1.0 mg/cm 2 .
  • the completed laminated film having the preferred thickness of base film and a wax employed as the additional lipid film has a desired thickness in the range of approximately 0.044 mm to 0.092 mm.
  • the preferred film-forming liquid used to make the base film is prepared frcm a blend of cellulose ethers including both methylcellulose and hydroxypropyl methylcellulose. That blend of cellulose ethers is combined with polyethylene glycol and a saturated fatty acid, all in a lipid-dissolving, ethanol-water solvent system.
  • the solvent system may include as much as approximately 80% ethanol and preferably is at least 55% ethanol. The maximum concentration of approximately 80% ethanol is the practical upper limit, beyond which there is a loss of solubility of the cellulose ethers.
  • the film-forming liquid is warmed to the extent necessary to thoroughly dissolve the fatty acids.
  • fatty acids in the concentration indicated to be dissolved at about 65°C use of a 55% ethanol solution allows fatty acids in the concentration indicated to be dissolved at about 65°C.
  • the film-forming solution is prepared with appropriate concentrations and then is spread on a glass plate or comparable supporting surface to a depth of approximately 0.25 mm.
  • the film is then dried at an air temperature of approximately 100°C. At that tamperature and that thickness, a drying time of 15 minutes usually is sufficient. Thereafter, the base film is allowed to cool to room temperature.
  • the wax used as. the additional lipid layer may then be deposited upon the hydrophobic surface, of the base film by any of several means to do so, as is discussed above, at a thickness in the range of 0.026 to 0.047 irm.
  • a factor of critical importance for the successful low terperature use of films of the embodiment being described is good adhesion between the base film and the additional lipid layer.
  • the need for such effective bonding becomes especially apparent at temperatures generally in use for frozen food applications. At those temperatures, poor adhesion or ineffective bonding leads to fracturing of the additional lipid layer and to its subsequent separation from the base film. This is accompanied by a reduction of the film's ability to act as a barrier to water vapor.
  • the lipid used for the additional lipid layer is a wax
  • good wax adhesion is evidenced by resistance to fracturing and maintenance of water vapor barrier properties upon prolonged storage at temperatures as low as -40°C.
  • the blend of cellulose ethers should include between 50% and 80% methylcellulose, with the balance being hydroxypropyl methylcellulose.
  • the preferred ratio is 70% methylcellulose and 30% hydroxypropyl methylcellulose.
  • the blend of cellulose ethers is believed to maximize bonding of the additional lipid layer to the base film while still maintaining satisfactory film-forming properties.
  • hydroxypropyl methylcellulose has a film-forming capability more effective than that of methylcellulose.
  • methylcellulose, being less hydrophilic than hydroxypropyl methylcellulose adheres more effectively to the additional lipid layer.
  • the blend produces a strong film to which the additional lipid layer bonds well.
  • the cellulose ethers referred to display gelation when heated in solution By use of the ethanol-water lipid-dissolving solvent system or comparable system to perform the dissolved lipid process discussed above, thermal gelation of the methylcellulose and hydroxypropyl methylcellulose during the drying phase of the formation of the base film, locks a certain percentage of the fatty acid included in the film-forming liquid throughout the bulk of the base film and also appears to prevent the fatty acid comprising the hydrophobic lipid layer from agglomerating into relatively large lipid globules. Consequently, the base film when dry has distributed within it small fatty acid crystals as integral components of the film.
  • the base film also has a layer, of fatty acid so situated at the surface of the film as to form a hydrophobic surface, but with an intimate physical interinvolvement of the fatty acid, lipid layer with the underlying hydrophilic polymer layer. It is thought that, when wax of the sort referred to above is used for the additional lipid layer and is spread over the base film in molten form, the fatty acid crystals embedded within and at the surface of the base film first melt beneath the hot wax and then resolidify as the applied wax cools and solidifies. It appears that this contributes to effective bonding between the base film and the wax additional lipid layer, probably by the melting of fatty acid crystals at the surface of the base film into the wax layer to increase the intimacy of the joining of the base film and wax additional lipid layer.
  • Polyethylene glycol is disclosed above as usefully incorporated into the film-forming liquid as a plasticizer to aid in the removal of dried films fr ⁇ n the plate or other substrate upon which they have been formed and otherwise to improve their durability.
  • polyethylene glycol also binds to and is miscible with many waxes. Consequently, it is believed that the presence of polyethylene glycol in the base film contributes to the intimate physical interaction of the base film and the additional lipid layer when that lipid layer is, wax, to promote effective adhesion of; the additional lipid layer to the base film.
  • ethanol was disclosed above as usable for converting the film-forming suspension into a true solution.
  • the essence of what is needed is a solvent that provides means for dissolving the lipid used in the base film and keeping that lipid dissolved until the hydrophilic polymer, whether a cellulose ether or otherwise, has polymerized to form a gel.
  • the non-aqueous solvent present in the lipid-dissolving solvent system and used as such a means must not interfere with the polymerizing or gelling process and must leave no residue that would be harmful if eaten.
  • solvents than ethanol could be so used as a dissolving means, such as acetone, isopropyl alcohol, methyl alcohol, and prcpyl alcohol.
  • polyethylene glycol was disclosed as a suitable plasticizer that also contributed to the adhesion of the additional lipid layer to the base film.
  • glycerol, propylene glycol, and other similar plasticizers capable of dissolving in high concentration the lipid of the additional lipid layer may be expected to function in a comparable manner.
  • a multicomponent food product can be made utilizing the film of the invention, as described above.
  • Use of the film is beneficial when a first component of the feed product and a second component have water vapor pressures and moisture characteristics such that water trannfer would tend to occur from the second component to the first component unless restrained.
  • an edible film of the sort described above is located between the first and second components, with the additional lipid layer oriented toward the second component. As a result, water transfer is retarded, and the multiccmponent food product may be stored without change from water transfer for longer periods of time than would otherwise be possible.
  • a film-forming liquid was prepared by dissolving 9 gm of hydroxypropyl methylcellulose in 100 ml of 90°C distilled water. After the hydroxypropyl methylcellulose was completely in solution, 200 ml of 95% ethanol was added. Next, 1 gram of polyethylene glycol was added to the solution. Finally, 3.4 gm of stearic acid was added' to the solution. The solution was warmed to between 70-75°C in order to melt and dissolve the stearic acid.
  • One hundred milliliters of the film-forming solution was added to a thin layer chromatography (TLC) spreader and plated onto three 8 inch by 8 inch glass TLC plates at a thickness of 0.75 itm.
  • TLC thin layer chromatography
  • the coated plates were then dried in an oven at approximately 90°C for 15 minutes, by which time a cohesive, edible, base film had formed. After drying, the plates were cooled, and the films were peeled from the plates.
  • the films had an average thickness of 0.04 mm and an average stearic acid concentration of 0.8 mg stearic acid per square centimeter of hydroxypropyl methylcellulose layer.
  • Base films were made by methods generally corresponding to that of Example 1. In particular 7 gm of methylcellulose and 3 gm of hydroxypropyl methylcellulose were dissolved in 100 ml of distilled water at 90°C. After complete dissolution of the cellulose ethers, 200 ml of 95% ethanol was added to the solution. This solution was thoroughly mixed. Then 6 gm of polyethylene glycol was added to. the solution. Finally; 9 gm of a fatty acid was added and the mixture was warmed to completely dissolve the fatty acid. In replications of this example, stearic acid, palmitic acid, and combinations of the two were used as the fatty acid.
  • the film-forming liquid was subsequently maintained at a tesperature of 65 ⁇ 1°C. Air bubbles were removed if necessary by reducing the pressure over the film-forming liquid.
  • Thirty-five ml of the film-forming liquid was added to a TLC spreader.
  • the film-forming liquid was spread onto four 8 x 8 inch TLC glass plates of conventional design, the film-forming liquid being spread at a thickness of approximately 0.25 mm.
  • the film-forming liquid was then dried in an oven at 100°C for 15 minutes to produce a cohesive cellulose ether-polyethylene glycol-fatty acid base film. After the drying procedure, the plates were cooled to room temperature.
  • the dried base films had an average thickness of 0.020 mm and an average fatty acid concentration of 0.60 mg/cm 2 of base film.
  • a food prepared in accordance with the present invention could include a plurality of components having different vapor pressures and/or moisture contents, such as pizza or filled pie crusts.
  • an edible film prepared in accordance with the present invention would be pre-formed and then positioned so as to separate the individual components.
  • Such edible films would include a base film having a hydrophilic polymer layer and a lipid layer adhered to and partly intermixed with the hydrophilic polymer layer such that the base film, comprising the hydrophilic polymer layer and the lipid layer, would have a preferred thickness in the range of 0.018 mm to 0.045 ran.
  • the base film lipid layer preferably would have a concentration of at least approximately 0.5 mg lipid per square centimeter of hydrophilic polymer layer.
  • An additional lipid layer would be laminated to the exposed, hydrophobic surface of the base film lipid layer and would be oriented toward the food component having the higher vapor pressure or moisture content, such as a pizza sauce or pie filling when compared to a crust. With this orientation, the film could maintain an existing food component vapor pressure or moisture gradient for substantial periods of time, thereby retarding water transfer from the component having a higher vapor pressure or moisture content to the component having a lower vapor pressure or moisture content. The film would be absorbed into the component layers upon heating or other cooking preparation exceeding 70°C.
  • a conventional French bread pizza food product consists of a loaf of French bread which is sliced horizontally to reveal the interior crumb structure, upon which is placed a mixture of tomato sauce, cheese, spices, and vegetables.
  • the product conventionally is shrink wrapped and blast frozen. It then may be stored in frozen storage for a substantial period of time during distribution and prior to consumption by the consumer.
  • a major sensory defect which develops during frozen storage is sogginess of the bread. This occurs as a result of water transfer from the high moisture tomato sauce to the lower moisture bread.
  • the driving force for water transfer in this particular case is not a vapor pressure gradient between sauce and bread, since the water activities of the two components in the frozen state are essentially identical.
  • the bread absorbs water during extended frozen storage of a French bread pizza food product, thereby limiting shelf life and consumer acceptability. It was found that transfer of water into the crumb structure of the bread can be significantly impeded by positioning a pre-formed, edible film prepared in accord with the present invention so as to separate the tomato sauce and bread components.
  • the films used in this particular example were prepared generally by the method of Example 2.
  • the dried base films had an average thickness of 0.020 mm and average fatty acid concentration of 0.60 mg/cm 2 of base film.
  • the additional hydrophobic layer laminated to the base film consisted of refined white beeswax, applied at a thickness of approximately 0.035 mm. Concentration of beeswax averaged 3.4 mg/cm 2 of film. Thickness of the resulting film averaged 0.055 mm.
  • French bread pizza food products were assembed by positioning a 41 ⁇ 2 " x 41 ⁇ 2" piece of the pre-formed film upon tee surface of the exposed crumb of a like-sized piece of French bread, the hycrcphobic beeswax surface oriented up and the hydrophilic cellulose ether layer oriented toward the bread. Twenty-two grams of a commercial pizza sauce were deposited upon the edible film and spread evenly over the surface.
  • the French bread pizza samples were prepared for evaluation by baking in a conventional oven for 10 minutes at 177°C, whereupon the edible film was absorbed into the component layers.
  • the edible film positioned at the interface between sauce and bread provided an effective impediment to movement of water into the bread.
  • Sensory evaluation of the baked product by a trained panel cf analysts revealed that desirable sensory attributes of freshly prepared product were maintained in the stored product throughout the storage period. Specifically, bread sogginess was found not to increase during storage, and the overall preference remained equal to the fresh product throughout the nine week storage period.

Abstract

An edible film for retarding water transfer among components of a multicomponent food product. The film includes a base film having a hydrophilic polymer layer and a base film lipid layer. The base film lipid layer has a hydrophobic surface presented away from the hydrophilic polymer layer. An additional lipid layer is laminated to the hydrophobic surface of the base film lipid layer. The invention further includes a method for making the edible film and a food product incorporating it.

Description

EDIBLE FILM BA RRIER RESISTANT TO WATER VAPOR TPANSFER
Related Application
This is a contiιτuation-in-part of co-pending patent application S.N. 628,723.
Field of the Invention
The present invention relates to edible film barrier materials that can be used to stabilize water vapor pressure and moisture gradients existing between individual components of a multicαπponent food product separated by the edible film. "Moisture" as used herein shal l refer to liquid water diffused or condensed in various quantities, so that unfrozen pizza sauce or pie filling may be referred to as moist.
Background of the Invention
Deleterious changes in the quality of food products can occur with inadvertent alteration of the water content of the food product. The driving force for water transfer in food products is primarily water partial pressure gradients existing between the food product and the environment or between cαrtponents of a multicαπponent food product. However, even in the absence of water partial pressure gradients, water potentially can migrate via liquid diffusion driven by such forces as water concentration gradients or capillary forces. Hereinafter, "vapor pressure" shall be understood as "partial pressure of water," unless expressly indicated otherwise. The partial pressures involved can be expressed in terms of water activity, (aw), which equals the partial pressure of water exerted by the food material divided by the partial pressure of pure water at the same temperature. Prevention of water transfer between the food product and the environment can be accorplished by using a water vapor impermeable packaging material, either edible or inedible. Prevention of water transfer among individual components of a multicomponent food product is more difficult. Edible food coatings have been used to retard water transfer within foods. However, the ability of such coatings to maintain vapor pressure gradients among food components for extended periods has not been proven. Those skilled in the art are generally cognizant of the use of carbohydrate, protein, and lipid coatings to retard water transfer in feeds. Lipids include hydrophobic compounds such as fats, oils, and waxes and are especially effective in retarding water transfer within foods. However, when lipids such as waxes are applied to food products, the coatings are not continuous. Instead, they contain pinholes and cracks that provide routes for water transfer. Carbohydrate compounds are capable of forming structurally continuous coatings, but these compounds are generally hydrophilic and hence are less effective in retarding water transfer in foods. Therefore, in the past, lipids have been used in conjunction with carbohydrates in order to form a continuous coating to prevent water transfer in foods.
In U.S. Patent No. 2,909,435 to Watters, et al., a double layer coating was applied sequentially on foods such as raisins. The first layer consisted of a polysaccharide, upon which was applied a second layer of a melted wax composition. The layers were applied to the food by brushing, spraying, or dipping, and they were dried after application. In U.S. Patent Kb. 3,323,922 to Durst, an aqueous solution was prepared from starch or a carboxymethyl cellulose and a plasticizer, and a lipid was suspended in the solution. The coating was then applied to a food product by brushing, dipping, or spraying, srd the coating was dried after application to the food product. U.S. Patent Nos. 3,471,303 and 3,471,304 to Hamdy, et al., disclosed two types of coating compositions having as one constituent a cellulose ether. The cellulose ether was plasticized by various fatty acid derivatives such as (1) an ester of a linear polysaccharide having alpha-glucoside linkages and a fatty acid having between 8 to 26 carbon atcms, or (2) a glyceride containing a fatty acid having between 6 to 20 carbon atoms, together with a fatty acid metal salt wherein the fatty acid contains between 16 and 22 carbon atααs. The coating composition in the Hamdy patents could be extruded as a non-layered, molten sheet over the food to be coated, and then dried.
U.S. Patent No. 3,997,674 to Ukai, et al., disclosed an aqueous solution used to coat foods such as fresh fruits. The coating solution contained a water soliible high polymer such as methylcellulose and also hydrophobic substances such as waxes or oils. In Ukai, the food product was coated and then dried.
Drying a food coating after application on a food has several disadvantages. It is difficult to control the thickness of such coatings. Furthermore, drying coated foods adds time and hence cost to the manufacture of such foods. Therefore, it would be advantageous to provide off-the-shelf, pre-formed films that could effectively retard or prevent water transfer between components having different aw values or different moisture contents in a multicomponent food product.
Summary of the Invention
The invention is summarized in that an edible film for retarding water transfer among components of a multicomponent food product includes a base film having a hydrophilic polymer layer and a base film lipid layer. The base film lipid layer has a hydrophobic surface presented away from the hydrophilic polymer layer. An additional lipid layer is laminated to the hydrophobic surface of the base film lipid layer.
The invention is further summarized in that a method for making an edible film for retarding water transfer among components of a multicomponent food product includes, the following steps. First, a film-forming liquid is prepared by dissolving an edible hydrophilic polymer and mixing an edible lipid in an aqueous solvent system. Then, the film-forming liquid is plated on a supporting surface to a selected depth and dried to gel the polymer and form a base film. The depth of film-forming liquid selected is one sufficient to contain enough polymer and lipid to result in a dried base film of a desired thickness and to contain enough lipid to form a substantially uniform lipid layer covering that surface of the base film which is presented away from the supporting surface. By these means, a base film may be formed having a hydrophilic polymer layer and a base film lipid layer having a hydrophobic surface presented away from the hydrophilic polymer layer. Finally, an additional edible lipid is applied to the hydrophobic surface of the base film lipid layer to form an additional lipid layer.
The invention is further summarized in that a multiccmponent food product includes a first component and a second component having water vapor pressures and moisture characteristics such that water transfer would tend to occur from the second component to the first component. The edible film of the invention, as summarized above, is located between the first and second components, with the additional lipid layer oriented toward the second component. An object of the present invention is to provide an edible, pre-formed, dry film that can retard moisture and water vapor transfer among components of a multiccmponent food product during extended storage times and over changing temperatures and humidities, and yet can be absorbed in the food product or otherwise be rendered unobjectionable during heating or other preparation of the food product.
A further object of the present invention is to provide a method for making edible pre-formed films capable of retarding moisture and water vapor transfer among components of a multicomponent food product over extended storage times.
Another object of the present invention is to provide a food product and method to make a food product that includes a plurality of components having different vapor pressures or moisture contents together with edible films separating individual components, which films can maintain existing vapor pressure and moisture gradients for substantial periods of time and thereby retard water transfer among the food components. Other objects, advantages, and features of the invention will be apparent from the following detailed description.
Description of the Preferred Embodiment
The present invention includes an edible film for retarding water transfer among components of a rrailticcmponent food product. The film has a base film having a hydrophilic polymer layer and a solid or semi-solid, edible lipid layer adhered to the hydrophilic polymer layer. In the film of the invention, the lipid layer of the base film is enhanced with an additional hydrophobic layer. The films of the invention may be quite thin, ranging from a practical mip-imum thickness of approximately 0.024 mm to as much as at least 0.10 mm.
The base film's hydrophilic polymer layer can be formed from any edible, water-soluble, film-forming carbohydrate that displays thermal gelation in the solvent system used. Suitable polymers include, by way of example only, cellulose ethers such as hydroxypropyl methylcellulose and methylcellulose. The base film's lipid layer is conprised of solid or semi-solid, edible lipids such as hydrogenated oils (e.g., palm oil and soybean oil), saturated fatty acids, and edible waxes (e.g., beeswax and paraffin wax). The exposed surface of the lipid layer is hydrophobic. The base film itself is an effective barrier to water transfer. When the base film. is placed between components of food having, differing vapor pressures or moisture contents with the hydrophobic surface oriented toward the component of higher vapor pressure or moisture content, the base film can maintain the existing vapor pressure or moisture gradient for substantial periods of time, effectively retarding water transfer among the feed components.
A one-step method can be used for making a base film according to the present invention. In the preferred emtodiment of this method, water, a water-soluble, lipid-dissolving solvent such as an alcohol, a hydrophilic polymer, and a lipid are combined to make a fito-forming liquid. The lipid-dissolving solvent is present in quantities effective to dissolve at least a portion of the lipid and not to interfere with the dissolving and gelling of the polymer. If an alcohol is used, the usual and preferred alcohol is ethanol. The film-forming liquid is warmed, if necessary, to melt lipids having high melting points. The film-forming liquid is then spread on a supporting surface such as a flat, smooth plate, preferably to a depth of between approximately 0.25 and 0.75 mm. This may be done by any appropriate means for spreading a liquid, including brushing, dipping, spraying, or the use of spreading means comparable to those used in conventional thin layer chromatography. The plate is then dried tor a time sufficient to form a cohesive layer on the plate. A substantial portion of the lipids situate themselves at the surface of the drying film-fonning liquid. The result is a distinguishable lipid layer demonstrating hydrophobic qualities. The process of spreading the film-forming liquid and drying it so as to form a base film shall be referred to herein as "plating." Various concentrations of ingredients may be employed in preparing the film-forming liquid, and the liquid may be spread at various thicknesses. Excessive amounts of solvents may lead to inefficient or inconvenient drying periods. Bcwever, there is no theoretical point at which the ccsx:entrations of polymer and lipid have becαre too small to allow formation of a base film. The lipid concentration must be sufficient to allow substantially complete coverage of the surface of the base film as it is drying so as to form a hydrophobic surface and must not be so great as to substantially interfere with the formation of a cohesive polymer layer. Concentrations and spreading thicknesses are εc adjusted as to produce a dried base film having the strength and handling characteristics desired. A base film minimum thickness of approximately 0.013 mm generally is necessary. Base film thicknesses of 0.018 to 0.045 mm have been found. to be preferred in many applications, although thicker base films may be made as well. When a fatty acid such as stearic or palmitic acid is used as the lipid, a lipid concentration of at least approximately 0.25 mg/cm2 is necessary. Concentrations of 0.50 to 0.80 mg/cm2 are preferred. After drying, the plate is cooled, and the film is removed from the plate. If the base film is to be used directly as a water transfer barrier, it can then be positioned on the food material or stored until the food components are assembled.
Improved base film mechanical characteristics are obtained when a plasticizer such as polyethylene glycol is added to the film-forming liquid. The base films so formulated are generally less fragile and easier to remove frcm the plate. Additional, desirable effects can be achieved if the alcohol or other lipid-dissolving solvent forming a part of the solvent system of the film-forming liquid is added in sufficient quantities and if the base film is dried at sufficiently high temperatures. A concentration of such a solvent can be achieved sufficient to create a solvent system capable of solubilizing seme lipids that would otherwise be in an emulsion form. For example, an alcohol concentration in excess of 55% is sufficient if ethanol is used. As the alcohol preferentially evaporates, a point will be reached in which part or all of the lipid is no longer dissolved, and a true suspension again is formed. However, if the hydrophilic polymer can be made to undergo gelation prior to that point, lipid can be trapped in the gel. As a consequence, when alcohol concentrations become so low that the lipid may no longer be held in true solution, at least a portion of the lipid remains widely dispersed throughout and trapped within the gel and the ultimately resulting film. A portion of the lipid sufficient to impart hydrophobic surface qualities does preferentially migrate to the exposed surface and form a moisture resistant barrier. The use of a lipid-dissolving solvent in this manner shall be referred to herein as the "dissolved lipid process."
Lipid globules in a suspension not subject to the dissolved lipid process just described are believed to be larger than the lipid globules formed when the gelation process helps to preserve dispersion of the lipid. It is believed that the smallness of the lipid globules formed when the dissolved lipid process is used contributes to the uniform distribution of lipids at the base film surface and to the resulting creation of a more effective moisture and water vapor-impervious hydrophobic layer. Examination of samples of such base film with the scanning electron microscope has revealed that the lipids at the hydrophobic surface form a lipid layer that does not have a sharply defined boundary with respect to the hydrophilic polymer. Instead, the lipid and the hydrophilic polymers form layers that mutually interpenetrate to seme extent, with fingers of lipid extending into the hydrophilic polymer layer and vice versa, thereby enhancing cohesion of the two components. It should be noted that an edible film utilizing a base film made by the dissolved lipid process as described is preferred and believed to exhibit superior mechanical strength and flexibility and water transfer barrier characteristics. However, the invention is not to be understood as limited, to the preferred embodiment just described. The aqueous solvent system used to prepare the film-forming liquid may alternatively contain an amount of water-soluble, lipid-dissolving solvent insufficient to dissolve any significant quantity of the base film lipid. Indeed the aqueous solvent system may be entirely without such a lipid-dissolving solvent. In such an event, the lipid is held within the film-forming solution as a suspension. If the lipid is sufficiently divided within the suspension, it is believed that gelation of the hydrophilic polymer may occur in such a manner as to entrap sane of the lipid within the hydrophilic polymer and, at any rate, will lead to a boundary between the hydrophilic polymer and the base film lipid layer that is characterized by sufficient interpenetration that an at least minimally adequate base film is formed capable of being incorporated in a film for retarding water transfer exhibiting the advantages of the invention.
Temperature control is important in preparing a base film by the described method. Film-forming liquids containing lipids with high melting points require high temperatures to melt and disperse the lipid. However, excessively high temperatures can result in a low viscosity of the film-forming liquid and poor control over base film thickness during plating. Also, when the dissolved lipid process is being used, excessively high temperatures must be avoided during plating, because extremely rapid vaporization of the alcohol or other lipid-dissolving solvent can occur, resulting in bubbles in the film-forming liquid and possible pin holes in the dried base film. Nevertheless, the film-forming liquid must be warm enough to prevent solidification of the lipids curing plating.
In producing the edible film of the invention, wherein the lipid layer of the base film is enhanced with an additional hydrophobic lipid layer to create a film composed of two layers that are laminated together. The base film shall be deemed to constitute the "bottom" layer of the edible film of the invention. The additional lipid layer is laminated to the base layer by any suitable means for applying an additional lipid layer to the hydrophobic surface. Thus, the additional lipid layer may be applied by brushing, dipping, spraying, or otherwise spreading or distributing a liquid or semi-liquid lipid over the hydrophobic surface of the base film. The additional lipid layer is then solidified. The solidification may be accomplished by cooling a lipid that has been warmed above its melting temperature. Similarly, a lipid held in an appropriate solution may he deposited by evaporating the solvent. Preferably, the first of these two methods is used. The additional lipid layer may be made of any lipid of the sort described above. However, although other lipid raterials such as fatty acids and triglycerides can be used for forming the additional lipid layer, solidified natural waxes such as beeswax and refined, paraffin waxes are preferred. Upon solidification, such waxes form an amorphous cr microcrystalline layer that is particularly effective to bar water vapor transfer. This effectiveness is believed to result from the nature of the crystalline structure of the waxes, which is so overlayered as to eliminate or minimize the rrajor route by which water vapor can migrate through a lipid layer, i.e. by penetration between adjacent crystals. It is emphasized that, although this is applicant's best current understanding of the mechanisms involved in the functioning of the additional lipid layer, that understanding is speculative and is offered for explanatory purposes only. It in no way is meant to limit the scope of the invention.
Especially suitable waxes include beeswax, candelilla wax, carnauba wax, rice bran wax, and the refined paraffin and microcrystalline waxes obtained from petroleum, all 'of which are described in the Food Chemical Codex. If such an edible, food-grade wax is utilized as the additional lipid layer, a thickness of at least approximately 0.011 mm is used, and a thickness in the range of 0.026 mm to 0.047 mm is preferred. The desirable wax content thus is approximately in the range 2.5 mg to 4.5 mg of wax per square centimeter of base film. The minimum wax content is approximately 1.0 mg/cm2. The completed laminated film having the preferred thickness of base film and a wax employed as the additional lipid film has a desired thickness in the range of approximately 0.044 mm to 0.092 mm.
In the fabrication of the embodiment of the edible film described, the preferred film-forming liquid used to make the base film is prepared frcm a blend of cellulose ethers including both methylcellulose and hydroxypropyl methylcellulose. That blend of cellulose ethers is combined with polyethylene glycol and a saturated fatty acid, all in a lipid-dissolving, ethanol-water solvent system. The solvent system may include as much as approximately 80% ethanol and preferably is at least 55% ethanol. The maximum concentration of approximately 80% ethanol is the practical upper limit, beyond which there is a loss of solubility of the cellulose ethers. The film-forming liquid is warmed to the extent necessary to thoroughly dissolve the fatty acids. For example, use of a 55% ethanol solution allows fatty acids in the concentration indicated to be dissolved at about 65°C. The film-forming solution is prepared with appropriate concentrations and then is spread on a glass plate or comparable supporting surface to a depth of approximately 0.25 mm. The film is then dried at an air temperature of approximately 100°C. At that tamperature and that thickness, a drying time of 15 minutes usually is sufficient. Thereafter, the base film is allowed to cool to room temperature. The wax used as. the additional lipid layer may then be deposited upon the hydrophobic surface, of the base film by any of several means to do so, as is discussed above, at a thickness in the range of 0.026 to 0.047 irm.
A factor of critical importance for the successful low terperature use of films of the embodiment being described is good adhesion between the base film and the additional lipid layer. The need for such effective bonding becomes especially apparent at temperatures generally in use for frozen food applications. At those temperatures, poor adhesion or ineffective bonding leads to fracturing of the additional lipid layer and to its subsequent separation from the base film. This is accompanied by a reduction of the film's ability to act as a barrier to water vapor. When the lipid used for the additional lipid layer is a wax, good wax adhesion is evidenced by resistance to fracturing and maintenance of water vapor barrier properties upon prolonged storage at temperatures as low as -40°C.
To achieve the good wax adhesion referred to, conformance to the following parameters is believed to be necessary when the preferred film-forming liquid just mentioned is used. The blend of cellulose ethers should include between 50% and 80% methylcellulose, with the balance being hydroxypropyl methylcellulose. The preferred ratio is 70% methylcellulose and 30% hydroxypropyl methylcellulose. The blend of cellulose ethers is believed to maximize bonding of the additional lipid layer to the base film while still maintaining satisfactory film-forming properties. Taken by itself, hydroxypropyl methylcellulose has a film-forming capability more effective than that of methylcellulose. However, methylcellulose, being less hydrophilic than hydroxypropyl methylcellulose, adheres more effectively to the additional lipid layer. The blend produces a strong film to which the additional lipid layer bonds well.
The cellulose ethers referred to display gelation when heated in solution. By use of the ethanol-water lipid-dissolving solvent system or comparable system to perform the dissolved lipid process discussed above, thermal gelation of the methylcellulose and hydroxypropyl methylcellulose during the drying phase of the formation of the base film, locks a certain percentage of the fatty acid included in the film-forming liquid throughout the bulk of the base film and also appears to prevent the fatty acid comprising the hydrophobic lipid layer from agglomerating into relatively large lipid globules. Consequently, the base film when dry has distributed within it small fatty acid crystals as integral components of the film. However, the base film also has a layer, of fatty acid so situated at the surface of the film as to form a hydrophobic surface, but with an intimate physical interinvolvement of the fatty acid, lipid layer with the underlying hydrophilic polymer layer. It is thought that, when wax of the sort referred to above is used for the additional lipid layer and is spread over the base film in molten form, the fatty acid crystals embedded within and at the surface of the base film first melt beneath the hot wax and then resolidify as the applied wax cools and solidifies. It appears that this contributes to effective bonding between the base film and the wax additional lipid layer, probably by the melting of fatty acid crystals at the surface of the base film into the wax layer to increase the intimacy of the joining of the base film and wax additional lipid layer.
Polyethylene glycol is disclosed above as usefully incorporated into the film-forming liquid as a plasticizer to aid in the removal of dried films frαn the plate or other substrate upon which they have been formed and otherwise to improve their durability. However, polyethylene glycol also binds to and is miscible with many waxes. Consequently, it is believed that the presence of polyethylene glycol in the base film contributes to the intimate physical interaction of the base film and the additional lipid layer when that lipid layer is, wax, to promote effective adhesion of; the additional lipid layer to the base film. Once again, the mechanics of this effect are not precisely known, and applicants are presenting only their best understanding of empirically observed results. Except when otherwise stated expressly, the particular concentrations, pH, temperatures, times, and reagents disclosed above are not critical. Thus, ethanol was disclosed above as usable for converting the film-forming suspension into a true solution. However, the essence of what is needed is a solvent that provides means for dissolving the lipid used in the base film and keeping that lipid dissolved until the hydrophilic polymer, whether a cellulose ether or otherwise, has polymerized to form a gel. Thus, the non-aqueous solvent present in the lipid-dissolving solvent system and used as such a means must not interfere with the polymerizing or gelling process and must leave no residue that would be harmful if eaten. It will be apparent that other solvents than ethanol could be so used as a dissolving means, such as acetone, isopropyl alcohol, methyl alcohol, and prcpyl alcohol. Similarly, polyethylene glycol was disclosed as a suitable plasticizer that also contributed to the adhesion of the additional lipid layer to the base film. However, glycerol, propylene glycol, and other similar plasticizers capable of dissolving in high concentration the lipid of the additional lipid layer may be expected to function in a comparable manner.
A multicomponent food product can be made utilizing the film of the invention, as described above. Use of the film is beneficial when a first component of the feed product and a second component have water vapor pressures and moisture characteristics such that water trannfer would tend to occur from the second component to the first component unless restrained. In the mu lticomponent food product of the invention, an edible film of the sort described above is located between the first and second components, with the additional lipid layer oriented toward the second component. As a result, water transfer is retarded, and the multiccmponent food product may be stored without change from water transfer for longer periods of time than would otherwise be possible.
Example 1 -- One-Step Method to Form Base Film
A film-forming liquid was prepared by dissolving 9 gm of hydroxypropyl methylcellulose in 100 ml of 90°C distilled water. After the hydroxypropyl methylcellulose was completely in solution, 200 ml of 95% ethanol was added. Next, 1 gram of polyethylene glycol was added to the solution. Finally, 3.4 gm of stearic acid was added' to the solution. The solution was warmed to between 70-75°C in order to melt and dissolve the stearic acid.
One hundred milliliters of the film-forming solution was added to a thin layer chromatography (TLC) spreader and plated onto three 8 inch by 8 inch glass TLC plates at a thickness of 0.75 itm. The coated plates were then dried in an oven at approximately 90°C for 15 minutes, by which time a cohesive, edible, base film had formed. After drying, the plates were cooled, and the films were peeled from the plates. The films had an average thickness of 0.04 mm and an average stearic acid concentration of 0.8 mg stearic acid per square centimeter of hydroxypropyl methylcellulose layer.
Example 2 -- Fabrication of Films with Additional Lipid Layer
Base films were made by methods generally corresponding to that of Example 1. In particular 7 gm of methylcellulose and 3 gm of hydroxypropyl methylcellulose were dissolved in 100 ml of distilled water at 90°C. After complete dissolution of the cellulose ethers, 200 ml of 95% ethanol was added to the solution. This solution was thoroughly mixed. Then 6 gm of polyethylene glycol was added to. the solution. Finally; 9 gm of a fatty acid was added and the mixture was warmed to completely dissolve the fatty acid. In replications of this example, stearic acid, palmitic acid, and combinations of the two were used as the fatty acid. The solution so constituted, and at a teπperature sufficient to allow the fatty acid to be completely dissolved, constituted a fito-forming liquid. The film-forming liquid was subsequently maintained at a tesperature of 65±1°C. Air bubbles were removed if necessary by reducing the pressure over the film-forming liquid. Thirty-five ml of the film-forming liquid was added to a TLC spreader. The film-forming liquid was spread onto four 8 x 8 inch TLC glass plates of conventional design, the film-forming liquid being spread at a thickness of approximately 0.25 mm. The film-forming liquid was then dried in an oven at 100°C for 15 minutes to produce a cohesive cellulose ether-polyethylene glycol-fatty acid base film. After the drying procedure, the plates were cooled to room temperature. The dried base films had an average thickness of 0.020 mm and an average fatty acid concentration of 0.60 mg/cm2 of base film.
Refined white beeswax was used as the lipid of the additional lipid layer. Molten beeswax was spread over the surface of the dried base films before their removal from the plates. The TLC spreader was preheated to 180°C and set to spread the molten beeswax at a thickness of approximately 0.035 mm. When the molten beeswax had so cooled as to solidify, the resulting film consisting of the base film with the applied additional lipid layer was peeled from the glass plate. Thickness of the resulting film averaged 0.055 mm. Concentration of beeswax averaged 3.4 mg/cm2 of film. Example 3 -- Preparation of Food Product (Hypothetical)
A food prepared in accordance with the present invention could include a plurality of components having different vapor pressures and/or moisture contents, such as pizza or filled pie crusts. Preferably, an edible film prepared in accordance with the present invention would be pre-formed and then positioned so as to separate the individual components. Such edible films would include a base film having a hydrophilic polymer layer and a lipid layer adhered to and partly intermixed with the hydrophilic polymer layer such that the base film, comprising the hydrophilic polymer layer and the lipid layer, would have a preferred thickness in the range of 0.018 mm to 0.045 ran. The base film lipid layer preferably would have a concentration of at least approximately 0.5 mg lipid per square centimeter of hydrophilic polymer layer. An additional lipid layer would be laminated to the exposed, hydrophobic surface of the base film lipid layer and would be oriented toward the food component having the higher vapor pressure or moisture content, such as a pizza sauce or pie filling when compared to a crust. With this orientation, the film could maintain an existing food component vapor pressure or moisture gradient for substantial periods of time, thereby retarding water transfer from the component having a higher vapor pressure or moisture content to the component having a lower vapor pressure or moisture content. The film would be absorbed into the component layers upon heating or other cooking preparation exceeding 70°C.
Example 4 -- Pizza Food Product
A conventional French bread pizza food product consists of a loaf of French bread which is sliced horizontally to reveal the interior crumb structure, upon which is placed a mixture of tomato sauce, cheese, spices, and vegetables. The product conventionally is shrink wrapped and blast frozen. It then may be stored in frozen storage for a substantial period of time during distribution and prior to consumption by the consumer. A major sensory defect which develops during frozen storage is sogginess of the bread. This occurs as a result of water transfer from the high moisture tomato sauce to the lower moisture bread. The driving force for water transfer in this particular case is not a vapor pressure gradient between sauce and bread, since the water activities of the two components in the frozen state are essentially identical. Instead, other mechanisms of water transfer are operative, such as liquid diffusion caused by an unfrozen water concentration gradient, liquid diffusion caused by the force of gravity acting upon unfrozen water, and liquid diffusion caused by capillary suction. The latter mechanism is probably the predominant driving force for water transfer considering the crumb structure at the bread-sauce interface.
Regardless of the nature of the driving force for water transfer, the bread absorbs water during extended frozen storage of a French bread pizza food product, thereby limiting shelf life and consumer acceptability. It was found that transfer of water into the crumb structure of the bread can be significantly impeded by positioning a pre-formed, edible film prepared in accord with the present invention so as to separate the tomato sauce and bread components. The films used in this particular example were prepared generally by the method of Example 2. The dried base films had an average thickness of 0.020 mm and average fatty acid concentration of 0.60 mg/cm2 of base film. The additional hydrophobic layer laminated to the base film consisted of refined white beeswax, applied at a thickness of approximately 0.035 mm. Concentration of beeswax averaged 3.4 mg/cm2 of film. Thickness of the resulting film averaged 0.055 mm.
French bread pizza food products were assembed by positioning a 4½ " x 4½" piece of the pre-formed film upon tee surface of the exposed crumb of a like-sized piece of French bread, the hycrcphobic beeswax surface oriented up and the hydrophilic cellulose ether layer oriented toward the bread. Twenty-two grams of a commercial pizza sauce were deposited upon the edible film and spread evenly over the surface.
Initial moisture contents of bread and sauce were 40.4 ± 0.2% (mean ± standard deviation) and 83.5 ± 0.5%, respectively. Hence the initial water concentration gradient between sauce and bread was 43.1%. Assembled samples of French bread pizza were σverwrapped with a cαtmercial packaging film, sealed, and blast frozen. Samples were subjected to accelerated shelf life testing at -6.7°C for nine weeks.
Following completion of the shelf life test, the French bread pizza samples were prepared for evaluation by baking in a conventional oven for 10 minutes at 177°C, whereupon the edible film was absorbed into the component layers. The edible film positioned at the interface between sauce and bread provided an effective impediment to movement of water into the bread. Sensory evaluation of the baked product by a trained panel cf analysts revealed that desirable sensory attributes of freshly prepared product were maintained in the stored product throughout the storage period. Specifically, bread sogginess was found not to increase during storage, and the overall preference remained equal to the fresh product throughout the nine week storage period. These sensory results exemplify the value of the present edible film invention in regard to minimizing deleterious changes in food product quality caused by water transfer.
It is to be understood that modification of the above-described edible film, method for making an edible film, food product, or method of making a food product is possible within the spirit of the present invention. Thus, the invention is not limited to the above-described preferred arbodiments. Instead, it embraces such modified forms thereof as come within the scope of the following claims.

Claims

CLAIMSWhat is claimed is:
1. An edible film for retarding water transfer among components of a multiccmponent food product, the film comprising
(a) a base film having a hydrophilic polymer layer and a base film lipid layer, the base film lipid layer having a hydrophobic surface presented away from the hydrophilic polymer layer; and (b) an additional lipid layer laminated to the hydrophobic surface of the base film lipid layer.
2. The film of Claim 1 wherein lipid globules are distributed within the hydrophilic polymer layer, and the hydrophilic polymer layer and the base film lipid layer mutually interpenetrate at the boundary therebetween.
3. The film of Claim 1 wherein the hydrophilic polymer layer includes a water soluble, film-forming carbohydrate.
4. The film of Claim 1 wherein the hydrophilic polymer layer includes a cellulose ether.
5. The film of Claim 4 wherein the hydrophilic polymer layer includes cellulose ethers including from 50 to 80% methyl cellulose with the remaining portion of the cellulose ethers consisting essentially of hydroxypropyl methylcellulose.
6. The film of Claim 1 wherein the base film lipid layer includes lipids selected from the group consisting of hydrogenated oils, saturated fatty acids, and edible waxes.
7. The film of Claim 1 wherein the base film has a thickness of at least approximately 0.013 mm.
8. The film of Claim 1 wherein the base film lipid layer consists essentially of a fatty acid, and the concentration of the fatty acid is at least approximately 0.25 mg/cm2 of film.
9. The film of Claim 1 wherein the additional lipid layer consists essentially of an edible wax and has a thickness of at least approximately 0.011 mm.
10. The film of Claim 1 wherein the additional lipid layer includes a wax and the base film includes a plasticizer soluble in aqueous diluents and also having the characteristic of dissolving waxes.
11. A method for making an edible film for retarding water transfer among components of a multicomponent food product, the method comprising the steps of:
(a) preparing a film-forming liquid by dissolving an edible hydrophilic polymer and mixing an edible lipid in an aqueous solvent system;
(b) plating the film-forming liquid on a supporting surface to a selected depth, and drying the film-forming liquid to gel the polymer and form a base film, the depth of film-forming liquid selected being one sufficient to contain enough polymer and lipid to result in a dried base film of a desired thickness and to contain enough lipid to form a substantially uniform lipid layer covering that surface of the base film which is presented away from the supporting surface, whereby a base film may be formed having a hydrophilic polymer layer and a base film lipid layer having a hydrophobic surface presented away from the hydrophilic polymer layer; and (c) applying additional edible lipid to the hydrophobic surface of the base film lipid layer to form an additional lipid layer.
12. The method of Claim 11 wherein the hydrophilic polymer is a water-soluble, film-forming carbohydrate.
13. The methcd of Claim 11 wherein the hydrophilic polymer includes a cellulose ether.
14. The methcd of Claim 11 wnerein the hydrophilic polymer includes cellulose ethers including from 50 to 80% methylcellulose with the remaining portion of the cellulose ethers consisting essentially of hydroxypropyl methylcellulose.
15. The method of Claim 11 wherein the lipid. used in the preparation of the film-forming liquid includes lipids selected frαn the group consisting of hydrogenated oils, saturated fatty acids, and edible waxes .
16. The method of Claim 11 wherein the lipid used to prepare the film-forming liquid consists essentially of a fatty acid, and the film-forming liquid is plated to a depth sufficient to result in a concentration of the fatty acid in the dried base film of at least approximately 0.25 mg/cm2 of film.
17. The methcd of Claim 11 wherein the step of applying additional lipid to form the additional lipid layer includes application of an edible wax to form an additional lipid layer having a thickness of at least approximately 0.011 mm.
18. The methcd of Claim 11 wherein the step of preparing a film-forming liquid includes dissolving in the solvent system a plasticizer soluble in aqueous diluents and also having the characteristic of dissolving waxes, and the step of applying an additional lipid to form the additional lipid layer includes so applying an edible wax.
19. The method of Claim 11 wherein the aqueous solvent system includes water and a water-soluble, lipid-dissolving solvent, the water and the lipid-dissolving solvent being present in quantities effective to dissolve both the polymer and at least a portion of the lipid; and the step of drying the film-forming liquid to form a base film includes holding at least part of the dissolved lipid of the film-forming liquid in solution until gelation of the hydrophilic polymer has begun.
20. The method of Claim 19 wherein the step of applying additional lipid to the hydrophobic surface of the base film includes the steps of applying the additional lipid of the additional lipid layer at a temperature sufficient to melt lipid of the base film lipid layer, and cooling the film until all of the lipid of the film is no longer liquid.
21. A multicomponent food product comprising
(a) a first component and a second component having water vapor pressures and moisture characteristics such that water transfer would tend to occur from the second component to the first component; and (b) an edible film conforming to the limitations of
Claim 1 located between the first and second components with the additional lipid layer oriented toward the second component.
22. The food product of Claim 21 wherein the film additionally conforms to the limitations of Claim 2.
23. The food product of Claim 21 wherein the film additionally conforms to the limitations of Claim 5.
24. The food product of Claim 21 wherein the film additionally conforms to the limitations of Claim 10.
PCT/US1986/002641 1985-12-16 1986-12-08 Edible film barrier resistant to water vapor transfer WO1987003453A1 (en)

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US809,531 1985-12-16

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EP0471558A2 (en) * 1990-08-14 1992-02-19 Unilever Plc Moisture barrier and its preparation
WO1993020710A1 (en) 1992-04-21 1993-10-28 Wm. Wrigley Jr. Company Use of edible film to prolong chewing gum shelf life
EP0638488A1 (en) * 1993-08-12 1995-02-15 Convenience Foods Limited Microwavable food product containing a moisture resistant edible internal barrier
WO1996011577A1 (en) * 1994-10-13 1996-04-25 Unilever N.V. Pre-moulded, filled or topped dough systems
WO1998049910A1 (en) * 1997-05-01 1998-11-12 Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) Encapsulated material with controlled release
US6428827B1 (en) 1999-04-01 2002-08-06 Wm. Wrigley Jr. Company Long flavor duration releasing structures for chewing gum and method of making
US6479082B1 (en) 1996-12-23 2002-11-12 Wm. Wrigley, Jr. Co. Process of increasing flavor release from chewing gum using hydroxypropyl cellulose and product thereof
WO2006002734A1 (en) * 2004-07-01 2006-01-12 Unilever N.V. Moisture barrier
US7981453B2 (en) 2004-12-29 2011-07-19 Kraft Foods Global Brands Llc Delivery system for low calorie bulking agents

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DE3643199A1 (en) * 1986-12-18 1988-06-30 Werner Georg Munk PACKAGING FOR FOOD AND ENJOYMENT AND METHOD FOR THEIR PRODUCTION
US4957754A (en) * 1986-12-18 1990-09-18 Suedmilch Aktiengesellschaft Container for foods
EP0471558A2 (en) * 1990-08-14 1992-02-19 Unilever Plc Moisture barrier and its preparation
EP0471558A3 (en) * 1990-08-14 1992-08-19 Unilever Plc Moisture barrier and its preparation
US5433960A (en) * 1992-04-21 1995-07-18 Wm. Wrigley Jr. Company Chewing gum including agent containing edible film
US5286502A (en) * 1992-04-21 1994-02-15 Wm. Wrigley Jr. Company Use of edible film to prolong chewing gum shelf life
US5409715A (en) * 1992-04-21 1995-04-25 Wm. Wrigley Jr. Company Use of edible film to prolong chewing gum shelf life
WO1993020710A1 (en) 1992-04-21 1993-10-28 Wm. Wrigley Jr. Company Use of edible film to prolong chewing gum shelf life
EP0638488A1 (en) * 1993-08-12 1995-02-15 Convenience Foods Limited Microwavable food product containing a moisture resistant edible internal barrier
WO1996011577A1 (en) * 1994-10-13 1996-04-25 Unilever N.V. Pre-moulded, filled or topped dough systems
US6479082B1 (en) 1996-12-23 2002-11-12 Wm. Wrigley, Jr. Co. Process of increasing flavor release from chewing gum using hydroxypropyl cellulose and product thereof
WO1998049910A1 (en) * 1997-05-01 1998-11-12 Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) Encapsulated material with controlled release
US6290988B1 (en) 1997-05-01 2001-09-18 Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) Encapsulated material with controlled release
US6428827B1 (en) 1999-04-01 2002-08-06 Wm. Wrigley Jr. Company Long flavor duration releasing structures for chewing gum and method of making
WO2006002734A1 (en) * 2004-07-01 2006-01-12 Unilever N.V. Moisture barrier
US7981453B2 (en) 2004-12-29 2011-07-19 Kraft Foods Global Brands Llc Delivery system for low calorie bulking agents
US8216621B2 (en) 2004-12-29 2012-07-10 Kraft Foods Global Brands Llc Delivery system for low calorie bulking agents

Also Published As

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JPS63501921A (en) 1988-08-04

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